Diamines for forming low dielectric constant resins, compositions, polyimides, low dielectric components, and electronic devices using the same.

Abstract

To achieve: a diamine for forming a polyimide film capable of being suitably used for a next generation communication equipment in which frequencies are heightening or and a radar and the like; a composition containing the diamine for forming a low dielectric constant resin; a polyamic acid using the diamine; and a polyimide film.SOLUTION: A composition for forming a low dielectric constant resin is a composition containing a compound having amino groups on both terminals as shown by formula (1). A dielectric constant of a cured product obtained by curing the composition without addition of any filler at 10 GHz is lower than 3.0. For example, each of A1, A2, and A3 is 1,4-cyclohexylene,1,4-cyclohexenylene, or 1,4-phenylene. At least one of A1 and A2 is 1,4-cyclohexenylene, each of Z1, Z2, Z3, and Z4 is a single bond or a 1-20C alkylene, and m1 is 0, 1, or 2.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to a composition for forming a low dielectric constant resin using a liquid crystal compound having amino as a polymerizable group, a low dielectric polyimide film, and a low dielectric component using the same. In particular, it relates to a material for high-frequency substrates and related materials, a low dielectric component using the same, and electronic equipment. [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 1)

[0003] Currently, the main materials for flexible high-frequency substrates are LCP and low-dielectric polyimide (mPI). LCP is a thermoplastic resin, which has many drawbacks, such as the need for molding and bonding at high temperatures and poor adhesion to other resins and to copper foil used as electrodes. On the other hand, mPI can be used with conventional polyimide film manufacturing equipment and copper foil lamination equipment, but currently it cannot be said to have high-frequency characteristics as good as LCP. Patent document 1 describes research into further lowering the dielectric constant of polyimide by introducing a large alicyclic ring into the tetracarboxylic acid skeleton. Furthermore, Patent Document 2 describes an investigation into using a diamine with a long skeleton consisting of a benzene ring into which fluorine has been introduced, and how to achieve low dielectric properties by reducing the density of fluorine and imide groups in the polyimide molecular chain. In addition, Patent Document 3 describes an investigation aimed at achieving low dielectric properties by introducing fluorine into the benzene ring or the alkylene moiety between the benzene rings. On the other hand, while studies using diamines with a main skeleton consisting of a cyclohexane ring and alkylene to reduce the dielectric strength of polyimides can be seen in university research (Non-Patent Literature 2), practical developments are rarely seen.

[0004] Furthermore, studies have been conducted to obtain cured products with higher thermal conductivity than those using bisphenol-type epoxy compounds with a bent structure by curing liquid crystalline epoxy compounds. While there are examples of using diamines with a linear structure by linking two aniline molecules with ethylene, or diamines with amino acids at both ends of an alkyl ether chain, there are no studies on achieving high thermal conductivity using diamines with a liquid crystalline structure that utilize a mesogenic skeleton containing cyclohexylene (Patent Documents 4 and 5). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-222644 [Patent Document 2] Japanese Patent Application Publication No. 11-217437 [Patent Document 3] Japanese Patent Publication No. 2007-099843 [Patent Document 4] Japanese Patent Publication No. 2006-265527 [Patent Document 5] International Publication No. 2015 / 170744 [Non-patent literature]

[0006] [Non-Patent Document 1] RF World No. 40, pp. 97-111 (2017) [Non-Patent Document 2] Polymer Papers, vol.61, No.1, pp39-48(2004) [Overview of the project] [Problems that the invention aims to solve]

[0007] As described above, the objective is to realize a diamine for forming polyimide films, a low dielectric constant resin forming composition containing the diamine, a polyamic acid using the diamine, and a polyimide film, which can be suitably used in next-generation communication equipment and radar, which are increasingly using high frequencies. [Means for solving the problem]

[0008] The inventors of the present invention have discovered that by polymerizing a diamine having few conjugated or polar groups and polymerizable groups with high linearity and symmetry of the molecule with a tetracarboxylic anhydride, and imidizing it by heating after film formation, it is possible to realize a diamine composition that can be molded using conventional polyimide film and flexible printed circuit board manufacturing processes and exhibits lower dielectric properties than conventional polyimide films, and that when used as a curing agent such as an epoxy compound, it is possible to realize a low dielectric constant resin with high thermal conductivity, thus completing the present invention. Molecules with high linearity often exhibit liquid crystal properties. By aligning the liquid crystal portions through stretching treatments during film formation, it is possible to reduce the dielectric loss tangent caused by molecular motion, and further improve heat resistance and thermal conductivity.

[0009] [1] A first aspect of the present invention is: This composition contains a compound represented by formula (1) having amino acids at both ends, and the relative permittivity of the cured product at 10 GHz is less than 3.0, and is a composition for forming a low dielectric constant resin. TIFF0007845001000001.tif16142 In formula (1), A 1, A 2 , and A 3 are each independently 1,4 - cyclohexylene, 1,4 - cyclohexenylene, 1,4 - phenylene, bicyclo[2.2.2]oct - 1,4 - diyl, bicyclo[3.1.0]hex - 3,6 - diyl, or fluorene - 2,7 - diyl, and in these rings, at least one - CH2 - may be replaced by - O -, at least one - CH= may be replaced by - N=, at least one hydrogen is halogen, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen may be replaced by halogen, and in this alkyl, at least one - CH2 - may be replaced by - O -, - CO -, - COO -, - OCO -, or - C=C -; A 1 and A 2 at least one of which is 1,4 - cyclohexylene; Z 1 , Z 2 , Z 3 , and Z 4 are each independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, 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 halogen; m1 is 0, 1, or 2; In the formula, when there are a plurality of Z 3 or A 3 they may be the same or different.

