Composition for forming low dielectric constant resin, low dielectric member, and electronic device using the same.

Abstract

The purpose of the present invention is to achieve a composition for forming a low dielectric constant resin which is suitable for use in a substrate for radar, next-generation communication devices and the like using higher frequencies, while having high heat dissipation properties.　The present invention enables the achievement of a polymerizable composition, which is able to be molded by a solution process, while exhibiting thermal conductivity and low dielectric properties lower than those of conventional liquid crystal polymers, by curing a polymerizable polycyclic compound that has less conjugates or polar groups, while exhibiting higher linearity or symmetry of each molecule.

Description

[Technical Field]

[0001] This invention relates to a composition for forming a low dielectric constant resin using a liquid crystal compound having polymerizable groups, and to a low dielectric member using the same. In particular, it relates to a material for high-frequency substrates and related materials, and to a low dielectric member and electronic equipment using the same. [Background technology]

[0002] In recent years, with the advent of 5G and beyond-5G and 6G communication devices, the frequency of electrical signals on electronic circuit boards and the frequency of radio waves transmitted and received by antennas have increased, leading to problems with signal loss in signal processing circuit boards and antenna boards. Therefore, there is a demand for resin materials with low dielectric constant and low dielectric loss tangent used in circuit boards, and resins such as liquid crystal polymer (LCP), polyphenylene ether (PPE), cycloolefin polymer (COP), and fluororesin (PTFE) are beginning to be used instead of conventional polyimide and epoxy resins. Low dielectric substrates currently have a dielectric constant of 3.0 or less, and those containing high thermal conductivity fillers have a dielectric constant of 3.5 or less. There is a need to develop materials with even lower dielectric constants. (Non-patent literature, RF World No. 40, pp. 97-111, 2017)

[0003] However, current materials for high-frequency substrates are thermoplastic resins, which have many drawbacks, such as requiring high temperatures for molding and bonding, and having poor adhesion to other resins and to copper foil electrodes. Patent document 1 describes an investigation into lowering the dielectric constant of liquid crystal polymers by examining their molecular structure. However, liquid crystal polymers have high melting points, requiring processing temperatures of 350°C or higher, making thermal lamination and bonding difficult. Patent Document 2 describes an investigation into how to varnish PPE resin by increasing its solubility in solvents through the study of its molecular structure. This would allow PPE resin to be formed into films by coating and used as an insulating varnish. However, it requires the use of a solvent with high dissolving power, and there are many problems, such as the possibility of redissolution in the solvent when laminating in multiple layers. Therefore, there is a need for the development of a low dielectric constant resin that can be coated and easily cured, similar to an insulating coating varnish.

[0004] On the other hand, the amount of information processed by LSIs for data processing is rapidly increasing, and consequently, the amount of heat generated is also increasing, so the heat dissipation capabilities of the electronic substrate itself are also becoming necessary. Patent document 3 describes that when a highly linear polymerizable liquid crystal compound is oriented and cured, it becomes more thermally conductive in the orientation direction than ordinary thermosetting resins, and Patent document 4 describes that by compounding a polymerizable liquid crystal compound with a heat dissipation filler, it is possible to form a thermosetting resin material with even higher thermal conductivity. However, in these examples, the focus is on increasing thermal conductivity, and low dielectric properties are not considered. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2019-189734 [Patent Document 2] Japanese Patent Publication No. 2009-67894 [Patent Document 3] Japanese Patent Publication No. 2006-265527 [Patent Document 4] Republished Gazette No. 2015 / 170744 [Overview of the project] [Problems that the invention aims to solve]

[0006] As described above, the objective is to realize a composition for forming low dielectric constant resins that can be suitably used in next-generation communication equipment and radar, which are increasingly using higher frequencies, and that also has high heat dissipation properties.

Means for Solving the Problems

[0007] The inventors of the present invention have found that by curing a liquid crystal compound having a polymerizable group with few conjugations and polar groups and having high linearity and symmetry of the molecule, a polymerizable composition that can be molded by a solution process and exhibits lower dielectric properties and thermal conductivity than conventional liquid crystal polymers can be realized, and thus completed the present invention. Furthermore, molecules with high linearity often exhibit liquid crystal properties. When the temperature range in which they exhibit liquid crystal properties is wide, orientation treatment is easy in that temperature region, and it becomes possible to control the orientation of molecules, similar to the stretching treatment in thermoplastic resins.

[0008] [1] The first aspect of the present invention is a composition containing a liquid crystal compound having a polymerizable group at the terminal, represented by formula (1), and having a relative dielectric constant at 10 GHz of a cured product of the composition lower than 3.0, which is a composition for forming a low dielectric resin. R 1a -Z 1 -A 1 -Z 2 -A 2 -(Z 3 -A 3 ) m1 -Z 4 -R 1b (1) In formula (1), A 1 、A 2 、and A 3These are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, bicyclo[2.2.2]octo-1,4-diyl, bicyclo[3.1.0]hex-3,6-diyl, or fluorene-2,7-diyl, in which at least one -CH2- may be replaced with -O-, at least one -CH= may be replaced with -N=, and at least one hydrogen is a halogen, or a C1- to C12 alkyl group in which at least one hydrogen may be replaced with a halogen, in which at least one -CH2- may be replaced with -O-, -CO-, -COO-, -OCO-, or -C=C-; Z 1 , Z 2 , Z 3 , and Z 4 These are independently single-bonded or C1-C20 alkylenes, in which at least one -CH2- may be replaced by -O-, -S-, -CO-, -COO-, -OCO-, -SO2-, -CH=CH-, -CF=CF-, -CH=N-, -N=CH-, or -N=N-, and at least one hydrogen may be replaced by a halogen; m1 is 0, 1, or 2. In the formula, Z 3 Or A 3 If there are multiple items, they may be the same or different. R 1a and R 1b These are independently selected groups from polymerizable groups represented by formulas (PG-1) to (PG-5), TIFF0007861630000001.tif58133 In equations (PG-1) to (PG-5), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, where q is 0 or 1, and R is present in the formula. b If there are multiple instances, they may be identical or different; A 1 and A 2 is 1,4-phenylene, and Z 2It is a single bond, m is 0, and R 1a and R 1b If the polymerizable group is represented by formula (PG-5), then Z 1 and Z 4 This alkylene has 3 to 20 carbon atoms, and in this alkylene, at least one -CH2- may be replaced with -O-, -S-, -CO-, -COO-, -OCO-, -SO2-, -CH=CH-, -CF=CF-, -CH=N-, -N=CH-, or -N=N-, and at least one hydrogen may be replaced with a halogen.

[0009] [2] A second aspect of the present invention is: In equation (1), R 1a and R 1b The composition for forming a low dielectric constant resin according to [1] is wherein the polymerizable group is independently represented by formula (PG-1) or (PG-5).

[0010] [3] A third aspect of the present invention is: The composition for forming a low dielectric constant resin according to [1] contains a liquid crystal compound having polymerizable groups at its terminals, represented by any of formulas (1-1) to (1-3). R 1a -Z 1 -A 1 -Z 2 -A 2 -Z 4 -R 1b (1-1) R 1a -Z 1 -A 1 -Z 2 -A 2 -Z 3 -A 3 -Z 4 -R 1b (1-2) R 1a -Z 1 -A 1 -Z 2 -A 2 -Z 3 -A 3-Z 3 -A 3 -Z 4 -R 1b (1-3) In formulas (1-1) to (1-3), A 1 , A 2 , and A 3 These are independently 1,4-cyclohexylene, 1,4-phenylene (where at least one hydrogen may be replaced by a halogen or an alkylene having 1 to 12 carbon atoms), bicyclo[2.2.2]octo-1,4-diyl, bicyclo[3.1.0]hex-3,6-diyl, and fluorene-2,7-diyl (where at least one hydrogen may be replaced by a halogen or an alkylene having 1 to 10 carbon atoms). Z 1 , Z 2 , Z 3 , and Z 4 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH2) a -COO-, -OCO-(CH2) a -, -CH=CH-, -SO2-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20. In the formula, Z 3 Or A 3 If there are multiple items, they may be the same or different. R 1a and R 1b These are independently polymerizable groups represented by formula (PG-1) or (PG-5), TIFF0007861630000002.tif2551 In formulas (PG-1) and (PG-5), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, where q is 0 or 1, and R is present in the formula. b If there are multiple items, they may be the same or different.

[0011] [4] The fourth aspect of the present invention is the composition for forming a low dielectric constant resin according to claim 1, which contains a liquid crystal compound represented by any one of formulas (1-1-1) to (1-1-3) and having a polymerizable group at the terminal. TIFF0007861630000003.tif55101 In formulas (1-1-1) to (1-1-3), Z 1 、Z 2 and Z 4 are independently a single bond, -(CH2) a -, -O(CH2) a -, -(CH2) a O-, -O(CH2) a O-, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH2) a -COO-, -OCO-(CH2) a -, -CH=CH-, -SO2-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20, X is fluorine or methyl, n is an integer from 0 to 4, including when n is 2 or more, and when there are a plurality of Xs in the formula, they may be the same or different, R 1a and R 1b are independently a polymerizable group represented by formula (PG-1) or (PG-5), TIFF0007861630000004.tif2958 In formulas (PG-1) and (PG-5), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, q is 0 or 1, and when there are a plurality of R b in the formula, they may be the same or different.

[0012] [5] The fifth aspect of the present invention is The composition for forming a low dielectric constant resin according to [1], which contains a liquid crystal compound having a polymerizable group at the terminal and is represented by any one of formulas (1-2-1) to (1-2-6). TIFF0007861630000005.tif105112 In formulas (1-2-1) to (1-2-6), Z 1 Z 2 Z 3 and Z 4 are independently a single bond, -(CH2) a -, -O(CH2) a -, -(CH2) a O-, -O(CH2) a O-, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -CH2CH2-COO-, -OCO-CH2CH2-, -SO2-, -CH=CH-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20, X is fluorine or methyl, n is an integer from 0 to 4, including when n is 2 or more, and when there are multiple Xs in the formula, they may be the same or different, R 1a and R 1b are independently a polymerizable group represented by formula (PG-1) or (PG-5), TIFF0007861630000006.tif2958 In formulas (PG-1) and (PG-5), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, q is 0 or 1, and when there are multiple Rs b in the formula, they may be the same or different.

[0013] [6] The sixth aspect of the present invention is The composition for forming a low dielectric constant resin according to [1], which contains a liquid crystal compound having a polymerizable group at the terminal and is represented by any one of formulas (1-3-1) to (1-3-9). TIFF0007861630000007.tif168129 In formulas (1-3-1) to (1-3-9), Z 1 , Z 2 , Z 3 and Z 4 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH2) a -COO-, -OCO-(CH2) a -, -CH=CH-, -SO2-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20. Z in the formula 3 They may be the same or different. X is either fluorine or methyl, n is an integer between 0 and 4. This includes the case where n is 2 or greater, and if there are multiple X values ​​in the expression, they may be the same or different. R 1a and R 1b These are independently polymerizable groups represented by formula (PG-1) or (PG-5), TIFF0007861630000008.tif2958 In formulas (PG-1) and (PG-5), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, where q is 0 or 1, and R is present in the formula. b If there are multiple items, they may be the same or different.

