Method for producing polymerizable liquid crystal compounds and use of polymerizable liquid crystal compounds

Abstract

A method for safely and stably producing a polymerizable liquid crystal compound is provided. The production method is a method for producing the following polymerizable liquid crystal compound (1), JPEG0007782745000019.jpg24109 A first step of obtaining the following compound (1B) from the following compound (1A); JPEG0007782745000020.jpg14103 and a second step of obtaining the polymerizable liquid crystal compound (1) from the following compound (1C) and the compound (1B). JPEG0007782745000021.jpg24115

Description

[Technical Field]

[0001] The present disclosure relates to a method for safely and stably producing a polymerizable liquid crystal compound that forms a low dielectric resin used in electronic components and electronic substrates that handle high frequencies for 5G and 6G. [Background technology]

[0002] In recent years, with the shift to 5G and beyond 5G and 6G in communication devices, the frequency of electrical signals on electronic circuit boards and the radio waves transmitted and received by antennas have become higher, resulting in signal loss problems in signal processing circuit boards and antenna boards. Furthermore, materials that do not impede the increased signal transmission speed are desired for insulating materials that contact the silicon chips and wiring materials inside semiconductor chips. Therefore, resin materials used in substrates and insulating materials are required to have low dielectric constants and low dielectric dissipation factors. Resins such as liquid crystal polymers (LCPs), polyphenylene ethers (PPEs), cycloolefin polymers (COPs), and fluororesins (PTFEs) are beginning to be used instead of conventional polyimides and epoxy resins. Low-dielectric substrates have a dielectric constant of 3.0 or less, and those containing high thermal conductive fillers have a dielectric constant of 3.5 or less, and there is a demand for the development of materials with even lower dielectric constants (Non-Patent Document 1).

[0003] However, current materials for high-frequency substrates are mainly thermoplastic resins, which have many drawbacks, such as the need to mold and bond them at high temperatures and poor adhesion between resins and to the copper foil that serves as the electrode. Patent Document 1 examines the molecular structure of liquid crystal polymers to achieve a lower dielectric constant. However, liquid crystal polymers have a high melting point, requiring processing temperatures of 350°C or higher, making thermal lamination and bonding to copper foil difficult.

[0004] Patent Document 2 examines the possibility of producing a varnish by increasing the solubility in organic solvents. By examining the molecular structure of PPE resin, it became possible to form a film from PPE resin using a coating method, making it possible to use it as an insulating varnish. However, this poses many problems, such as the need to use an organic solvent with high solubility and limited freedom in polymer design when trying to adjust properties other than dielectric properties. Therefore, there is a need to develop a low-dielectric-constant resin that can be applied and easily cured like an insulating coating varnish.

[0005] Regarding insulating materials for semiconductors, Patent Document 3 shows an epoxy resin with a low dielectric constant that has increased crosslinking. As such, currently mainstream low-dielectric epoxy compounds are often designed to be multifunctional with many crosslinking points, and the crosslinking suppresses molecular vibrations that cause dielectric loss, but this does not sufficiently reduce the dielectric constant, and there are many cases where epoxy resins are replaced with other resins.

[0006] Furthermore, with the increase in communication traffic, the amount of heat generated by semiconductor chips for data processing is also increasing, and since power semiconductor chips that generate a large amount of heat are being mounted on antenna substrates, there is a growing demand for heat dissipation properties in electronic substrates, and therefore there is a demand for the development of resins with high thermal conductivity. Patent Document 4 describes that when a highly linear polymerizable liquid crystal compound is oriented and cured, it has higher thermal conductivity in the orientation direction than ordinary thermosetting resins, and Patent Document 5 describes that by combining a polymerizable liquid crystal compound with a heat-dissipating filler, it is possible to form a thermosetting resin material with even higher thermal conductivity.