[0010] [2] The second aspect of the present invention is a composition for forming a low - dielectric - constant resin according to [1], containing a compound represented by any one of formulas (1 - 1) to (1 - 3). TIFF0007845001000002.tif41126 In formulas (1 - 1) to (1 - 3), A 1 , A 2 , and A3 These are independently 1,4-cyclohexylene, 1,4-phenylene (where at least one hydrogen may be replaced by a halogen or an alkyl group 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 alkyl group having 1 to 10 carbon atoms). A 1 and A 2 At least one of them is 1,4-cyclohexylene; 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.

[0011] [3] A third aspect of the present invention is: The composition for forming a low dielectric constant resin, as described in [1], contains a compound represented by formula (1-1-1) or (1-1-2). TIFF0007845001000003.tif36102 In equations (1-1-1) and (1-1-2), Z 1 , Z 2 and Z 4 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) aO-, -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 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.

[0012] [4] A fourth aspect of the present invention is: The composition for forming a low dielectric constant resin described in [1] contains a compound represented by any of the formulas (1-2-1) to (1-2-5). TIFF0007845001000004.tif98125 In formulas (1-2-1) to (1-2-5), 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-, -CH2CH2-COO-, -OCO-CH2CH2-, -SO2-, -CH=CH-, -OCF2-, or -CF2O-, where a is an integer from 1 to 20; 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.

[0013] [5] A fifth aspect of the present invention is: The composition for forming a low dielectric constant resin described in [1] contains a compound represented by any of the formulas (1-3-1) to (1-3-8). TIFF0007845001000005.tif107154 TIFF0007845001000006.tif56140 In formulas (1-3-1) to (1-3-8), 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; The case includes n being 2 or greater, and if there are multiple X values ​​in the expression, two of them may be the same or different.

[0014] [6] A sixth aspect of the present invention is: A compound represented by any of the formulas (1-1-1a), (1-1-2a), (1-2-4a), (1-2-5a), (1-3-3a), (1-3-4a), and (1-3-6a) to (1-3-8a), wherein the relative permittivity at 10 GHz of a cured product obtained by curing a composition containing the compound is lower than 3.0. TIFF0007845001000007.tif67150 TIFF0007845001000008.tif88161 In equations (1-1-1a), (1-1-2a), (1-2-4a), (1-2-5a), (1-3-3a), (1-3-4a), and (1-3-6a)~(1-3-8a), Z 2and Z 3 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-, or -CH=CH-, where a is an integer from 1 to 20; m is an integer between 0 and 20; M is either 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, Z 3 If there are multiple instances of , m, or M, two of them may be the same or different.

[0015] [7] The seventh aspect of the present invention is This is a polyamic acid synthesized from a composition for forming a low dielectric constant resin described in any one of items [1] to [5].

[0016] [8] The eighth aspect of the present invention relates to: [7] This is a low dielectric constant polyimide resin obtained by molding and then imidizing the polyamic acid described in [7].

[0017] [9] The ninth aspect of the present invention relates to This is a low dielectric constant resin obtained by curing a composition for forming a low dielectric constant resin described in any one of items [1] to [5].

[0018]

[10] A tenth aspect of the present invention is: A composition for forming a low dielectric constant resin according to any one of [1] to [5], containing an inorganic filler.

[0019]

[11] An eleventh aspect of the present invention is: The composition for forming a low dielectric constant resin described in

[10] is such that the thermal conductivity of the cured product is 0.5 W / m·K or higher.

[0020]

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

[10] or

[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, silica, titanium oxide, tin oxide, holmium oxide, calcium oxide, magnesium hydroxide, aluminum hydroxide, cordierite, and mullite.

[0021]

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

[10] or

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

[0022]

[14] A fourteenth aspect of the present invention is This low dielectric constant resin insulating film is a polymer molded article obtained by imidizing or curing a composition for forming a low dielectric constant resin described in any one of items [1] to [5] and

[10] to

[13] with heat.

[0023]

[15] A fifteenth 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 thermally imidizing or curing a composition for forming a low dielectric constant resin described in any one of items [1] to [5] and

[10] to

[13] .

[0024]

[16] A sixteenth aspect of the present invention is: This low dielectric constant resin part is a polymer molded article obtained by imidizing a composition for forming a low dielectric constant resin described in any one of items [1] to [5] and

[10] to

[13] with heat.

[0025]

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

[14] to

[16] . [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. [Brief explanation of the drawing]

[0027] [Figure 1] This graph shows the light transmittance of Example 2 and Comparative Example 2. [Best Mode for Carrying Out the Invention]

[0028] 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.

[0029] 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.

[0030] "Compound (1)" means the 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)," "Compound (1-1)," "Compound (1-2)," "Compound (1-3)," etc. are collectively referred to as "Compound (1)." "Composition (1)" means a 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 any two A 3 They may be the same or different. Multiple compounds (1) are A 3 When any two A 3 They may be the same or different. This rule applies to Z 3 This also applies to other symbols such as X, and to the base symbol, etc.

[0031] [Liquid crystal compound] The compound (1) used in the present invention is preferably a liquid crystalline compound having a rod-shaped mesogenic skeleton and polymerizable groups, and exhibiting liquid crystalline properties. Liquid crystalline compounds have high polymerization reactivity, a wide liquid crystalline phase temperature range, and good miscibility. Furthermore, compound (1) readily becomes homogeneous when mixed with other liquid crystalline compounds or polymerizable compounds.

[0032] Ring structure A of compound (1) 1 , A 2 , or A 3 , and the bonding 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.