[0014] [7] A seventh aspect of the present invention is: In formula (1), R 1a and R 1b However, the polymerizable group is represented by formula (PG-1), which is the composition for forming the low dielectric constant resin described in [1]. TIFF0007861630000009.tif2827 In formula (PG-1), R bR is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, and the formula contains R b If there are multiple items, they may be the same or different.

[0015] [8] An eighth aspect of the present invention is: A compound represented by formula (1-1-1a) or (1-2-1a), wherein the relative permittivity at 10 GHz of a cured product obtained by curing a composition containing the compound is lower than 3.0. TIFF0007861630000010.tif43144 In equations (1-1-1a) and (1-2-1a), R b These are hydrogen, halogens, -CF3, or alkyl groups having 1 to 5 carbon atoms. Z 2 and Z 3 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH2) a -COO-, -OCO-(CH2) a -, -CH=CH-, -SO2-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20. m is an integer between 0 and 20. M is a single bond or oxygen, X is either fluorine or methyl, n is an integer between 0 and 4. This includes the case where n is 2 or greater, and if there are multiple X values ​​in the expression, they may be the same or different. In the formula, R b If there are multiple instances of , m, or M, they may be the same or different.

[0016] [9] A ninth aspect of the present invention is: A compound represented by formula (1-1-2a), (1-1-3a), (1-2-5a), or (1-2-6a), wherein the relative permittivity at 10 GHz of a cured product obtained by curing a composition containing the compound is lower than 3.0. TIFF0007861630000011.tif80148 In equations (1-1-2a), (1-1-3a), (1-2-5a), and (1-2-6a), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, Z 2 and Z 3 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH2) a -COO-, -OCO-(CH2) a -, -CH=CH-, -SO2-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20. m is an integer between 0 and 20. M is a single bond or oxygen, X is either fluorine or methyl, n is an integer between 0 and 4. This includes the case where n is 2 or greater, and if there are multiple X values ​​in the expression, they may be the same or different. In the formula, R b If there are multiple instances of , m, or M, they may be the same or different.

[0017]

[10] The tenth aspect of the present invention is A composition for forming a low dielectric constant resin according to any one of [1] to [7], containing a nonpolymerizable liquid crystal compound.

[0018]

[11] An eleventh aspect of the present invention is: A composition containing an inorganic filler, as described in any one of [1] to [7] and

[10] , wherein the cured product of the composition has a thermal conductivity of 1.0 W / m·K or more, and is a composition for forming a low dielectric constant resin.

[0019]

[12] A twelfth aspect of the present invention is: A composition for forming a low dielectric constant resin, comprising an inorganic oxide as described in any one of [1] to [7] and

[10] to

[11] , wherein the thermal conductivity of the cured product obtained by curing the composition is 1.0 W / m·K or more. Alternatively, a composition according to any one of items [1] to [7] and

[10] to

[11] , which contains a nitride filler, and is a composition for forming a low dielectric constant resin, wherein the thermal conductivity of the cured product obtained by curing the composition is 10 W / m·K.

[0020]

[13] A thirteenth aspect of the present invention is: The composition for forming a low dielectric constant resin according to

[11] is wherein the inorganic filler is at least one selected from aluminum nitride, boron nitride, silicon nitride, diamond, graphite, silicon carbide, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, titanium oxide, tin oxide, holmium oxide, calcium oxide, magnesium hydroxide, aluminum hydroxide, cordierite, and mullite.

[0021]

[14] A fourteenth aspect of the present invention is: The composition for forming a low dielectric constant resin according to

[11] is wherein the inorganic filler is aluminum nitride, boron nitride, silicon nitride, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, titanium oxide, or magnesium hydroxide.

[0022]

[15] A fifteenth aspect of the present invention is This low dielectric constant resin insulating film is a polymer molded article obtained by curing a composition for forming a low dielectric constant resin described in any one of items [1] to [7] and

[10] to

[14] with heat or ultraviolet light.

[0023]

[16] A sixteenth aspect of the present invention is: A low dielectric constant resin film or low dielectric constant resin sheet is a polymer molded article obtained by curing a composition for forming a low dielectric constant resin described in any one of items [1] to [7] and

[10] to

[14] with heat or ultraviolet light.

[0024]

[17] A seventeenth aspect of the present invention is: This low dielectric constant resin part is a polymer molded article obtained by curing a composition for forming a low dielectric constant resin described in any one of items [1] to [7] and

[10] to

[14] with heat or ultraviolet light.

[0025]

[18] The eighteenth aspect of the present invention is The electronic device uses a polymer-forming material as described in any one of items

[15] to

[17] . [Effects of the Invention]

[0026] The composition for forming a highly linear, low-dielectric resin for low-dielectric members of the present invention, in addition to its low dielectric properties, has high applicability, heat dissipation, and transparency, as well as excellent properties such as chemical stability, heat resistance, hardness, and mechanical strength. Therefore, it is suitable for applications such as low-dielectric circuit boards, substrates for low-dielectric antennas, low-dielectric coatings, and low-dielectric adhesives. [Best Mode for Carrying Out the Invention]

[0027] The following describes in detail the composition, compound, insulating film, film, and method for manufacturing resin parts for forming low dielectric constant resins according to the present invention. The terms used herein are defined as follows. "Liquid crystal compounds" is a general term for compounds that have liquid crystal phases such as the nematic phase and the smectic phase, and compounds that do not have a liquid crystal phase but possess physical properties unique to liquid crystals, such as dielectric anisotropy, refractive index anisotropy, and magnetic susceptibility anisotropy, and are useful as components of liquid crystal compositions. Furthermore, "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0028] The meaning of phrases such as "at least one -CH2- in the alkyl group may be replaced with -O-, -CO-, etc." is illustrated with an example. For instance, groups in which at least one -CH2- in C4H9- is replaced with -O- or -CH=CH- include C3H7O-, CH3-O-(CH2)3-, CH3-O-CH2-O-, H2C=CH-(CH2)3-, CH3-CH=CH-(CH2)2-, and CH3-CH=CH-CH2-O-. Thus, the phrase "at least one" means "at least one selected without distinction." Furthermore, considering the stability of the compound, CH3-O-CH2-O-, where oxygen atoms are not adjacent to each other, is preferred over CH3-OO-CH2-, where oxygen atoms are adjacent to each other.

[0029] "Compound (1)" means the liquid crystal compound represented by formula (1) above, and may also mean at least one of the compounds represented by formula (1). The same applies to "Compound (1-1)," and Compound (1-1) and Compound (1-2) are collectively referred to as "Compound (1)." "Composition (1)" means a liquid crystal composition containing at least one compound selected from Compound (1). "Polymer (1)" means a liquid crystal polymer obtained by polymerizing Composition (1). One Compound (1) contains multiple A 3 When a compound (1) has A, any two A can be the same or different. 3 They may be the same or different. This rule applies to Z 3 Yes, R b This also applies to other symbols such as X, and to the base symbol, etc.

[0030] [Liquid crystal compound] The compound (1) used in the present invention has a liquid crystal skeleton (a rod-shaped mesogenic skeleton) and polymerizable groups, and exhibits high polymerization reactivity, a wide liquid crystal phase temperature range, and good miscibility. When this compound (1) is mixed with other liquid crystal compounds or polymerizable compounds, it readily becomes homogeneous.

[0031] Terminal group R of compound (1)1a or R 1b , ring structure A 1 , A 2 Or A 3 and the binding group Z 1 , Z 2 , Z 3 or Z 4 By appropriately selecting these elements, physical properties such as the liquid crystal phase region can be arbitrarily adjusted. The effects of the terminal groups, ring structure, and type of bonding group on the physical properties of compound (1), as well as preferred examples thereof, are described below.

[0032] <Terminal group R 1 :R 1a and R 1b ) Terminal group R of compound (1) 1 This is a polymerizable group represented by any of the formulas (PG-1) to (PG-5). TIFF0007861630000012.tif58133 In equations (PG-1) to (PG-5), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, and q is 0 or 1. Also R b If there are multiple items, they may be the same or different.

[0033] Preferred examples include polymerizable groups represented by formulas (PG-1a) to (PG-1d), (PG-2a), (PG-3a), (PG-4a), and (PG-5a) to (PG-5g). TIFF0007861630000013.tif91157

[0034] Of these preferred polymerizable groups, (PG-1a) to (PG-1d), (PG-2a), and (PG-4a) have α,β unsaturated ketone structures, and can therefore be polymerized by various means to form polymers with larger molecular weights. (PG-3a) has a vinyl group adjacent to an electron-donating group, and can therefore be polymerized by various means to form polymers with larger molecular weights. (PG-5a) to (PG-5g) have strained cyclic ethers, and can therefore be polymerized by various means to form polymers with larger molecular weights.

[0035] The polymerizable groups represented by formulas (PG-1) to (PG-5) can be selected appropriately depending on the film manufacturing conditions. For example, when manufacturing films using commonly used photocuring, acrylic groups or methacrylic groups represented by formula (PG-1) are preferred due to their high curability, solubility in solvents, and ease of handling.

[0036] <Ring structure A :A 1 , A 2 and A 3 > Preferred examples of ring structure A of compound (1) are 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2 These include 5-diyl, pyridazine-3,6-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9-fluorofluorene-2,7-diyl, and 9,9-difluorofluorene-2,7-diyl. Further preferred examples include 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, and 2-methyl-1,4-phenylene. Particularly preferred examples are 1,4-cyclohexylene or 1,4-phenylene.

[0037] The stereochemistry of 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or tetrahydronaphthalene-2,6-diyl is preferred in trans configuration over cis. Since 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are structurally identical, the latter is not used as an example. This rule also applies to relationships such as that between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.

[0038] When at least one ring in ring structure A is 1,4-phenylene, the orientational order parameter and magnetic anisotropy are large. Also, when at least two rings are 1,4-phenylene, the temperature range of the liquid crystal phase is wide and the transparency point is high. Preferred examples of substitutions where at least one hydrogen atom on the 1,4-phenylene ring may be replaced include fluorine, C1-C5 alkyl groups, -CF3, or -OCF3, resulting in a lower melting point and higher solubility. Furthermore, the molecular polarizability is reduced, leading to a lower dielectric constant. Additionally, the suppression of molecular motion results in lower dielectric loss.

[0039] When at least one ring is 1,4-cyclohexylene, the transparency point is high, the relative permittivity is very low, the dielectric loss is low, and the viscosity is low. Also, when at least two rings are 1,4-cyclohexylene, the transparency point is high, the relative permittivity is very low, the dielectric loss is low, and the viscosity is low. If at least one ring is a fused ring such as a naphthalene ring, decahydronaphthalene ring, or fluorene ring, the molecular volume is large and the relative permittivity is low.

[0040] <Binding group Z :Z 1 , Z 2 , Z 3and Z 4 > A preferred example of the bonding group Z in compound (1) is a single bond, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH2) a -COO-, -OCO-(CH2) a -, -CH=CH-, -SO2-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20. A more preferred example is a single bond, -(CH2) a -,-(CH2) a O-, -O(CH2) a -, -O(CH2) a Examples include O-, -COO-, or -OCO-. A particularly preferred example is a single bond, -(CH2) a -,-(CH2) a O-, -O(CH2) a -, or -O(CH2) a The timescale is O-, where a is an integer between 1 and 20.