[0007] Patent Document 6 describes a resin-forming composition that uses a polymerizable liquid crystal that has a low dielectric constant and also high thermal conductivity. The composition emphasizes high thermal conductivity, as well as affinity and adhesiveness with inorganic materials such as thermally conductive fillers, and therefore has a structure that includes multiple ether bonds within the molecule.

[0008] Non-Patent Documents 2 and 3 describe the characteristics of titanium silicalite-1 (TS-1), the mechanism of oxidation reactions, and general examples of its use in organic synthesis, but there are no examples of its application to alkenyl halides.

[0009] Many publications, including Non-Patent Document 4, describe examples of synthesizing alkyl halide epoxides from alkenyl halides using metachloroperbenzoic acid (mCPBA). However, metachloroperbenzoic acid is expensive and uses a chlorine-based solvent that places a high burden on the environment, making it unsuitable for production. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 2019-189734 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-67894 [Patent Document 3] Patent No. 7499994 [Patent Document 4] Japanese Patent Application Laid-Open No. 2006-265527 [Patent Document 5] International Publication No. 2015 / 170744 [Patent Document 6] International Publication No. 2022 / 092063 [Non-patent literature]

[0011] [Non-Patent Document 1] Hiroyuki Fukunaga and Yoshiyuki Hamato, "Basics and Selection of High-Speed / High-Frequency Boards," RF World, CQ Publishing, 2017, No. 40, pp. 97-111 [Non-patent document 2] iScience 27, 109064, March 15, 2024 [Non-patent document 3] Eupopean Journal of Organic Chemistry, “Chemoselective Epoxidation of Allyloxybenzene by Hydrogen Peroxide Over MFI-Type Titanosilicate”, 2020, p.2260-2263 [Non-patent document 4] Macromolecues, “Photoinduced Alignment of Ferroelectric Liquid Crystals Using Azobenzene Polymer Networks of Polyethers and Polyepoxides”, 2003, vol.36, No.24 Summary of the Invention [Problem to be solved by the invention]

[0012] The problem to be solved by the present disclosure is to realize a method for safely and stably producing a polymerizable liquid crystal compound. [Means for solving the problem]

[0013] As a result of intensive research to solve the above problems, the present inventors have found that by using the production method according to the present disclosure, a polymerizable liquid crystal compound (1) described below, which is used in a composition for forming a low dielectric constant resin, can be produced safely and stably with high yield and purity, with little environmental impact, and at low cost.

[0014] A composition containing polymerizable liquid crystal compound (1) obtained by the production method according to the present disclosure exhibits high heat resistance after curing, a low dielectric constant and low dielectric dissipation factor in the high-frequency range, and high heat dissipation. This allows for the realization of a low-dielectric-constant resin-forming composition, which is a curable resin composition. The use of the low-dielectric-constant resin-forming composition according to the present disclosure can provide materials suitable for applications in next-generation communication devices and radars in the high-frequency range.

[0015] The present disclosure includes the following aspects. [1] A method for producing the following polymerizable liquid crystal compound (1), JPEG0007782745000001.jpg24109 A first step of obtaining the following compound (1B) from the following compound (1A); JPEG0007782745000002.jpg14103 a second step of obtaining the polymerizable liquid crystal compound (1) from the following compound (1C) and the compound (1B), JPEG0007782745000003.jpg24115 In compound (1A) and compound (1B), n is an integer from 2 to 12, X is a halogen; In the compound (1C) and the polymerizable liquid crystal compound (1), R m are independently alkyl or alkoxy having 1 to 4 carbon atoms, s is independently an integer of 0 to 4, and when s is 2 or more, R m may be the same or different, n is an integer from 2 to 12, p is 0 or 1; A method for producing a polymerizable liquid crystal compound. [2] The first step involves obtaining compound (1B) from compound (1A) using a peroxide and a catalyst. The manufacturing method described in [1] above. [3] the peroxide includes hydrogen peroxide or peracetic acid; The catalyst comprises titanium silicalite-1 (TS-1); The manufacturing method described in [2] above. [4] In the first step, the solvent used comprises ethyl acetate. The manufacturing method according to [2] or [3] above. [5] In the first step, the reaction temperature is set to 0 to 40°C. The manufacturing method according to any one of [2] to [4] above. [6] In the second step, the polymerizable liquid crystal compound (1) is obtained from the compound (1C) using the compound (1B) and a base. The method for producing according to any one of the above [1] to [5]. [7] The base includes potassium carbonate, cesium carbonate, or tripotassium phosphate. The manufacturing method described in [6] above. [8] The base comprises tripotassium phosphate; The manufacturing method described in [7] above. [9] In the second step, the reaction temperature is set to 0 to 40°C. The manufacturing method according to any one of [6] to [8] above.