[0033] <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, 2,6-difluoro-1,4-phenylene, and 2-methyl-1,4-phenylene. A particularly preferred example is 1,4-cyclohexylene.

[0034] 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.

[0035] 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 which may replace at least one hydrogen atom on the 1,4-phenylene ring 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, molecular motion is suppressed, resulting in lower dielectric loss.

[0036] When at least one ring is 1,4-cyclohexylene, the transparency point is high, the relative permittivity is low, the dielectric loss is low, and the viscosity is low. When two or more rings are 1,4-cyclohexylene, the transparency point is high, the melting point is low, the relative permittivity is very low, the dielectric loss is very 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.

[0037] <Binding group Z :Z 1 , Z 2 , Z 3 and 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) aO-, -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. More preferred examples are a single bond, -(CH2) a -, -(CH2) a O-, -O(CH2) a -, or -O(CH2) a O-. Particularly preferred examples are -(CH2) a -, -(CH2) a O-, -O(CH2) a -, or -O(CH2) a O-, where a is an integer from 1 to 20.

[0038] When the linking group Z is a single bond, -(CH2) a -, -(CH2) a O-, -O(CH2) a -, -O(CH2) a O-, -CF2O-, or -OCF2-, the viscosity becomes low. Also, when the linking group Z is -(CH2) a [[ID=3L]]-, -(CH2) a O-, -O(CH2) a -, or -O(CH2) a O- and a is about 2 to 12, the melting point decreases, the solubility in organic solvents is high, the molecular length becomes long, so the temperature range of the liquid crystal phase becomes wide, and the dielectric loss tangent is small.

[0039] When the compound (1) has two rings, the viscosity is low, and when it has three or more rings, the clearing point is high. In this specification, basically, a six-membered ring and a condensed ring containing a six-membered ring are regarded as a ring. For example, a three-membered ring, a four-membered ring, or a five-membered ring alone is not regarded as a ring. Also, a condensed ring such as a naphthalene ring, a decahydronaphthalene ring, and a fluorene ring is regarded as one ring.

[0040] As described above, by appropriately selecting the type of ring structure A, the type of bonding group Z, the number of rings, etc., a compound having the desired physical properties can be obtained. Examples of preferred compounds (1) include those of formulas (1-1-1) to (1-1-2), (1-2-1) to (1-2-5), and (1-3-1) to (1-3-8). TIFF0007845001000009.tif37105 TIFF0007845001000010.tif103132 TIFF0007845001000011.tif103149 TIFF0007845001000012.tif59151

[0041] In equations (1-1-1)~(1-1-2), (1-2-1)~(1-2-5), and (1-3-1)~(1-3-8), 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.

[0042] A more preferred example of compound (1) is shown below. TIFF0007845001000013.tif74165 TIFF0007845001000014.tif91167 In equations (1-1-1a)~(1-1-2a), (1-2-4a)~(1-2-5a), (1-3-3a), (1-3-4a), and (1-3-6a)~(1-3-8a), Z 2 and Z 3 These are independent, single bonds, -(CH2) a -, -O(CH2) a -,-(CH2) a O-, -O(CH2) a O-, or -CH=CH-, 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, Z 3 If there are multiple instances of , m, or M, they may be the same or different.

[0043] [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 Series (Maruzen).

[0044] 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).

[0045] (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 2 Compound (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.

[0046] TIFF0007845001000015.tif52137

[0047] (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.

[0048] TIFF0007845001000016.tif33122

[0049] (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.

[0050] TIFF0007845001000017.tif25130

[0051] (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.

[0052] TIFF0007845001000018.tif35122

[0053] (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.

[0054] TIFF0007845001000019.tif34151

[0055] (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.

[0056] TIFF0007845001000020.tif55147

[0057] (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.

[0058] TIFF0007845001000021.tif34151

[0059] (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.

[0060] TIFF0007845001000022.tif37146

[0061] (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 2 Compound (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].

[0062] TIFF0007845001000023.tif55119

[0063] [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.

[0064] <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.

[0065] 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.

[0066] Preferred styrene derivatives include, for example, styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, and α-methylstyrene.

[0067] 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.

[0068] 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.

[0069] Preferred fumaric acid derivatives include, for example, dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclopentyl fumarate, and dicyclohexyl fumarate.

[0070] 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.

[0071] <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 having groups that can polymerize with the amino group at the terminal end of compound 1, such as epoxy groups and oxetane groups, at one or both ends as polymerizable groups are preferred as the polymerizable liquid crystal compounds. Furthermore, even polymerizable liquid crystal compositions that do not polymerize with aminos, such as acrylic, oxetane, maleimide, and vinyl, may be compounds that can be compounded with the polymerizable liquid crystal compound represented by compound (1) by forming semi-IPN structures or polymer alloy structures with other compounds.

[0072] <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.

[0073] <Tetracarboxylic acid dianhydride> By using compound (1) as a raw material to synthesize polyimide resin and polyamic acid, which is a precursor of polyimide resin, it is possible to achieve a lower dielectric constant due to a reduction in electron conjugation and higher heat resistance, such as a lower glass transition temperature, due to the linearity of molecules derived from the liquid crystal structure. To synthesize polyamic acid, a precursor to polyimide resin, using compound (1), compound (1) and the same molar amount of tetracarboxylic dianhydride should be dissolved in a solvent and polymerized. If the tetracarboxylic acid side contains undehydrated components, the reactivity will be low and polymerization will often not occur. In such cases, using more tetracarboxylic acid will allow for the acquisition of a higher molecular weight polyamic acid. If the molecular weight becomes too high, the required molecular weight can be obtained by adding dicarboxylic dianhydride as a reaction stopper or by partially hydrolyzing the polymerized polyamic acid. After drying, the obtained polyamic acid is heated above the imidization temperature to obtain polyimide.