[0041] The bonding group Z is a single bond, -(CH2) a -,-(CH2) a O-, -O(CH2) a -, -O(CH2) a When the bond group Z is O-, -CF2O-, or -OCF2-, the viscosity decreases. Also, when the bond group Z is -(CH2) a -,-(CH2) a O-, -O(CH2) a -, or -O(CH2) a When it is O- and a is around 2 to 12, the melting point decreases, solubility in organic solvents increases, the molecular length increases, the temperature range of the liquid crystal phase widens, and the dielectric loss tangent is small.

[0042] When compound (1) has two rings, its viscosity is low, and when it has three or more rings, its transparency point is high. In this specification, a 6-membered ring and fused rings containing a 6-membered ring are generally considered to be rings, while 3-membered rings, 4-membered rings, and 5-membered rings alone are not considered rings. Furthermore, fused rings such as naphthalene rings, decahydronaphthalene rings, and fluorene rings are considered to be a single ring.

[0043] As described above, terminal group R a By appropriately selecting the type of ring structure A and bonding group Z, the number of rings, etc., a compound having the desired physical properties can be obtained. Examples of preferred compounds (1) include formulas (1-1-1) to (1-1-3), (1-2-1) to (1-2-6), and (1-3-1) to (1-3-6). TIFF0007861630000014.tif5192 TIFF0007861630000015.tif107115 TIFF0007861630000016.tif112130

[0044] In equations (1-1-1)~(1-1-3), (1-2-1)~(1-2-6), and (1-3-1)~(1-3-6), Z 1 , Z 2 , Z 3 and Z 4 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-,, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH2) a -COO-, -OCO-(CH2) a -, -CH=CH-, -SO2-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20. Z in the formula 3 They may be the same or different. X is either fluorine or methyl, n is an integer between 0 and 4. This includes the case where n is 2 or greater, and if there are multiple X values ​​in the expression, they may be the same or different. R 1a and R 1b These are independently polymerizable groups represented by formula (PG-1) or (PG-5), TIFF0007861630000017.tif2585 In formulas (PG-1) and (PG-5), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, where q is 0 or 1, and R is present in the formula. b If there are multiple items, they may be the same or different.

[0045] A more preferred example of compound (1) is shown below. TIFF0007861630000018.tif119142 In equations (1-1-1a)~(1-1-3a), (1-2-1a), (1-2-5a), and (1-2-6a), R b These are hydrogen, fluorine, -CF3, or an alkyl group having 1 to 5 carbon atoms. Z 2 and Z 3 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-, -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH2) a -COO-, -OCO-(CH2) a -, -CH=CH-, -SO2-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20. m is an integer between 0 and 20. M is a single bond or oxygen, X is either fluorine or methyl, n is an integer between 0 and 4. This includes the case where n is 2 or greater, and if there are multiple X values ​​in the expression, they may be the same or different. In the formula, R b If there are multiple instances of , m, or M, they may be the same or different.

[0046] [Method for synthesizing compound (1)] Compound (1) can be synthesized by combining known techniques in organic synthesis. Methods for introducing the desired terminal groups, ring structures, and bonding groups into the starting materials are described in textbooks such as Houben-Wyle (Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart), Organic Syntheses (John Wily & Sons, Inc.), Organic Reactions (John Wily & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), and New Experimental Chemistry Course (Maruzen).

[0047] The method for introducing the binding group Z is explained in schemes 1 to 9 below. In these schemes, MSG 1 and MSG 2 represents a monovalent organic group having at least one ring, and Hal represents a halogen. Multiple MSGs used in the scheme below 1 (or MSG) 2 The compounds (1A) to (1M) in the scheme below correspond to compound (1) above. These methods can be applied to the synthesis of optically active compound (1) and optically inert compound (1).

[0048] (Scheme 1) Compounds in which Z is a single bond As shown below, MSG is produced by reacting arylboric acid (S1) with a compound (S2) synthesized by a known method in the presence of an aqueous carbonate solution and a catalyst such as tetrakis(triphenylphosphine)palladium. 1 and MSG 2Compound (1A) can be synthesized in which a single bond is introduced between the two. This compound (1A) can also be synthesized by reacting compound (S3), which is synthesized by known methods, with n-butyllithium, then zinc chloride, and then further reacting it with compound (S2) in the presence of a catalyst such as dichlorobis(triphenylphosphine)palladium.

[0049] TIFF0007861630000019.tif52137

[0050] (Scheme 2) Compounds where Z is -CH=CH- As shown below, MSG is produced by reacting a phosphorus ylide generated by reacting a phosphonium salt (S5), synthesized by a known method, with a base such as potassium t-butoxide, with an aldehyde (S4). 1 and MSG 2 Compound (1B) in which -CH=CH- is introduced between the two isomers can be synthesized. Depending on the reaction conditions and substrate, the cis isomer may be produced, so the cis isomer can be isomerized to the trans isomer by known methods as needed.

[0051] TIFF0007861630000020.tif33122

[0052] (Scheme 3) Compounds where Z is -(CH2)2- As shown below, by hydrogenating the compound (1B) obtained as described above in the presence of a catalyst such as palladium carbon, MSG is produced. 1 and MSG 2 A compound (1C) having -(CH2)2- can be synthesized between them.

[0053] TIFF0007861630000021.tif25130

[0054] (Scheme 4) Compounds where Z is -(CF2)2- As shown below, MSG is produced by fluorinating diketone (S6) with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst, according to the method described in J. Am. Chem. Soc., 2001, 123, 5414. 1 and MSG 2 A compound (1D) having -(CF2)2- between the two can be synthesized.

[0055] TIFF0007861630000022.tif35122

[0056] (Scheme 5) Compounds where Z is -(CH2)4- As shown below, a compound having -(CH2)2-CH=CH- is synthesized using the phosphonium salt (S7) instead of the phosphonium salt (S5) according to the method of Scheme 2, and then catalytically hydrogenated in the same manner as in Scheme 3 to obtain MSG 1 and MSG 2 Compound (1E) can be synthesized in which -(CH2)4- is introduced between the two.

[0057] TIFF0007861630000023.tif34151

[0058] (Scheme 6) Compounds where Z is -CH2O- or -OCH2- As shown below, compound (S4) is reduced with a reducing agent such as sodium borohydride to obtain compound (S8). This is halogenated with hydrobromic acid or the like to obtain compound (S9). By reacting this compound (S9) with compound (S10) in the presence of potassium carbonate, MSG is produced. 1 and MSG 2 Compounds (1F) can be synthesized in which -OCH2- (or -CH2O-) is introduced between the two.

[0059] TIFF0007861630000024.tif55147

[0060] (Scheme 7) Compounds where Z is -COO- or -OCO- As shown below, compound (S3) is reacted with n-butyllithium, followed by carbon dioxide, to obtain a carboxylic acid (S11). This compound (S11) and phenol (S10) are dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to obtain MSG. 1 and MSG 2 A compound (1G) can be synthesized in which -COO- (or -OCO-) is introduced between the two.

[0061] TIFF0007861630000025.tif34151

[0062] (Scheme 8) Compounds where Z is -CF=CF- As shown below, compound (S3) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain compound (S12). Subsequently, compound (S2) is treated with n-butyllithium and then reacted with compound (S12) to obtain MSG. 1 and MSG 2 A compound (1H) in which -CF=CF- is introduced between the two isomers can be synthesized. By selecting the synthesis conditions, it is also possible to produce the cis isomer.

[0063] TIFF0007861630000026.tif37146

[0064] (Scheme 9) Compounds in which Z is -CF2O- or -OCF2- As shown below, compound (1G) obtained by the method described in Scheme 7 above is treated with a sulfurizing agent such as Lawson's reagent to obtain compound (S16). This compound (S16) is fluorinated with a pyridine hydrogen fluoride complex and N-bromosuccinimide (NBS) to obtain MSG 1 and MSG 2Compound (1M) having -CF2O- (or -OCF2-) between the two can be synthesized. Compound (1M) can also be synthesized by fluorinating compound (S16) with (diethylamino)sulfate trifluoride (DAST). Furthermore, the method described in P. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480. It is also possible to generate these bonding groups by [method / action].

[0065] TIFF0007861630000027.tif55119

[0066] [Liquid crystal composition] The composition (1) in the present invention contains at least one compound (1) and consists of two or more compounds. That is, composition (1) may consist of two or more compounds (1), or it may consist of a combination of at least one compound (1) and at least one compound other than compound (1). Such components other than compound (1) are not particularly limited, but examples include polymerizable compounds other than compound (1) (hereinafter also referred to as "other polymerizable compounds"), non-polymerizable liquid crystalline compounds, optically active compounds, polymerization initiators, solvents, and fillers.

[0067] <Other polymerizable compounds> Composition (1) may also contain other polymerizable compounds as components. Preferred polymerizable compounds are those that do not reduce film-forming properties and mechanical strength. These polymerizable compounds are classified into those that are not liquid crystalline and those that are. Examples of polymerizable compounds that are not liquid crystalline include vinyl derivatives, styrene derivatives, (meth)acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, and itaconic acid derivatives. Preferred examples of these derivatives are shown below.

[0068] Preferred vinyl derivatives include, for example, vinyl chloride, vinyl fluoride, vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, N-vinylacetamide, pt-butyl benzoate, vinyl N,N-dimethylaminobenzoate, vinyl benzoate, ethyl vinyl ether, hydroxybutyl monovinyl ether, t-amyl vinyl ether, cyclohexanedimethanol methyl vinyl ether, α,β-vinylnaphthalene, methyl vinyl ketone, and isobutyl vinyl ketone.

[0069] Preferred styrene derivatives include, for example, styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, and α-methylstyrene.

[0070] Preferred (meth)acrylic acid derivatives include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO-added triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, bisphenol A EO-added diacrylate, bisphenol A glycidyl diacrylate (trade name: "Viscoat 700" manufactured by Osaka Organic Chemical Co., Ltd.), polyethylene glycol diacrylate dimethyl itaconate, and the like.

[0071] Preferred sorbic acid derivatives include, for example, sodium sorbate, potassium sorbate, lithium sorbate, 1-naphthylmethylammonium sorbate, benzylammonium sorbate, dodecylammonium sorbate, octadecylammonium sorbate, methyl sorbate, ethyl sorbate, propyl sorbate, isopropyl sorbate, butyl sorbate, t-butyl sorbate, hexyl sorbate, octyl sorbate, octadecyl sorbate, cyclopentyl sorbate, cyclohexyl sorbate, vinyl sorbate, allyl sorbate, and propagyl sorbate.

[0072] Preferred fumaric acid derivatives include, for example, dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclopentyl fumarate, and dicyclohexyl fumarate.

[0073] Preferred itaconic acid derivatives include, for example, diethyl itaconate, dibutyl itaconate, and diisopropyl itaconate. In addition to these, many other polymerizable compounds can be used, such as butadiene, isoprene, and maleimide.