[0074] <Tetracarboxylic acid dianhydride> The tetracarboxylic dianhydride is not particularly limited, and known ones can be used. For example, aromatic tetracarboxylic dianhydrides of the following chemical formulas (H-1 to H-24) and (F-1 to F-51) can be used. Using aliphatic tetracarboxylic dianhydrides or bulky tetracarboxylic dianhydrides makes it easier to obtain the desired low dielectric constant polyimide, but it tends to become physically brittle. Therefore, it is possible to adjust the physical properties by using one or more types of aromatic tetracarboxylic dianhydrides simultaneously to match the desired properties. When thermal conductivity is important, structures with a skeleton that has as much linearity as possible, such as (H-1), (H-12), (H-15) to (H-18) or (F-1), (F-15) to (F-17), (F-29), (F-31), and (F-50), are preferred.

[0075] <Aromatic tetracarboxylic dianhydride> TIFF0007845001000024.tif246149

[0076] TIFF0007845001000025.tif194146 TIFF0007845001000026.tif4135

[0077] <Aliphatic tetracarboxylic dianhydride> TIFF0007845001000027.tif233154

[0078] TIFF0007845001000028.tif244143

[0079] TIFF0007845001000029.tif249116

[0080] <Epoxy compounds> When compound (1) is used as a curing agent for epoxy compounds (oxiranes or oxetanes), compared to using ordinary diamine compounds with aromatic rings, there is less electron conjugation and the linearity of the molecular chain is higher due to the liquid crystal structure, resulting in a cured product with a low dielectric constant and high heat resistance such as a high Tg. The epoxy compound is not particularly limited, and known compounds can be used.

[0081] Oxiranes include diglycidyl ethers of bisphenols such as biphenol, bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetrachlorobisphenol A, and tetrabromobisphenol A; polyglycidyl ethers of novolac resins such as phenol novolac, cresol novolac, brominated phenol novolac, and orthocresol novolac; ethylene glycol, polyethylene glycol, polypropylene glycol, butanediol, 1,6-hexanediol, and neopentylglycerol. Diglycidyl ethers of alkylene glycols such as chol, trimethylolpropane, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A, sorbitol polyglycidyl ether, tris(2,3-epoxypropyl) isocyanurate, triglycidyl tris(2-hydroxyethyl) isocyanurate, glycidyl esters such as glycidyl esters of hexahydrophthalic acid and diglycidyl esters of dimer acid, and 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (trade name of Daicel Corporation). Celoxide 2021P), 3,4-Epoxycyclohexylethyl-3',4'-Epoxycyclohexanecarboxylate, 3,4-Epoxy-6-methylcyclohexyl-3',4'-Epoxy-6'-methylcyclohexanecarboxylate, Vinylcyclohexene dioxide, 3,4-Epoxy-4-methylcyclohexyl-2-propylene oxide, 2-(3,4-Epoxycyclohexyl-5,5-Spiro-3,4-Epoxy)cyclohexane-m- Dioxane, bis(3,4-epoxycyclohexyl) adipate, bis(3,4-epoxycyclohexylmethyl) adipate, lactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, bis(3,4-epoxycyclohexyl) ether, bis(3,Examples include alicyclic epoxy compounds such as 4-epoxycyclohexylmethyl) ether, tetra(3,4-epoxycyclohexylmethyl)butanetetracarboxylate, bis(3,4-epoxycyclohexylmethyl)-4,5-epoxytetrahydrophthalate, 1,2:8,9-diepoxylimonene, and bis(3,4-epoxycyclohexyl)diethylsiloxane. These epoxy compounds may be used individually or in combination.

[0082] Examples of oxetanes include 3-ethyl-3-hydroxymethyl oxetane (product name OXT-101 from Toagosei Co., Ltd.), 3-ethyl-3-(phenoxymethyl)oxetane (product name OXT-211 from Toagosei Co., Ltd.), 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (product name OXT-212 from Toagosei Co., Ltd.), 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (product name OXT-121 from Toagosei Co., Ltd.), and bis(3-ethyl-3-oxetanylmethyl) ether (product name from Toagosei Co., Ltd.) Examples include OXT-221), aliphatic carboxylic acid oxetane compounds (e.g., adipate bisoxetane), aromatic carboxylic acid oxetane compounds (e.g., terephthalate bisoxetane), alicyclic carboxylic acid oxetane compounds (e.g., cyclohexanedicarboxylic acid bisoxetane), and aromatic isocyanate oxetane compounds (e.g., MDI bisoxetane). These oxetanes may be used individually or in combination. Furthermore, by using them in combination with epoxy compounds, precise structural control becomes possible by taking advantage of their differences in reactivity.

[0083] To further improve thermal conductivity, it is preferable to use epoxy compounds (oxirane or oxetane) that also have a liquid crystal structure as their framework. Preferred epoxy compounds with a liquid crystal framework are those described in, for example, Japanese Patent Publication No. 5084148 and Japanese Patent Publication No. 6653793. By using epoxy compounds with a liquid crystal framework, the linearity of the polymer after polymerization is increased, and the thermal conductivity in the orientation direction is greatly improved. Even without orientation treatment, large crystalline domains are formed, and the thermal conductivity of these crystalline domains increases, thereby increasing the overall thermal conductivity of the cured product.

[0084] Preferred epoxy or urethane compounds with a liquid crystal framework are shown by formulas (Ep-1) to (Ep-64). TIFF0007845001000030.tif248123

[0085] TIFF0007845001000031.tif220136

[0086] TIFF0007845001000032.tif174137

[0087] TIFF0007845001000033.tif231148

[0088] TIFF0007845001000034.tif179148

[0089] TIFF0007845001000035.tif173161

[0090] TIFF0007845001000036.tif216166

[0091] TIFF0007845001000037.tif199160

[0092] In chemical formulas (Ep-1) to (Ep-65), Z 1These are single bonds, -(CH2)2-, -(CF2)2-, -(CH2)4-, -CH2O-, -OCH2-, -(CH2)3O-, -O(CH2)3-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CH=CHCOO-, -OCOCH=CH-, -(CH2)2COO-, -OCO(CH2)2-, -C≡C-, -C≡C-COO-, -OCO-C≡C-, -C≡C-CH=CH-, -CH=CH-C≡C-, -CH=N-, -N=CH-, -N=N-, -OCF2-, or -CF2O-. Note that there are multiple Z 1 They may be the same or different.

[0093] Z 2 These are -(CH2)2-, -(CF2)2-, -(CH2)4-, -CH2O-, -OCH2-, -(CH2)3O-, -O(CH2)3-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CH=CHCOO-, -OCOCH=CH-, -(CH2)2COO-, -OCO(CH2)2-, -C≡C-, -C≡C-COO-, -OCO-C≡C-, -C≡C-CH=CH-, -CH=CH-C≡C-, -CH=N-, -N=CH-, -N=N-, -OCF2-, or -CF2O-.

[0094] Z 3 These are single bonds or alkylenes with 1 to 20 carbon atoms. In the alkylene, at least one -CH2- may be replaced with -O-, -S-, -CO-, -COO-, or -OCO-, at least one -CH2CH2- may be replaced with -CH=CH-, -CF=CF-, -CH=N-, -N=CH-, -N=N-, -N(O)=N-, or -C≡C-, and at least one hydrogen may be replaced with a halogen.

[0095] Y 1 and Y 2 This represents a single bond or an alkylene having 1 to 20 carbon atoms, preferably an alkylene having 1 to 10 carbon atoms, in which any -CH2- may be replaced with -O-, -S-, -CO-, -COO-, -OCO- or -CH=CH-. Particularly preferred Y1 or Y 2 This refers to alkylenes in which one or both of the -CH2- groups at one or both ends of an alkylene with 1 to 10 carbon atoms are replaced with -O- groups. m is an integer between 1 and 6, preferably between 2 and 6, and more preferably between 2 and 4.

[0096] X is a substituent of 1,4-phenylene or fluorene-2,7-diyl, in which at least one hydrogen may be replaced by a halogen, alkyl, or alkyl fluoride.

[0097] PG is a polymerizable group represented by formula (2-1) or (2-2). TIFF0007845001000038.tif3899 In formulas (2-1) to (2-2), R b is hydrogen, halogen, -CF3, or an alkyl group having 1 to 5 carbon atoms, and q is 0 or 1.

[0098] <Hardening agent> When compound (1) is used as a curing agent for epoxy compounds, curing agents of other structures may be included as additional components. Examples of preferred curing agents are shown below.

[0099] Additional amine-based curing agents include 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 Examples include 2-diaminocyclohexane, 3,9-dipropanamine-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine, and N-aminoethylpiperazine. Compound (1) acts as an aliphatic diamine curing agent, resulting in a low dielectric constant, but the cured product tends to be hard and brittle. When combined with an aromatic diamine, a cured product with both low dielectric constant and flexibility can be obtained.

[0100] <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.

[0101] The filler can take the shape of a spherical, amorphous, fibrous, rod-shaped, cylindrical, or plate-shaped material. When the cured product is film-like or sheet-like, a spherical, fibrous, or woven fiber cross-like shape is preferred. When the cured product is a three-dimensional component, a spherical or amorphous shape is preferred. 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-like crystalline boron nitride is used, or the liquid crystal compound is easily oriented perpendicularly to the plate-like structure, or easily oriented along the plate-like structure. Whether it is oriented perpendicularly 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 can reduce the thermal expansion coefficient of the molded body.

[0102] 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 kneading and dispersion become impossible, so selection is preferable depending on the application. When dispersion is required, 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.

[0103] 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.

[0104] <Solvent> Composition (1) may contain a solvent. Polymerization of the composition for forming a low dielectric constant resin containing compound (1) may be carried out in a solvent or without a solvent. A composition containing compound (S01) containing a solvent may be coated onto a substrate, for example by a spin coating method, and then the solvent may be removed before imidization or thermal polymerization.

[0105] 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.

[0106] <Other additives> Since the composition for forming a low dielectric constant resin containing compound (1) has high polymerizability, a stabilizer may be added to facilitate handling. Any known stabilizer can be used without limitation. 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.

[0107] [Low dielectric constant resin] Another embodiment of the present invention, the low dielectric constant resin, is a cured product of the above-described low dielectric constant resin forming composition and can be used in sheet-like, film-like, plate-like, fibrous, and three-dimensional shaped parts (insulating parts of connectors), as well as being 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 has excellent thermal conductivity, heat resistance, rigidity, elasticity, moldability, chemical resistance, and dimensional stability.

[0108] 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.

[0109] 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 align the molecules.

[0110] 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.

[0111] 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 curing agents with a bent structure, such as 4,4'-diaminodiphenylmethane. 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 an appropriately crystalline polymerizable composition.