[0074] <Other polymerizable liquid crystal compounds> Composition (1) may contain polymerizable liquid crystal compounds other than compound (1). From the viewpoint of the expression of the liquid crystal phase of the polymerizable liquid crystal composition and compatibility with compound (1) and organic solvents, compounds represented by formulas (M1), (M2), or (M3) are preferred as the polymerizable liquid crystal compounds. TIFF0007861630000028.tif69138 In equations (M1), (M2), and (M3), A MThis group is independently a divalent group selected from 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, and in this divalent group, at least one hydrogen may be replaced with fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkoxycarbonyl, or C1-C5 alkanoyl. Z M These are independently single bonds, -OCH2-, -CH2O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF2O-, -OCF2-, -CH2CH2-, -CF2CF2-, -CH=CHCOO-, -OCOCH=CH-, -CH2CH2COO-, -OCOCH2CH2-, -COOCH2CH2-, -CH2CH2OCO-, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH3)-, -C(CH3)=N-, -N=N-, -C≡C-, -CH=NN=CH-, or -C(CH3)=NN=C(CH3)-. X M These are hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, C1-C20 alkyl, C1-C20 alkenyl, C1-C20 alkoxy, or C1-C20 alkoxycarbonyl. Y M These are independently single bonds, -O-, -COO-, -OCO-, or -OCOO-, Q M These are single bonds, -O-, -COO-, or -OCO-, q is an integer from 1 to 6, c and d are independent integers between 0 and 3, and the relationship 1 ≤ c + d ≤ 6, and a is an integer between 0 and 20. R M It is hydrogen or methyl.

[0075] <Non-polymerizable liquid crystalline compounds> Composition (1) may also contain a liquid crystalline compound that does not have polymerizable groups. Examples of such non-polymerizable liquid crystalline compounds are listed in LiqCryst (LCI Publisher GmbH, Hamburg, Germany), a database of liquid crystalline compounds. By polymerizing composition (1) containing the non-polymerizable liquid crystalline compound, composite materials of the polymer of compound (1) and the liquid crystalline compound can be obtained. In such composite materials, for example, the non-polymerizable liquid crystalline compound is present in a polymer network, such as a polymer-dispersed liquid crystal.

[0076] <Polymerization initiator> Composition (1) may also contain a polymerization initiator as a component. Depending on the polymerization method of composition (1), the polymerization initiator may be, for example, a photoradical polymerization initiator, a photocationic polymerization initiator, or a thermal radical polymerization initiator.

[0077] The photoradical polymerization initiator is not particularly limited and any known one can be used. Examples include 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacrididine, 9,10-benzphenazine, benzophenone / Michlar's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / p-dimethylaminobenzoate methyl mixture, and benzophenone / methyltriethanolamine mixture. Examples of commercially available products include the "Darocure Series 1173, 4265" and the "IrgaCure Series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, 2959" manufactured by Chiba Specialty Co., Ltd.

[0078] The photocationic polymerization initiator is not particularly limited and any known one can be used, for example, "Sylacure UVI-6990, 6974" manufactured by UCC Corporation, "Adeka Optomer SP-150, 152, 170, 172" manufactured by Asahi Denka Co., Ltd., "Photoinitiator 2074" manufactured by Rhodia Corporation, "Irga Cure 250" manufactured by Ciba Specialty Co., Ltd., and "DTS-102" manufactured by Midori Chemical Co., Ltd.

[0079] Preferred initiators for thermal radical polymerization include, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide (DTBPO), t-butyl peroxydiisobutyrate, lauroyl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), and azobiscyclohexanecarbonilate (ACN).

[0080] Preferred initiators for anionic polymerization, coordination polymerization, and living polymerization include, for example, alkali metal alkyl compounds such as n-C4H9Li and t-C4H9Li-R3Al, aluminum compounds, and transition metal compounds. <Hardening agent> When composition (1) contains a compound having a cyclic ether group as a component, it may also contain a curing agent as a component. Examples of preferred curing agents are shown below.

[0081] As amine-based curing agents, 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 Examples include -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, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine, and N-aminoethylpiperazine.

[0082] Examples of acid anhydride-based curing agents include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, ethylene glycol bis-anhydrotrimethylate, glycerin bis(anhydrotrimellitate) monoacetate, dedecenyl succinic anhydride, and chloride anhydride.

[0083] Examples of phenolic curing agents include 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 novolac, xylylene novolac, and bisphenol A novolac. In addition to the above, curing agents described in Japanese Patent Publication No. 2004-256687, Japanese Patent Publication No. 2002-226550, etc., can also be used.

[0084] The active ester curing agent is not particularly limited and known agents can be used. Examples include "HPC-8000H-65T" from DIC Corporation as an active ester compound containing a dicyclopentadiene-type diphenol structure, "EXB-8150-65T" from DIC Corporation as an active ester compound containing a naphthalene structure, "DC808" from Mitsubishi Chemical Corporation as an active ester compound containing an acetylated phenol novolac, "YLH1026" from Mitsubishi Chemical Corporation as an active ester compound containing a benzoylated phenol novolac, "DC808" from Mitsubishi Chemical Corporation as an active ester curing agent that is an acetylated phenol novolac, and "YLH1026" from Mitsubishi Chemical Corporation as an active ester curing agent that is a benzoylated phenol novolac.

[0085] Furthermore, as curing accelerators, cycloamidine compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene, and 5,6-dibutylamino-1,8-diazabicyclo[5.4.0]-7-undecene; and to these cycloamidine compounds, maleic anhydride, 1,4-benzoquinone, 2,5-tholquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, and 2,3-dimethoxy-5-methyl Compounds having intramolecular polarization obtained by adding quinone compounds such as -1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, diazophenylmethane, and phenolic resins that have π bonds; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; 2-methylimidazole, 2-phenylimidazole, 2-phenyl Examples include imidazole compounds such as nyl-4-methylimidazole; derivatives of the imidazole compounds; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine; phosphorus compounds having intramolecular polarization obtained by adding compounds having π bonds, such as maleic anhydride, the above-mentioned quinone compounds, diazophenylmethane, and phenolic resins, to the organic phosphine compounds; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and N-methylmorpholine tetraphenylborate; derivatives of the tetraphenylboron salts; and adducts of phosphine compounds such as triphenylphosphonium-triphenylborane and N-methylmorpholine tetraphenylphosphonium-tetraphenylborate with the tetraphenylboron salts.

[0086] <Inorganic fillers as fillers> Inorganic fillers can be added to improve thermal conductivity, mechanical strength, and viscosity. For example, fillers with high thermal conductivity may include metal nitrides such as aluminum nitride, boron nitride, and silicon nitride; carbides such as diamond, graphite, and silicon carbide; metal oxides such as magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, titanium oxide, tin oxide, holmium oxide, and calcium oxide; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; silicate compounds such as cordierite or mullite; and metal fillers such as gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, and stainless steel. Preferably, boron nitride and silicon oxide, which have low dielectric constants, are preferred, and hexagonal boron nitride (h-BN) is particularly preferred because it has a low dielectric constant and high thermal conductivity. While thermal conductivity and other properties increase with higher inorganic filler content, inorganic fillers generally have a higher relative permittivity and lower dielectric loss tangent compared to resin components. Therefore, increasing the amount of filler increases the dielectric constant. Consequently, it is preferable to fill only the required amount, within a range that does not exceed the desired dielectric constant.

[0087] Examples of filler shapes include spherical, amorphous, fibrous, rod-shaped, cylindrical, and plate-shaped. The filler shape is preferably one that does not hinder the orientation of the polymerizable liquid crystal compound when it forms the liquid crystal phase. The type, shape, size, and amount of filler can be appropriately selected according to the purpose. If the resulting low-dielectric-constant molded body requires insulation, a conductive filler is acceptable as long as the desired insulation, dielectric constant, and dielectric loss are maintained. Preferably, plate-shaped crystalline boron nitride is used, as this facilitates the orientation of the liquid crystal compound perpendicular to the plate-like structure, or the orientation of the liquid crystal compound along the plate-like structure. Whether the orientation is perpendicular or along the plate depends on the affinity between the polymerizable liquid crystal compound and the filler. Using a polymerizable liquid crystal compound with fine-particle spherical silicon oxide can increase the viscosity of the molten material or solution, while using a silicate compound is preferable because it reduces the thermal expansion coefficient of the molded body.

[0088] The average particle size of spherical or irregularly shaped fillers is preferably 0.1 to 200 μm, more preferably 1 to 100 μm. A particle size of 0.1 μm or more provides good thermal conductivity, while a particle size of 200 μm or less allows for increased packing efficiency. For fibrous fillers, longer fiber lengths improve tensile strength, but this makes mixing and dispersion impossible, so selection should be based on the application. When dispersed, the average particle size of fibrous fillers is preferably 0.01 to 200 μm, more preferably 0.1 to 100 μm. A particle size of 0.1 μm or more provides good thermal conductivity, while a particle size of 200 μm or less allows for increased mechanical strength. In this specification, the average particle size is based on particle size distribution measurement using laser diffraction and scattering methods. Specifically, using analysis based on Fraunhofer diffraction theory and Mie scattering theory, the median diameter is defined as the diameter at which the larger and smaller particles are equal in volume (by volume) when a powder is divided into two parts from a certain particle size using a wet method. The amount of filler is preferably such that the low dielectric constant molded body contains 20 to 95% by weight of filler after curing. More preferably, it is 50 to 95% by weight. A filler of 20% by weight or more is preferable because it increases thermal conductivity. A filler of 95% by weight or less is preferable because it prevents the low dielectric constant molded body from becoming brittle.

[0089] As the filler, commercially available products that have undergone surface treatment such as dispersion treatment or waterproofing treatment may be used as is, or the surface treatment agent may be removed from the commercially available product. Alternatively, untreated fillers may be treated with silane coupling agents, affinity agents, surface tension modifiers, settling inhibitors, coagulation inhibitors, etc., before use.

[0090] <Solvent> Composition (1) may contain a solvent. Polymerization of composition (1) may be carried out in or without a solvent. Composition (1) containing a solvent may be applied to a substrate, for example by a spin coating method, and then the solvent may be removed before photopolymerization. Alternatively, after photocuring, post-treatment may be performed by heating to an appropriate temperature and thermal curing.

[0091] Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, cyclohexane, methylcyclohexane, cyclopentanone, cyclohexanone, and PGMEA. These solvents may be used individually or in combination of two or more. Furthermore, there is little point in limiting the proportion of solvent used during polymerization; it should be determined on a case-by-case basis, taking into account polymerization efficiency, solvent costs, energy costs, etc.

[0092] <Other additives> Since compound (1) and composition (1) have high polymerizability, stabilizers may be added to facilitate handling. Such stabilizers can be any known substances without limitation, such as hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT). For applications requiring a low dielectric loss tangent (low tanδ) and a high glass transition temperature, it is preferable to add a crosslinking agent. The crosslinking agent is preferably one that chemically bonds with the polymerizable groups of the liquid crystal compound having polymerizable groups at the ends of the present invention, thereby forming a three-dimensional crosslink.

[0093] [Low dielectric constant resin] Another embodiment of the present invention, the low dielectric constant resin, is a cured product for forming the low dielectric constant resin described above. It can be used in sheet-like, film-like, plate-like, fibrous, and three-dimensional shaped parts (such as the insulating portion of a connector), and can also be used as a coating agent, adhesive, or filler. Because this low dielectric constant resin is a cured product of the above-described composition, it has a low dielectric constant, and because it uses a polymerizable liquid crystal compound as the polymer, it also exhibits excellent thermal conductivity, heat resistance, rigidity, elasticity, moldability, chemical resistance, and dimensional stability.

[0094] When a low-dielectric resin exhibits liquid crystalline properties, molecular orientation can be controlled by orientation treatment before curing. Relative permittivity and thermal conductivity exhibit anisotropy depending on the molecular orientation. For example, in dielectric and thermal design of electronic substrates, it becomes possible to design the substrate so that the area directly beneath a heat-generating IC has high thermal conductivity in the thickness direction, while other areas are oriented laterally to spread heat over a wider area, enabling more advanced material design. The orientation method can be controlled by the following methods.