[0112] The low dielectric constant molded article of the present invention consists of a composition for forming a low dielectric constant resin containing compound (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 applied to 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 applying composition (1) containing a solvent to an oriented 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.

[0113] The following describes in detail a method for producing a film as a low dielectric constant molded article using a composition for forming a low dielectric constant resin that contains a solvent compound (1). First, the 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, curtain coating, flow coating, print coating, microgravure coating, gravure coating, wire bar coating, dip coating, spray coating, and meniscus coating.

[0114] 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.

[0115] Furthermore, when using a composition for forming a low dielectric constant resin containing compound (1) as a low dielectric constant insulating coating, it is also preferable to perform orientation treatment on the substrate surface before coating. Orientation treatment methods include, for example, simply forming an orientation film on the substrate; rubbing the substrate with a rayon cloth after forming an orientation film; directly rubbing the substrate with a rayon cloth; oblique deposition of silicon dioxide; and rubbing-free orientation using a stretched film, photo-alignment film, or ion beam. In some cases, a desired orientation can be achieved without treating the substrate surface. For example, while surface treatment such as rubbing is often omitted when forming homeotropic orientation, rubbing may be performed to achieve higher orientation.

[0116] 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 achieved.

[0117] 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.

[0118] 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).

[0119] Examples of the above-mentioned substrates include plastic film substrates and glass-reinforced resin 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 their partially saponified products, 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.

[0120] 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.

[0121] <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.

[0122] 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.

[0123] For the coating method, a wet coating method is preferable to ensure uniform coating of the composition. Among wet coating methods, the spin coating method is preferred for small-scale production as it is simple and allows for homogeneous film formation. When productivity is a priority, gravure coating, die coating, bar coating, reverse coating, roll coating, slit coating, dipping, spray coating, kiss coating, reverse kiss coating, air knife coating, curtain coating, inkjet, flexographic printing, screen printing, and rod coating methods are preferred. The wet coating method can be appropriately selected from these methods depending on the required film thickness, viscosity, curing conditions, etc.

[0124] When manufacturing sheets, a casting method is used in which the composition is coated onto a release-treated substrate using the method described above and then peeled off. When manufacturing structures, a mold can be used, and resin molding methods such as press molding, injection molding, and various 3D printer molding methods (extrusion deposition modeling) can be employed. After molding, it is possible to remove the mold and perform final curing, or to perform final curing while still in the mold.

[0125] [Examples] The present invention will be further described in detail by examples (including examples of the preparation of compounds, compositions, polymers, resins, etc.). The present invention is not limited by these examples.

[0126] [Synthesis Example of Compound (1)] Compound (1) was synthesized according to the procedures shown in 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 device characteristics of Compound (1), the composition, the polymer, the resin, etc. were measured by the following methods.

[0127] [NMR Analysis] For the measurement, JNM-ECZR manufactured by JEOL Ltd. was used. 1 For 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 integration times. 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 integration times. 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.

[0128] [Gas Chromatography Analysis] For the measurement, a GC-2014 type 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 and 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.

[0129] [HPLC Analysis] For the measurements, 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 YMC Corporation. The eluent was a mixture of acetonitrile and water as appropriate. As detectors, UV detectors, RI detectors, CORONA detectors, etc. were used as appropriate. When using a UV detector, the detection wavelength was set to 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 μL of this solution was introduced into the sample chamber. A Shimadzu C-R7Aplus was used as the recorder.

[0130] <UV-visible spectroscopy> A PharmaSpec UV-1700 manufactured by Shimadzu Corporation 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.

[0131] <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.

[0132] (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."

[0133] 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.

[0134] [Synthesis Example 1] Compound (S01: Compound (1-1-2a), Z 2 Synthesis of compounds where is a single bond, M is oxygen, and m=3. TIFF0007845001000039.tif2490 TIFF0007845001000040.tif55164 4,4'-Bicyclohexyldiol (S01-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.

[0135] (1st stage) Under a nitrogen atmosphere, 15.0 g, 75.8 mmol of 4,4'-dicyclohexanediol (S01-a), 40 wt% potassium hydroxide (3.00 g / 53.6 mmol), and 10 mL of water were dissolved in 100 mL of dichloromethane. Acrylonitrile (20.1 g, 378.9 mmol) was added dropwise at room temperature, and the mixture was heated and stirred at 40°C for 3 days. 100 mL of dichloromethane was added to the reaction mixture, and the mixture was filtered. After washing three times with water, 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 the product was concentrated under reduced pressure at 40°C to obtain compound (S01-b) (20.8 g, 68.4 mmol).

[0136] (Second stage) Under a nitrogen atmosphere, a solution of aluminum chloride (7.60 g, 57.1 mmol) in tetrahydrofuran (THF) (100 mL) was cooled to below 5°C, and lithium aluminum hydride (4.50 g, 118.4 mmol) was slowly added in small amounts while stirring for 30 minutes. The reaction mixture was cooled to below 10°C, and the compound (S01-b) obtained in the previous step (15.0 g, 49.3 mmol) was added in a THF (50 mL) solution. The mixture was added dropwise and stirred for 1 day. After that, the reaction mixture was cooled to below 10°C, ethyl acetate (100 mL) was added dropwise, followed by (2N) sodium hydroxide solution (62.5 mL), and stirred for 30 minutes. Ethyl acetate (100 mL) was added to the reaction mixture and filtered. The resulting filtrate was washed three times with pure water, and the organic layer was concentrated under reduced pressure at 40°C. The resulting residue was isolated by silica gel column chromatography (solvent: chloroform / methanol / aqueous ammonia = 1 / 1 / 0.1 (volume ratio)), and the product was concentrated under reduced pressure at 40°C to obtain compound (S01) (12.8 g, 68.4 mmol). Also, compounds 1 The H-NMR signals were as follows: δ(ppm;MeOD):3.59-3.57(t,4H), 3.20-3.18(tt,2H), 3.02-2.99(t,4H), 2 .06-2.04(m,4H), 1.88-1.84(m,4H), 1.78-1.76(m,4H), 1.18-1.00(m,10H)

[0137] [Synthesis of polyamic acid solution] When polyimide is synthesized using the polymerizable compound (S01) of the present invention, it is thought that the electron conjugation decreases due to the alicyclic compound, which can lower the dielectric constant and reduce the dielectric loss tangent. 0.313 g of polymerizable compound (S01), 0.175 g of cyclobutanetetracarboxylic dianhydride (CBDA) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and 0.039 g of pyromellitic acid dianhydride (PMDA) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. were measured out into a 20 ml screw-cap bottle in a molar ratio of 5:4:1. 2.11 g of N-methyl-2-pyrrolidinone (NMP) manufactured by Kanto Chemical Co., Ltd. was added, and the mixture was stirred with a magnetic stirrer for 15 hours to allow polymerization. To ensure no unreacted material remained, the mixture was stirred for an additional hour in a 50°C water bath to obtain polyamic acid solution 1.

[0138] [Material property evaluation] [Example 1] <Preparation of samples for relative permittivity measurement> The synthesized polyamic acid solution 1 was applied to a 5cm x 10cm area of ​​a 75μm thick Kapton film of A5 size so that the thickness after drying would be 40μm. After drying on a hot plate at 80°C for 30 minutes, the film was placed in a hot air circulating oven at 200°C and heated for 1 hour to obtain a polyimide thin film 1. Using a Pinnacle® mold capable of cutting the cured polyimide thin film, along with the Kapton substrate, into 3.0 mm x 100 mm strips, strip-shaped samples were cut out.

[0139] <Methods for evaluating relative permittivity and thermal conductivity> Strips punched out with a die were connected to a vector network analyzer (MS46522B-043, Anritsu Corporation) and a cavity resonator (10 GHz: TM mode) manufactured by AET Corporation to measure the resonant frequency shift and attenuation. The relative permittivity and dielectric loss tangent (tanδ) were calculated using software from the same company. To minimize the influence of moisture content in the strips when comparing data, the strips were formed the day before measurement, and the evaluation of the relative permittivity began after the samples were left to stand for more than 60 minutes in a laboratory at a temperature of 20°C and humidity of 48%. Since the measured values ​​were taken with the polyimide substrate included, the thickness and dielectric properties of the polyimide substrate and the thickness of the sample portion alone were measured with a micrometer, and the relative permittivity and tanδ of the sample portion alone were calculated using a spreadsheet worksheet from AET Corporation.

[0140] [Comparative Example 1] Polyamic acid solution 2 was prepared by replacing the polymerizable compound (S01) with 1,4-diaminodiphenylmethane (DDM) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and samples were prepared in the same manner as in Example 1. The dielectric constant and thermal conductivity were measured, and the results are presented as Example 2. The composition ratio of the synthesized polyamic acid solutions is shown in Table 1, and the dielectric properties of the samples obtained by forming films and imidizing them are shown in Table 2.

[0141] Molar ratio of synthesized polyamic acid TIFF0007845001000041.tif21140

[0142] Acid dielectric properties TIFF0007845001000042.tif15102

[0143] Optical properties [Example 2] By using the polymerizable compound (S01) of the present invention and reducing electron conjugation, it may be possible to produce transparent polyimides. To measure the visible light transmittance, polyamic acid solution 1 was applied to an alkali-free glass substrate, but it cracked and peeled off from the glass. Therefore, polyamic acid solution 3 was synthesized by adding DDM to the diamine of the present invention. Using this polyamic acid solution 3, a layer was coated onto an alkali-free glass substrate to a thickness of approximately 40 μm and fired under the same conditions as in Example 1. The light transmittance in the range of 350 nm to 900 nm was measured using a Shimadzu UV2456 ultraviolet-visible spectrophotometer. The results are shown in Figure 1. Furthermore, using the same solution as in Example 1, the substrate was changed from glass to Kapton film, and the dielectric properties were measured in the same manner as in Example 1. As a result, the relative permittivity was 2.31 and tanδ was 0.015, indicating that transparency could be achieved while maintaining a small dielectric loss tangent.

[0144] Molar ratio of synthesized polyamic acid TIFF0007845001000043.tif15139

[0145] [Comparative Example 2] The light transmittance was measured using polyamic acid solution 2 in the same manner as in Example 2. The results are shown in Figure 1.

[0146] Comparing Example 1 with Comparative Example 1, it can be seen that when a polyimide film is fabricated using the polymerizable compound (S01) of the present invention, a lower dielectric constant and lower dielectric loss tangent are possible compared to when using the widely used DDM. Furthermore, by comparing Example 2 with Comparative Example 2, it can be seen that when a polyimide film is fabricated using the polymerizable compound (S01) of the present invention, absorption in the short-wavelength region is significantly suppressed compared to when using DDM, the characteristic yellowish-brown color of polyimide is almost eliminated, and a transparent polyimide thin film can be fabricated.

[0147] By using the polymerizable compound (S01) of the present invention in a composite material of epoxy resin and a high thermal conductivity filler, the linearity of the molecular structure of the resin component is increased, and as a result, phonon conduction, which transfers heat within the polymer, becomes more linear, which is expected to increase the thermal conductivity of the cured product.