[0095] Methods for controlling the orientation of mesogenic moieties of liquid crystal molecules in compositions for forming low dielectric constant resins include treating the filler surface with a silane coupling agent or orientation agent having orientation capabilities, and aligning the molecules using the self-orientation-regulating force of the composition itself. These methods may be performed individually or in combination of two or more. Examples of orientation states controlled by such orientation control methods include homogeneous, twisted, homeotropic, hybrid, bent, and spray orientation, which can be appropriately determined depending on the application and the orientation control method. Furthermore, during film formation or molding, shear stress can be applied to the liquid crystal state before curing to physically orient the molecules.

[0096] The orientation temperature is in the range of room temperature to 250°C, preferably room temperature to 200°C, and more preferably room temperature to 180°C. The heat treatment time is in the range of 5 seconds to 2 hours, preferably 10 seconds to 60 minutes, and more preferably 20 seconds to 30 minutes. If the heat treatment time is shorter than the above range, the temperature of the layer made of composition (1) may not be raised to the predetermined temperature, and if it is longer than the above range, productivity may decrease. Note that the above heat treatment conditions vary depending on the type and composition ratio of the compounds used in composition (1), the presence and content of polymerization initiators, etc., and therefore these are only approximate ranges. In particular, if the temperature is higher than the polymerization initiation temperature, the resin will harden before orientation occurs, and a low dielectric constant resin with molecular chains oriented in a specific direction cannot be obtained.

[0097] Examples of polymerization methods for composition (1) include radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization. However, to immobilize the molecular arrangement or helical structure, thermal polymerization or photopolymerization using light or heat, such as electron beams, ultraviolet light, visible light, or infrared light (heat rays), is suitable. Thermal polymerization is preferably carried out in the presence of a radical polymerization initiator, and photopolymerization is preferably carried out in the presence of a photo-radical polymerization initiator. For example, a polymer in which the arrangement of liquid crystal molecules is immobilized can be obtained by a polymerization method in which ultraviolet light or electron beams are irradiated in the presence of a photo-radical polymerization initiator. The resulting polymer (1) may be a homopolymer, random copolymer, alternating copolymer, block copolymer, or graft copolymer, and can be appropriately selected depending on the application.

[0098] When fixing the orientation of composition (1) by photopolymerization, ultraviolet light or visible light is usually used. The wavelength of the light used for irradiation is in the range of 150 to 500 nm, preferably 250 to 450 nm, and more preferably 300 to 400 nm. Examples of light sources for irradiation include low-pressure mercury lamps (germicidal lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), and short-arc discharge lamps (ultra-high-pressure mercury lamps, xenon lamps, mercury xenon lamps), and ultraviolet light-emitting diodes. Among these, metal halide lamps, xenon lamps, ultraviolet light-emitting diodes, and high-pressure mercury lamps are preferred.

[0099] The wavelength range of the light source can be selected by installing a filter or the like between the light source and composition (1) to allow only a specific wavelength range to pass through. The amount of light emitted from the light source is 2 to 5000 mJ / cm². 2 Preferably 10 to 3000 mJ / cm² 2 more preferably 100-2000 mJ / cm² 2 This is within the specified range. The temperature conditions during light irradiation are preferably set in the same way as the heat treatment temperature described above.

[0100] The conditions for fixing the orientation of composition (1) by thermal polymerization are as follows: the thermosetting temperature is in the range of room temperature to 350°C, preferably room temperature to 250°C, more preferably 50°C to 200°C; and the curing time is in the range of 5 seconds to 10 hours, preferably 1 minute to 5 hours, more preferably 5 minutes to 1 hour. After polymerization, it is preferable to cool slowly to suppress stress strain, etc. Alternatively, reheating may be performed to alleviate strain, etc.

[0101] The polymer whose orientation has been controlled as described above, or the polymer in the polymerization process, may be further oriented in any desired direction by mechanical operations such as stretching. The isolated polymer (1) may be dissolved in a solvent and oriented on an orientation-treated substrate to be processed into a film or the like, or two polymers may be mixed and processed, or multiple polymers may be laminated. Preferred solvents include, for example, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide dimethylacetal, tetrahydrofuran, chloroform, 1,4-dioxane, bis(methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, trifluoroethyl acetate, hexafluoro-2-propanol, 2-methoxyethyl acetate, methyl ethyl ketone, cyclopentanone, and cyclohexanone. These may also be used in combination with common organic solvents such as acetone, benzene, toluene, heptane, and methylene chloride.

[0102] Even if a composition for forming a highly linear, low-dielectric-constant resin does not exhibit liquid crystalline properties, or exhibits a very narrow liquid crystalline phase, if it has high crystallinity, it forms domains with axes aligned in a certain direction, resulting in higher thermal conductivity compared to polymerizable compounds such as bisphenol A structures. Furthermore, orientation and crystallinity can be controlled by slowly curing the material from an isotropic liquid state while a polymer sheet surface with aligned orientation directions or a crystalline resin filler is present as a core for crystal growth. However, excessively high crystallinity tends to reduce flexibility, so it is necessary to use a polymerizable composition with appropriate crystalline properties.

[0103] The low dielectric constant molded article of the present invention consists of the above composition (1) and is used in the form of a sheet, film, thin film, fiber, molded article, etc. Preferred forms are film and thin film. Film and thin film are obtained by polymerizing composition (1) while it is coated on a substrate or release film, or while it is sandwiched between flat plates such as a substrate or mold. Alternatively, it can be obtained by coating composition (1) containing a solvent onto an orientation-treated substrate and then removing the solvent. Furthermore, film can also be obtained by press molding the polymer. In this specification, the film thickness of a sheet is 1 mm or more, the film thickness is 5 μm or more, preferably 10 to 500 μm, more preferably 20 to 300 μm, and the film thickness is less than 5 μm.

[0104] The following describes in detail a method for producing a film as a low dielectric constant molded body using a solvent-containing composition (1). First, composition (1) is applied to a release-treated substrate, and the solvent is dried and removed to form a coating layer of uniform thickness. Examples of application methods include spin coating, roll coating, caten coating, flow coating, print coating, microgravure coating, gravure coating, wire barcode coating, dip coating, spray coating, and meniscus coating.

[0105] The solvent can be removed by drying, for example, by air drying at room temperature, drying on a hot plate, drying in a drying oven, or by blowing warm or hot air. The conditions for solvent removal are not particularly limited; it is sufficient to dry the coating layer until the solvent is mostly removed and the fluidity of the coating layer is lost. Depending on the type and composition ratio of the compounds used in composition (1), the molecular orientation of the liquid crystal molecules in the coating layer may be completed during the drying process. In such cases, the coating layer that has gone through the drying process can be subjected to the polymerization process without going through the heat treatment process described above. However, in order to make the orientation of the liquid crystal molecules in the coating layer more uniform, it is preferable to heat the coating layer that has gone through the drying process to the liquid crystal phase emergence temperature to orient it in the liquid crystal state, and then fix the orientation by photopolymerization or thermal polymerization treatment.

[0106] Furthermore, when composition (1) is used as a low dielectric constant insulating coating, it is also preferable to perform orientation treatment on the substrate surface before coating. Examples of orientation treatment methods include simply forming an orientation film on the substrate, rubbing the substrate with a rayon cloth after forming an orientation film on the substrate, rubbing the substrate directly with a rayon cloth, or obliquely depositing silicon oxide, or using a stretched film, a photo-alignment film, or an ion beam for rubbing-free orientation. In addition, it is sometimes possible to form a desired orientation state without treating the substrate surface. For example, when forming homeotropic orientation, surface treatment such as rubbing is often not performed, but rubbing may be performed to achieve higher orientation.

[0107] The orientation film is not particularly limited as long as it can control the orientation of composition (1), and known orientation films can be used. For example, polyimide, polyamide, polyvinyl alcohol, alkylsilane, alkylamine, or lecithin-based orientation films are preferred. Silane coupling agents are also preferred when vertical orientation is required.

[0108] Any method can be used for the rubbing process described above. Typically, a rubbing cloth made of materials such as rayon, cotton, and polyamide is wrapped around a metal roll or the like, and the roll is rotated and moved while in contact with the substrate or alignment film, or the substrate is moved while the roll is fixed.

[0109] Furthermore, to obtain a more uniform orientation, an orientation control additive may be included in composition (1). Examples of such orientation-controlling additives include imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and its esters, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropyl betaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamines, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkylethylene oxide adducts, perfluoroalkyltrimethylammonium salts, oligomers having a perfluoroalkyl group and a hydrophilic group, oligomers having a perfluoroalkyl group and a lipophilic group, urethanes having a perfluoroalkyl group, and organosilicon compounds having a primary amino group (e.g., alkoxysilane type, linear siloxane type, and three-dimensional condensation type silsesquioxane type organosilicon compounds).

[0110] Examples of the above-mentioned substrates include plastic film substrates such as polyimide, polyamideimide, polyamide, polyetherimide, polyetheretherketone, polyetherketone, polyketone sulfide, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyacetal, polycarbonate, polyarylate, acrylic resin, polyvinyl alcohol, polypropylene, cellulose, triacetylcellulose or partially saponified thereof, epoxy resin, phenolic resin, norbornene resin, as well as glass substrates such as alkali glass, borosilicate glass, and flint glass; metal substrates such as aluminum, iron, and copper; and inorganic substrates such as silicon.

[0111] The above-mentioned film substrate may be a uniaxially oriented film or a biaxially oriented film. The above-mentioned film substrate may be subjected to a surface treatment such as saponification, corona treatment, or plasma treatment in advance. A protective layer that is not affected by the solvent contained in the above-mentioned composition (1) may be formed on these film substrates. Examples of materials that can be used as a protective layer include polyvinyl alcohol. Furthermore, an anchor coat layer may be formed to improve the adhesion between the protective layer and the substrate. Such an anchor coat layer may be made of either inorganic or organic material, as long as it improves the adhesion between the protective layer and the substrate. The composition for forming low dielectric constant resins of the present invention is useful for low dielectric substrates, low dielectric sheets, low dielectric coatings, low dielectric adhesives, low dielectric molded products, and the like.

[0112] <Manufacturing method> The following describes in detail a method for producing a composition for forming a low dielectric constant resin, and a method for producing a low dielectric constant high heat-resistant substrate and a low dielectric constant high heat-resistant insulating layer from the composition.

[0113] The composition for forming low dielectric constant resins according to the present invention can be used as a liquid resin raw material in the temperature range in which the liquid crystal phase or isotropic phase is exhibited, or it can be used after being dissolved in a solvent. To prepare the solution, the polymerizable liquid crystal composition, the necessary solvent, filler, and additives are added, and the mixture is stirred and degassed using a stirrer until the composition is uniform. For example, a rotation-orbit mixer can be used, stirring at 2000 rpm for 10 minutes, followed by degassing at 2200 rpm for 10 minutes. In addition to a rotation-orbit mixer, dispersion can be carried out using a stirring motor, a swivel, a three-roll mill, a ball mill, a rotation-orbit mill, a planetary mill, a bead mill, a jet mill, etc.