[0148] [Example 3] 0.21 g of polymerizable compound (S01), 0.25 g of liquid crystalline bifunctional epoxy compound (S02: synthesized by the method described in Japanese Patent Publication No. 6653793), and 0.46 g of boron nitride (PTX-25, manufactured by Momentive Performance Materials LLC) were measured into an agate mortar and mixed. A 0.2 mm thick PTFE sheet with a 25 mm diameter through-hole was placed on top of another 0.2 mm thick PTFE sheet. After the 25 mm layer had hardened, a slightly larger amount of the mixed powder than needed to fill the 25 mm hole was added, and another 0.2 mm thick PTFE sheet was placed on top to create a simple resin mold. This sandwich-type mold was sandwiched between two A4-sized 3 mm thick aluminum plates and cured at 180°C for 1 hour under a pressure of 10 MPa using a manual heating press. After 1 hour of curing, the heater was turned off, and the mold was held in the press until the temperature reached 80°C. After confirming that the temperature had dropped below 80°C, the PTFE mold containing the hardened sample was removed from the press machine, and the disc-shaped sample was carefully removed, taking care not to break it. TIFF0007845001000044.tif35139

[0149] [Thermal conductivity measurement] The obtained disc-shaped sample was placed in the in-plane sample holder of a NanoFlash LFA447 thermal diffusivity measuring instrument manufactured by Netch Japan Co., Ltd., and blackened with a commercially available graphite spray to determine the thermal diffusivity in the planar direction. After the measurement, a 10 mm x 10 mm sample was cut from the disc-shaped sample, blackened, and the thermal diffusivity in the thickness direction was determined using a standard sample holder. Furthermore, the specific heat was determined using DSC and the density was determined using the Archimedes method with a precision balance using the remaining portion, and the thermal conductivity was determined by multiplying these values.

[0150] [Comparative Example 3] Samples were prepared in the same manner as in Example 3, except that the curing agent was changed from a polymerizable compound (S01) to DDM, and the thermal conductivity was determined. Table 4 summarizes the thermal conductivity of Example 3 and Comparative Example 3.

[0151] TIFF0007845001000045.tif21148

[0152] Comparing Example 3 with Comparative Example 3, it can be seen that when a liquid crystalline compound is selected as the epoxy compound, the thermal conductivity can be improved in both the planar and thickness directions by using a polymerizable compound (S01).

[0153] [Example 4] A polymerizable compound (S01) was used as the curing agent, and a commercially available biphenyl-type epoxy compound (YX4000H, manufactured by Mitsubishi Chemical Corporation) was used as the epoxy compound. Disc-shaped samples were prepared, and their thermal conductivity was measured.

[0154] [Comparative Example 4] DDM was used as the curing agent, and a commercially available biphenyl-type epoxy compound (manufactured by Mitsubishi Chemical Corporation: YX4000H) was used as the epoxy compound. Disc-shaped samples were prepared, and their thermal conductivity was measured. Table 5 summarizes Example 4 and Comparative Example 4.

[0155] TIFF0007845001000046.tif15110

[0156] Comparing Example 4 with Comparative Example 4, it can be seen that when a non-liquid crystallinity compound is used as the epoxy compound, the thermal conductivity can be improved in both the planar and thickness directions by using a polymerizable compound (S01) as the curing agent. Furthermore, comparing Example 3 and Example 4, it can be seen that the polymerizable compound (S01) of the present invention, when combined with a compound that also has liquid crystalline properties on the epoxy side, yields a thermosetting composite material with extremely high thermal conductivity. Thus, it can be seen that the polymerizable compound (S01) of the present invention is useful for forming polyimide resins with low dielectric constant, low dielectric loss tangent, and high transparency, as well as epoxy resin composite materials with high thermal conductivity.

Claims

1. A compound represented by formula (1-1-2a). (1-1-2a), Z ２ It is a single bond; m is an integer between 0 and 20; M is oxygen; If there are multiple instances of m or M in an expression, any two of them may be the same or different.

2. A composition for forming a low dielectric constant resin, comprising the compound described in claim 1.

3. A polyamic acid synthesized from the composition for forming a low dielectric constant resin described in claim 2.

4. A low dielectric constant polyimide resin obtained by molding and then imidizing the polyamic acid described in claim 3.

5. A low dielectric constant resin obtained by curing the composition for forming a low dielectric constant resin according to claim 2.

6. A composition for forming a low dielectric constant resin according to claim 2, comprising an inorganic filler.

7. The composition for forming a low dielectric constant resin according to claim 6, wherein the thermal conductivity of the cured product is 0.5 W / m·K or higher.

8. The composition for forming a low dielectric constant resin according to claim 6, 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, silica, titanium oxide, tin oxide, holmium oxide, calcium oxide, magnesium hydroxide, aluminum hydroxide, cordierite, and mullite.

9. The composition for forming a low dielectric constant resin according to claim 6, wherein the inorganic filler is aluminum nitride, boron nitride, silicon nitride, magnesium oxide, aluminum oxide, zinc oxide, silica, titanium oxide, or magnesium hydroxide.

10. A low dielectric constant resin insulating film is a polymer molded article obtained by imidizing or curing the composition for forming a low dielectric constant resin according to claim 2 by heat.

11. A low dielectric constant resin film or low dielectric constant resin sheet, which is a polymer molded article obtained by thermally imidizing or curing the composition for forming a low dielectric constant resin according to claim 2.

12. A low dielectric constant resin part that is a polymer molded article obtained by imidizing the composition for forming a low dielectric constant resin according to claim 2 by heat.

13. An electronic device using a polymer-forming material according to any one of claims 10 to 12.

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