[0114] For the coating method, in order to uniformly coat the low dielectric constant polymerizable composition, it is preferable to use a wet coating method. Among the wet coating methods, when producing a small amount, the spin coating method, which enables simple and homogeneous film formation, is preferable. When emphasizing productivity, the 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 method, curtain coating method, inkjet method, flexographic printing method, screen printing method, rod coating method, etc. are preferable. The wet coating method can be appropriately selected according to the required film thickness, viscosity, curing conditions, etc. from these methods.

[0115] When manufacturing a sheet, the casting method of coating and peeling the composition on a release-treated substrate by the above method or the like can be used. When manufacturing a structure, resin molding methods such as the press molding method, injection method, and various 3D printer molding methods (extrusion lamination method) can be used using a mold. After molding, it is possible to perform final curing after removing the mold or to perform final curing while still in the mold.

[0116] [Examples] The present invention will be described in more detail by examples (including production examples of compounds, compositions, polymers, resins, etc.). The present invention is not limited by these examples.

[0117] [Synthesis Example of Compound (1)] Compound (1) was synthesized according to the procedures shown in the examples such as Synthesis Example 1. Unless otherwise specified, the reaction was carried out under a nitrogen atmosphere. The synthesized compound was identified by methods such as NMR analysis. The element characteristics of Compound (1), composition, polymer, resin, etc. were measured by the following methods.

[0118] [NMR Analysis] For the measurement, JNM-ECZR manufactured by JEOL was used. 1For the measurement of 1H-NMR, the sample was dissolved in a deuterated solvent such as CDCl3, and the measurement was carried out at room temperature under the conditions of 500 MHz and 16 accumulations. Tetramethylsilane was used as an internal standard. 19 For the measurement of 19F-NMR, CFCl3 was used as an internal standard and the measurement was carried out with 32 accumulations. In the description of the nuclear magnetic resonance spectrum, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sex means sextet, m means multiplet, and br means broad.

[0119] <Gas Chromatographic Analysis> For the measurement, a GC-2014 gas chromatograph manufactured by Shimadzu Corporation was used. The column used was a capillary column DB-1 (length 30 m or 15 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. Nitrogen (1 ml / min) was used as the carrier gas. The temperature of the sample vaporization chamber was set at 300 °C, and the temperature of the detector (FID) part was set at 300 °C. The sample was dissolved in an appropriate solvent such as acetone, prepared into a 1 wt% solution, and 1 μl of the obtained solution was injected into the sample vaporization chamber. For the recorder, a GCSolution system manufactured by Shimadzu Corporation etc. was used.

[0120] <HPLC Analysis> For the measurement, a Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. The column used was a YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle size 5 μm) manufactured by Waters. The eluent was prepared by appropriately mixing acetonitrile and water. As the detector, a UV detector, an RI detector, a CORONA detector etc. were appropriately used. When a UV detector was used, the detection wavelength was set at 254 nm. The sample was dissolved in acetonitrile, prepared into a 0.1 wt% solution, and 1 μL of this solution was introduced into the sample chamber. For the recorder, a C-R7Aplus manufactured by Shimadzu Corporation was used.

[0121] <Ultraviolet-Visible Spectrophotometric Analysis> A Shimadzu PharmaSpec UV-1700 was used for the measurements. The detection wavelength was set from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, which was then placed in a quartz cell (optical path length 1 cm) for measurement.

[0122] <Measurement sample> When measuring the phase structure and transition temperature (transparency point, melting point, polymerization initiation temperature, etc.), the compound itself was used as the sample. (1) Phase structure The sample was placed on a hot plate (Mettler FP-52 hot stage) of a melting point analyzer equipped with a polarizing microscope. The phase state and its changes were observed using a polarizing microscope while the sample was heated at a rate of 3°C / min, and the type of phase was identified.

[0123] (2) Transition temperature (°C) A high-sensitivity differential scanning calorimeter, X-DSC7000, manufactured by SSI Nanotechnology, was used for the measurements. The sample was heated and cooled at a rate of 3-5°C / min, and the transition temperature was determined by extrapolating the starting point of the endothermic or exothermic peak associated with the phase change of the sample. The melting point and polymerization initiation temperature of the compound were also measured using this instrument. The temperature at which a compound transitions from solid to liquid crystal phases such as the smectic phase and nematic phase is sometimes abbreviated as the "lower limit temperature of the liquid crystal phase." The temperature at which a compound transitions from the liquid crystal phase to liquid is sometimes abbreviated as the "transparency point."

[0124] Crystals were represented by C. When different types of crystals could be distinguished, they were represented as C1, C2, etc. Smectic phases were represented by S, and nematic phases by N. Within the smectic phase, when smectic A, smectic B, smectic C, or smectic F phases could be distinguished, they were represented as S. A S B S C , or S F This was expressed as follows. Liquid (isotropic) was represented as I. The transition temperature was expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from crystal to nematic phase is 50.0°C, and the transition temperature from nematic phase to liquid is 100.0°C.

[0125] [Synthesis Example 1] Compound (S01: Compound (1-1-1a) with R b Both are CH3, n=0, m=0, M and Z 2 Synthesis of compounds in which the bond is a single bond. TIFF0007861630000029.tif2167 4,4'-biphenyldiol (S01-a) is commercially available, for example, from Fujifilm Wako Pure Chemical Industries, Ltd.

[0126] TIFF0007861630000030.tif24160 Under a nitrogen atmosphere, a solution of 4,4'-biphenyldiol (S01-a) (10.0 g, 53.70 mmol), N,N'-dicyclohexylcarbodiimide (DCC) (24.4 g, 118.2 mmol), and 4-dimethylaminopyridine (DMAP) (3.94 g, 32.22 mmol) in dichloromethane (100 mL) was cooled to -10°C and stirred. Methacrylic acid (9.71 g, 112.8 mmol) was added dropwise to the resulting solution, and the temperature was gradually raised to room temperature while stirring for 6 hours. Dichloromethane (100 mL) was added to the reaction mixture, filtered, washed three times with water, and the organic layer was concentrated under reduced pressure at 40°C. The resulting residue was isolated by silica gel column chromatography (solvent: toluene / ethyl acetate = 5 / 1 (volume ratio)) and concentrated under reduced pressure at 40°C. The compound was then purified by recrystallization filtration (heptane / ethyl acetate = 3 / 3v) and further dried under reduced pressure to obtain compound (S01) (11.8 g, 36.52 mmol). The transition temperature of compound (S01) was C 150.9 I (°C). The polymerization initiation temperature was 171.9°C.

[0127] Also, compounds 1 The H-NMR signals were as follows: δ(ppm;CDCl3):7.58-7.56(d,4H), 7.19-7.18(d,4H), 6.37(qd,2H), 6.21(qd,2H), 2.07(dd,6H)

[0128] [Synthesis Example 2] Compound (S02: Compound (1-1-3a) with R b Both are CH3, n=0, m=0, M and Z 2 Synthesis of compounds in which the bond is a single bond. TIFF0007861630000031.tif2167 4,4'-Bicyclohexyldiol (S02-a) is commercially available, for example, from Fujifilm Wako Pure Chemical Industries, Ltd. This raw material was purified using common methods such as recrystallization filtration, and the trans isomer was isolated.

[0129] TIFF0007861630000032.tif24159 Compound (S02) (3.60 g, 10.76 mmol) was obtained by using 4,4'-bicyclohexyldiol (S02-a) instead of 4,4'-biphenyldiol (S01-a) in the same manner as described in Synthesis Example 1 of Example 1. The transition temperature of this compound (S01) was C 113.0 I (°C). The polymerization initiation temperature was 118.8°C.

[0130] Also, compounds 1 The H-NMR signals were as follows: δ(ppm;CDCl3):6.06(qd,2H), 5.52-5.51(qd,2H), 4.71-4.65(tt,2H), 2.05-2.00( m, 4H), 1.92-1.91(dd,6H), 1.80-1.77(m,4H), 1.38-1.36(m,4H), 1.15-1.08(m,6H)

[0131] [Synthesis Example 3] Compound (S03: Compound (1-1-1a) with R b Both are CH3, n=0, m=6, M is oxygen, Z 2 Synthesis of compounds in which the bond is a single bond. TIFF0007861630000033.tif20112 4,4'-biphenyldiol (S03-a) is commercially available, for example, from Fujifilm Wako Pure Chemical Industries, Ltd. TIFF0007861630000034.tif45166

[0132] (Paragraph 1) In a nitrogen atmosphere, a solution of 4,4''-biphenyldiol (S01-a) (10.0 g, 53.70 mmol), sodium hydroxide (4.51 g, 112.8 mmol), and 6-bromo-1-hexanol (20.4 g, 112.8 mmol) in N,N-dimethylformamide (100 mL) was heated and stirred at 60 °C for 6 hours. The reaction solution was filtered as it was, and the crystals were washed three times with ethanol and then dried under reduced pressure to obtain compound (S03-b) (14.0 g, 36.22 mmol).

[0133] (Paragraph 2) Using the compound (S03-b) obtained in the previous step and 4,4'-bicyclohexyldiol (S02-a) instead of 4,4'-biphenyldiol (S01-a), compound (S03) (2.90 g, 5.55 mmol) was obtained by the same method as described in Synthesis Example 1 of Example 1. The transition point of this compound (S03) was C 61.9 I (°C). The polymerization initiation temperature was 163.3 °C.

[0134] Also, the 1 1H-NMR signals of the compound were as follows. δ (ppm; CDCl3): 7.45 - 7.43 (d, 4H), 6.94 - 6.91 (d, 4H), 6.09 (qd, 2H), 5.54 - 5.53 (qd, 2H), 4.17 - 4.14 (t, 4H), 3.99 - 3.97 (t, 4H), 1.93 (dd, 6H), 1.84 - 1.78 (tt, 4H), 1.74 - 1.68 (tt, 4H), 1.55 - 1.42 (m, 8H)

[0135] [Synthesis Example 4] Compound (S04: Compound (1-1-3a), where R b are both CH3, n = 0, m = 6, M is oxygen , Z 2 is a single bond) synthesis TIFF0007861630000035.tif22125 4,4'-Dicyclohexanol (S02-a) is a synthetic example. 2 I used the same thing.

[0136] TIFF0007861630000036.tif22100 TIFF0007861630000037.tif66165

[0137] (1st stage) Under a nitrogen atmosphere, 2,3-dihydro-2H-pyran (27.9 g, 331.3 mmol) was added to a solution of 6-bromo-1-hexanol (50.0 g, 276.1 mmol) and pyridinium-p-toluenesulfonate (6.94 g, 27.7 mmol) in dichloromethane (500 mL), and the mixture was stirred at the same temperature for 2 hours. The reaction mixture was poured into water, the organic layer was washed three times with water, and the resulting organic layer was concentrated under reduced pressure to obtain compound (S04-b) (68.5 g, 258.3 mmol).

[0138] (Second stage) Under a nitrogen atmosphere, 4,4'-dicyclohexanol (S02-a) (7.12 g, 35.9 mmol) was added to a solution of 55% sodium hydride (3.29 g, 75.5 mmol) in N,N-dimethylformamide (100 mL) at 10 °C. After stirring this solution at 40 °C for 30 minutes, the compound (S04-b) (20.0 g, 75.5 mmol) obtained in the previous step was added, and the mixture was heated and stirred at 60 °C for 18 hours. The reaction mixture was slowly added to water and extracted with toluene (300 mL). The organic layer was washed three times with water, and the resulting organic layer was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: toluene / ethyl acetate = 2 / 1 (volume ratio)) to obtain compound (S04-c) (11.4 g, 20.1 mmol).

[0139] (3rd stage) Under a nitrogen atmosphere, the previously obtained compound (S04-c) (11.4 g, 20.1 mmol) and pyridinium-p-toluenesulfonate (6.94 g, 27.7 mmol) were mixed in methanol (200 mL) / THF (200 mL) and stirred at the same temperature for 2 hours. The reaction mixture was poured into water and extracted with ethyl acetate (500 mL). The organic layer was washed three times with water, and the resulting organic layer was concentrated under reduced pressure to obtain the white crystalline compound (S04-d) (8.00 g, 20.0 mmol).

[0140] (4th stage) Compound (S04) (7.78 g, 14.5 mmol) was obtained by using compound (S04-d) instead of 4,4'-biphenyldiol (S01-a) in the same manner as described in Synthesis Example 1 of Example 1. The transition temperature of this compound (S01) was C 40.6 I (°C). The polymerization initiation temperature was 173.8°C.

[0141] Also, compounds 1 The H-NMR signals were as follows: δ(ppm;CDCl3): 6.02(qd,2H), 5.53-5.52(qd,2H), 4.13-4.10(t,4H), 3.43(t,4H), 3.11-3.06(tt,2H), 2.05-1.99(m, 4H), 1.93- 1.92(dd,6H), 1.76-1.71(m,4H), 1.69-1.63(m,4H), 1.57-1.51(m,4H), 1.39-1.32(m,8H), 1.19-1.09(m,4H), 1.06-0.91(m,6H)

[0142] [Synthesis Example 5] Compound (S07: Compound (1-1-3), R 1a and R 1b is equation (PG-5), R b This is hydrogen, q=0, Z 1 , Z 2 and Z 4 Both are for the synthesis of compounds with -OCH2- TIFF0007861630000038.tif2062 The same 4,4'-dicyclohexanol (S02-a) used in Synthesis Example 1 was employed.

[0143] TIFF0007861630000039.tif25142 Under a nitrogen atmosphere, 4,4'-dicyclohexanol (S02-a) (5.00 g, 25.3 mmol) was added to a solution of 55% sodium hydride (2.42 g, 55.56 mmol) in N,N-dimethylformamide (60 mL) at 10°C. After stirring this solution at 40°C for 30 minutes, epibromohydrin (10.4 g, 75.8 mmol) was added, and the mixture was heated and stirred at 40°C for 3 days. The reaction mixture was slowly added to water and extracted with toluene (200 mL). The organic layer was washed three times with water, and the resulting organic layer was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: toluene / ethyl acetate = 4 / 1 (volume ratio)) to obtain compound (S07) (5.10 g, 16.5 mmol). The transition temperature of compound (S07) was C 38.3 I (°C). The polymerization initiation temperature was 137.1°C.

[0144] Also, compounds 1 The H-NMR signals were as follows: δ(ppm;CDCl3):3.71-3.68(dd,2H), 3.46-3.42(dd,2H), 3.24-3.17(tt,2H), 3.14-3.10(m,2H), 2.79-2.7 8(dd,2H), 2.60-2.59(dd,2H), 2.08-2.01(m,4H), 1.77-1.71(m,4H), 1.23-1.12(m, 4H), 1.05-0.92(m,6H)

[0145] [Material property evaluation] [Example 1] <Preparation of samples for relative permittivity measurement> The synthesized polymerizable compound (S01) was placed on top of a 1mm thick A4-sized PTFE sheet. A 0.5mm thick A4-sized PTFE sheet with a 1.5mm x 60mm through-slit in the center was then placed on top of this sheet. 20% more polymerizable compound than needed to fill the through-slit was then added to the slit. Care was taken to prevent the polymerizable compound from scattering due to static electricity, and the 1mm thick A4-sized PTFE sheet was placed on top of that. The layered sheets were sandwiched between 5mm thick aluminum plates and placed in a Toyo Seiki Co., Ltd. mini test press set to 190°C. The sheet was pressurized to 3MPa while degassing, heated to 210°C, and cured for 30 minutes. The pressing pressure was set to 3MPa to prevent the PTFE mold from collapsing. A 0.5 mm × 1.5 mm × 60 mm strip-shaped sample was evaluated as a low dielectric constant resin after curing.

[0146] <Methods for evaluating relative permittivity and thermal conductivity> After hardening, the resonant frequency shift and attenuation of the hardened paper strips were measured using cavity resonators (CP431 for 1 GHz, CP531 for 10 GHz) manufactured by Kanto Electronics Applied Development Co., Ltd., connected to a network analyzer (Agilent Technologies (now Keysight) E8361A). The relative permittivity was calculated using software from the same company. To minimize the influence of moisture content in the paper strips when comparing data, the strips were shaped the day before measurement, and the evaluation of the relative permittivity began after the samples had been left to stand for more than 60 minutes in a laboratory at a temperature of 20°C and humidity of 48%. Furthermore, the strip-shaped samples after measuring the dielectric constant were cut into approximately 1.5 mm square pieces, and the thermal diffusivity in the thickness direction was measured using an iPhase Mobile Type 1 thermal diffusivity measuring device, and the specific heat was measured using a Rigaku Thermo Plus EVO2 DSC-8231 (DSC) high-sensitivity differential scanning calorimeter. Since the sample size was small and the density could not be measured, the density was assumed to be 1.1, and the thermal conductivity was evaluated in a simplified manner. Because the material was formed by heating and pressing, the molecular chains are oriented in the planar direction, meaning that the thermal conductivity is being measured in the direction of poor thermal conductivity (Abstracts of the 37th Symposium on Thermophysical Properties, C223 Influence of surface treatment on synergistic effects on the thermal conductivity of liquid crystalline epoxy resin composite materials, 2016).

[0147] [Example 2] Samples were prepared in the same manner as in Example 1 except that the polymerizable compound was changed to (S02) and the temperature during pressing was changed to 150°C, and the relative permittivity and thermal conductivity were measured.

[0148] [Example 3] Samples were prepared in the same manner as in Example 2 except that the polymerizable compound was changed to (S05) and the curing temperature was set to 200°C, and the relative permittivity and thermal conductivity were measured. In addition, 5% by weight of V-601 oil-soluble azo polymerization initiator manufactured by Fuji Film Wako Pure Chemical Corporation was added to (S05) as an initiator. 0.05 g of a curing agent was added to 1.00 g of (S05). TIFF0007861630000040.tif39136 Compound (S05) was synthesized by the method described in Japanese Patent No. 5084148.

[0149] [Example 4] Samples were prepared in the same manner as in Example 2 except that the polymerizable compound was changed to (S06) and the curing temperature was set to 180°C, and the relative permittivity was measured. To (S06), a calculated amount of 4,4'-diamino-1,2-diphenylethane (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a curing agent based on the epoxy equivalent. 0.20 g of a curing agent was added to 0.68 g of (S06). TIFF0007861630000041.tif26100 Compound (S06) was synthesized by the method described in Japanese Patent No. 5084148.

[0150] [Example 5] Samples were prepared in the same manner as in Example 2 except that the polymerizable compound was changed to (S03), and the relative permittivity and thermal conductivity were measured.

[0151] [Comparative Example 1] Kapton 500H (thickness: 125 μm) manufactured by Toray DuPont Co., Ltd. was cut into 1.5 mm × 100 mm using a cutter knife, and the relative permittivity and thermal conductivity were measured in the same manner as in Example 1.

[0152] [Comparative Example 2] A 2mm thick transparent acrylic sheet manufactured by Hikari Co., Ltd. was processed into a 1mm x 2mm x 100mm sheet using a coping saw and sandpaper, and the relative permittivity and thermal conductivity were measured in the same manner as in Example 1.

[0153] Table 1 summarizes the relative permittivity and thermal conductivity measured in Examples 1-4 and Comparative Examples 1-2. [Table 1] TIFF0007861630000042.tif47143

[0154] The dielectric constant measurements revealed that while widely used polyimide films and commercially available acrylic resins have a dielectric constant of 3.0 or higher at 10 GHz, Examples 1-4 have a dielectric constant lower than 3.0, indicating that they are compositions suitable for use in high-frequency circuit boards. In particular, Example 2 has a low dielectric constant, achieving a dielectric constant comparable to that of PTFE substrates. Comparing Example 1 and Example 2, Example 2 has a lower dielectric constant. This is thought to be because the bicyclohexyl structure has less electron conjugation than the biphenyl structure. Also, comparing Example 3 and Example 4, Example 3 has a lower dielectric constant. While it was thought that a tri-ring structure has fewer polymerizable groups and is effective for lower dielectric constants than a bi-ring structure, it is more likely that the more ester bonds connecting the benzene rings, the higher the dielectric constant.

[0155] On the other hand, in the measurement of thermal conductivity, a comparison between Example 1 and Example 2 shows that the bicyclohexyl structure has higher thermal conductivity than biphenyl and structures in which benzene rings are linked by ester bonds. This indicates that, although thermal energy is transmitted by phonon conduction in materials other than metals, (S02) of the present invention uses a trans-type (is-type) bicyclohexyl intermediate, similar to liquid crystal materials, and therefore has high linearity, thus efficiently conducting phonons. Furthermore, the difference in thermal conductivity between the biphenyl structure and the structure in which benzene rings are linked by ester bonds is that biphenyl is slightly better, but not as large as the difference between bicyclohexyl and biphenyl. In a comparison between Example 2 and Example 5, it can be seen that as the alkyl chain between the bicyclohexyl skeleton and the polymerizable group becomes longer, the thermal diffusivity decreases slightly, but the dielectric constant also decreases. This is thought to be because the number of polymerizable groups that increase the dielectric constant decreases as the alkyl chain lengthens, and phonon conduction becomes slightly less efficient due to the softer molecular chain. In fact, while the cured sheet produced in Example 1 was very brittle and easily cracked, a flexible sheet was obtained in Example 5.

[0156] [Evaluation of the thermal conductivity of high heat dissipation filler composite materials] <Preparation of samples for thermal conductivity measurement> [Example 6] For applications requiring heat dissipation, the polymerizable compound of the present invention is expected to be used in combination with a high heat dissipation filler. Therefore, the heat dissipation performance was evaluated by measuring the thermal conductivity of a compound formed by combining the low dielectric constant resin-forming compound with a boron nitride filler in a volume ratio of 50:50. 0.44 g of the polymerizable compound (S01) and 0.80 g of boron nitride (PolarTherm PTX-25, manufactured by Momentive Performance Materials Japan LLC) were mixed in a mortar and pestle. Using the same method as for dielectric constant measurement samples, a 25 mmφ × 0.5 mm thick disc (for measuring thermal diffusivity in the planar direction) and a 10 mm × 10 mm × 0.5 mm square (for measuring thermal diffusivity in the thickness direction) were prepared using a heated press and a PTFE mold. The pressing pressure was set to 3 MPa to prevent the PTFE mold from collapsing. Since typical electronic circuit boards are not molded / cured under the same high pressure as high-filler heat-dissipating resin components, molding was performed under these conditions.

[0157] <Thermal conductivity evaluation> The specific heat (measured using the DSC mentioned above) and specific gravity (measured using a specific electron scale hydrometer DME-220 manufactured by Shinko Denshi Co., Ltd.) of the fabricated composite material were determined in advance. The thermal conductivity in the in-plane direction and thickness direction was calculated by multiplying these values ​​by the thermal diffusivity obtained using a LFA467 thermal diffusivity measuring device and accompanying software manufactured by Netch Japan Co., Ltd.

[0158] [Example 7] Samples were prepared in the same manner as in Example 6, except that the polymerizable compound was changed to (S02), and the thermal conductivity was evaluated.

[0159] [Example 8] The polymerizable compound was changed to a mixture of 0.11 g of (S01) and 0.33 g of (S02). First, (S02) was placed in an aluminum cup and placed on a hot plate. The hot plate was set to a temperature of 140°C to melt it, and then (S01) was melted into it. (S01) alone did not melt unless the set temperature was 190°C or higher. Boron nitride powder was added to the melt of (S01) and (S02) and mixed with a spatula. After cooling, the mixture was ground in a mortar, and a sample was prepared in the same manner as in Example 6, and the thermal conductivity was evaluated.

[0160] [Example 9] Samples were prepared in the same manner as in Example 6, except that the polymerizable compound was changed to (S06) and the curing temperature was set to 200°C, and the dielectric constant was measured. 4,4'-diamino-1,2-diphenylethane (manufactured by Wako Pure Chemical Industries, Ltd.) was added to (S06) as a curing agent in an amount calculated from epoxy equivalents. 0.20 g of curing agent was added to 0.68 g of (S06).

[0161] [Comparative Example 3] Samples were prepared in the same manner as in Example 5, except that the polymerizable compound was changed to jER807 manufactured by Mitsubishi Chemical Corporation and the curing agent was changed to 4,4'-diamino-1,2-diphenylethane (manufactured by Wako Pure Chemical Industries, Ltd.), and the thermal conductivity was measured.

[0162] Table 2 summarizes the thermal conductivity measured in Examples 6-9 and Comparative Example 3. [Table 2] TIFF0007861630000043.tif31122

[0163] A comparison of Example 6 and Example 7 shows that, as with the comparison of Example 1 and Example 2, using a polymerizable compound with a trans-type bicyclohexyl structure (S02) results in higher thermal conductivity in both the planar and thickness directions compared to using a biphenyl structure (S01). In this experiment, a PTFE sheet was used as the mold, so the pressure did not rise as much as with a hard metal mold combining convex and concave shapes, and the aggregated boron nitride was not crushed. Therefore, it is thought that the difference in thermal conductivity between the planar and thickness directions is small, even though boron nitride was used. Due to the lower pressure, the absolute value of the thermal conductivity is lower compared to when molding under conditions for curing a highly filled heat-dissipating resin (Example 9, Patent Document 4).

[0164] On the other hand, mixing (S01) and (S02) increases the thermal conductivity in the planar direction. This is thought to be because (S02) has a low transition temperature, and (S01), which has a higher transition temperature, dissolves in the liquid S02, making it more fluid, or because some molecules polymerize during melting, increasing the degree of orientation of the elongated molecules.

[0165] Furthermore, when (S01) and (S02) were cured without filler, they had low flexibility and broke when a circular sample for thermal conductivity measurement was being scraped with a utility knife. However, by extending the alkyl between the ring structure and the polymerizable group, flexibility increases, as in (S03) and (S04), and the number of benzene rings and polymerizable groups, which increase the dielectric constant, can be reduced, allowing for the expectation of a low dielectric constant. Thus, by using the highly linear polycyclic polymerizable compound of the present invention, it is possible to form electronic substrates and their peripheral components that have a low dielectric constant and high thermal conductivity.

[0166] [Example 10] 0.36 g of polymerizable compound (S07) and 0.53 g of DIC Corporation's active ester curing agent HPC-8000-65ST were mixed together. A solution of 1.1 g of toluene and 0.05 g of Hokko Chemical Industry Co., Ltd.'s curing accelerator TBP-3S was then added and the mixture was stirred. This mixed solution was applied to a polyimide film (Toray DuPont Kapton 300H) to a thickness of approximately 40 μm after drying. The solvent was dried on a hot plate at 80°C for 3 minutes, and then the film was placed in an oven and cured at 150°C in a nitrogen gas atmosphere for 1 hour.

[0167] Samples formed on polyimide film were cut into 50mm squares, and the resonant frequency shift and attenuation were measured using AET Corporation's cavity resonators (TE mode 10GHz and 28GHz) connected to a vector network analyzer (Anritsu MS46522B-043). The relative permittivity was calculated using AET's software. Since the measured values ​​represent a two-layer structure of polyimide film and cured film, the dielectric constant of the cured film alone was calculated using AET's calculation sheet, using the values ​​measured for the polyimide film only. To minimize the influence of moisture content in the samples when comparing data, the measuring equipment was placed in a room with constant air conditioning, and the samples were allowed to settle on the lab bench for at least 60 minutes before measurement began.

[0168] [Comparative Example 4] Samples were prepared in the same manner as in Example 9, except that the epoxy compound was changed to YX4000H manufactured by Mitsubishi Chemical Corporation, which has a biphenyl skeleton, and the dielectric constant was measured.

[0169] [Comparative Example 5] Samples were prepared in the same manner as in Example 9, except that the epoxy compound was changed to jER807 manufactured by Mitsubishi Chemical Corporation, which has a bisphenol F skeleton, and the dielectric constant was measured.

[0170] Table 3 shows the measurement results of the relative permittivity for Example 10 and Comparative Example 4. [Table 3] TIFF0007861630000044.tif26139

[0171] A comparison of Example 10 with Comparative Examples 4 and 5 shows that the polymerizable cyclohexane ring compound of the present invention has a low dielectric constant even when epoxy is used, and the dielectric constant can be kept low even when glass fibers are composited with it, making it suitable for use in low-dielectric substrates. [Industrial applicability]

[0172] The composition for forming a highly linear, low-dielectric resin for low-dielectric members of the present invention, in addition to its low dielectric properties, possesses excellent properties such as high coatability, heat dissipation, transparency, chemical stability, heat resistance, hardness, and mechanical strength. Therefore, it can be suitably used in low-dielectric circuit boards, low-dielectric antenna substrates, low-dielectric coatings, and low-dielectric adhesives. Furthermore, because it exhibits low dielectric constant and high thermal diffusivity at 10 GHz and 28 GHz, it is particularly suitable for use as an electronic circuit board and its peripheral components used in high-frequency ranges. Moreover, in addition to the above properties, it exhibits high heat dissipation, making it useful for high-heat-dissipation material applications.

Claims

1. A composition for forming a low dielectric constant resin, comprising a liquid crystal compound having polymerizable groups at its terminals, represented by formula (1-1), wherein the relative dielectric constant of the cured product of the composition is less than 3.0 at 10 GHz. R １ａ -Z １ -A １ -Z ２ -A ２ -Z ４ -R １ｂ (1-1) In formula (1-1), A １ and A ２ are each independently 1,4-cyclohexylene or 1,4-phenylene, Z １ and Z ４ Independently, - (CH ２ ) ａ -, -O(CH ２ ) ａ -, - (CH ２ ) ａ O-, or -O(CH ２ ) ａ O-, where a is an integer from 1 to 16, and A １ and A ２ When both are 1,4-phenylene, a is an integer from 3 to 16. Z ２ It is a single bond, R 1a and R １ｂ These are independently polymerizable groups represented by formula (PG-1) or (PG-5), In formulas (PG-1) and (PG-5), R ｂ is hydrogen or methyl, q is 0, and R is in the formula ｂ If there are multiple items, they may be the same or different.

2. A composition for forming a low dielectric constant resin according to claim 1, comprising a liquid crystal compound having polymerizable groups at its terminals, represented by any of formulas (1-1-1) to (1-1-3). In formulas (1-1-1) to (1-1-3), Z １ and Z ４ Independently, - (CH ２ ) ａ -, -O(CH ２ ) ａ’ -, - (CH ２ ) ａ’ O-, where a in equation (1-1-1) is an integer from 3 to 16, and a in equations (1-1-2) and (1-1-3) is an integer from 1 to 16. Z ２ It is a single bond, n is 0, R １ａ and R １ｂ These are independently polymerizable groups represented by formula (PG-1) or (PG-5), In formulas (PG-1) and (PG-5), R ｂ is hydrogen or methyl, q is 0, and R is in the formula ｂ If there are multiple items, they may be the same or different.

3. In equation (1-1), R １ａ and R １ｂ The composition for forming a low dielectric constant resin according to claim 1, wherein the polymerizable group is represented by formula (PG-1). In formula (PG-1), R ｂ is hydrogen or methyl, and R is in the formula. ｂ If there are multiple items, they may be the same or different.

4. A compound represented by formula (1-1-1a), wherein the relative permittivity at 10 GHz of a cured product obtained by curing a composition containing the compound is lower than 3.

0. In formula (1-1-1a), R ｂ It is methyl, Z ２ It is a single bond, m is an integer between 3 and 16. M is a single bond or oxygen, n is 0, In the formula, R ｂ If there are multiple instances of , m, or M, they may be the same or different.

5. A compound represented by formula (1-1-2a) or (1-1-3a), wherein the relative permittivity at 10 GHz of a cured product obtained by curing a composition containing the compound is less than 3.

0. In equations (1-1-2a) and (1-1-3a), R ｂ It is methyl, Z ２ It is a single bond, m is an integer between 1 and 16. M is a single bond or oxygen, n is 0, In the formula, R ｂ If there are multiple instances of , m, or M, they may be the same or different.

6. A composition for forming a low dielectric constant resin according to any one of claims 1 to 3, comprising a nonpolymerizable liquid crystal compound.

7. A composition for forming a low dielectric constant resin, comprising an inorganic filler, according to any one of claims 1 to 3 and 6, wherein the thermal conductivity of the cured product obtained by curing the composition is 1 W / m·K or more.

8. A composition for forming a low dielectric constant resin, comprising an inorganic filler, according to any one of claims 1 to 3 and 6, wherein the thermal conductivity of the cured product obtained by curing the composition is 1 W / m·K or more. A composition for forming a low dielectric constant resin, comprising a nitride filler or a nitride filler, wherein the thermal conductivity of the cured product obtained by curing the composition is 10 W / m·K or more.

9. The composition for forming a low dielectric constant resin according to claim 8, wherein the inorganic filler is at least one selected from aluminum nitride, boron nitride, silicon nitride, diamond, graphite, silicon carbide, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, titanium oxide, tin oxide, holmium oxide, calcium oxide, magnesium hydroxide, metal oxides of aluminum hydroxide, cordierite, and mullite.

10. The composition for forming a low dielectric constant resin according to claim 8, wherein the inorganic filler is aluminum nitride, boron nitride, silicon nitride, magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, titanium oxide, or magnesium hydroxide.

11. A low dielectric constant resin insulating film is a polymer molded article obtained by curing a composition for forming a low dielectric constant resin according to any one of claims 1 to 3 and 6 to 9 with heat or ultraviolet light.

12. A low dielectric constant resin film or low dielectric constant resin sheet, which is a polymer molded article obtained by curing a composition for forming a low dielectric constant resin according to any one of claims 1 to 3 and 6 to 9 with heat or ultraviolet light.

13. A low dielectric constant resin part is a polymer molded article obtained by curing a composition for forming a low dielectric constant resin according to any one of claims 1 to 3 and 6 to 9 with heat or ultraviolet light.

14. An electronic device using a polymer-forming material according to any one of claims 11 to 13.

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