[10] The polymerizable liquid crystal compound (1) is a compound selected from the following compounds (1-1-1) to (1-1-6), JPEG0007782745000004.jpg10297 In compounds (1-1-1) to (1-1-6), R m is independently methyl or methoxy; n is an integer from 2 to 12; The method for producing according to any one of the above [1] to [9].

[11] The polymerizable liquid crystal compound (1) is a compound selected from the following compounds (1-2-1) to (1-2-6), JPEG0007782745000005.jpg108111 In compounds (1-2-1) to (1-2-6), Rm is independently methyl or methoxy; s is an integer from 0 to 4, and when s is 2 or more, R m may be the same or different, n is an integer from 2 to 12; The method for producing according to any one of the above [1] to [9].

[12] Use of a polymerizable liquid crystal compound produced by the production method according to any one of the above [1] to

[11] . [Effects of the Invention]

[0016] The present disclosure can provide a method for safely and stably producing a polymerizable liquid crystal compound. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 shows a simplified mold made of polyimide film, which was fabricated for the purpose of controlling the thickness of a molten composition and preventing the melt from leaking out when measuring the dielectric properties of a composition containing the compound synthesized in the Examples. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, as one embodiment, a method for producing the polymerizable liquid crystal compound (1) according to the present disclosure will be described. Furthermore, the following will be described in detail: the polymerizable liquid crystal compound (1) (also referred to as compound (1)) obtained by the production method according to the present disclosure; a composition for forming a low dielectric constant resin containing at least one selected from the polymerizable liquid crystal compounds (1); a low dielectric constant resin insulating film, a low dielectric constant resin sheet, a low dielectric constant resin part, which are polymer molded articles of a low dielectric constant resin obtained by curing the composition with heat or ultraviolet light; and an electronic device using the polymer molded article.

[0019] The terms used in this specification are as follows. "Liquid crystal compound" is a general term for compounds that have a liquid crystal phase such as a nematic phase or a smectic phase, and compounds that do not have a liquid crystal phase but have physical properties specific to liquid crystals such as dielectric anisotropy, refractive index anisotropy, and magnetic susceptibility anisotropy, and are useful as components of liquid crystal compositions. Alignment treatment is easy in the liquid crystal temperature range, and the molecular orientation can be controlled in the same way as stretching treatment of thermoplastic resins.

[0020] "Compound (1)" means a polymerizable liquid crystal compound represented by the above formula (1), and may also mean at least one compound represented by formula (1). The same applies to "compound (1-1)" and the like, and compounds (1-1), (1-2), and (1-3) may also be collectively referred to as "compound (1)." In one compound (1), two or more R m may be the same or different. m When any two R m may be the same or different. This rule also applies to other symbols, groups, etc.

[0021] The term "polymer (1)" refers to at least one polymer obtained by polymerizing compound (1). As with "compound (1)," polymers of compounds (1-1), (1-2), and (1-3) may also be collectively referred to as "polymer (1)."

[0022] "Composition (1)" refers to a composition containing at least one compound selected from the compounds (1), that is, a composition for forming a low dielectric constant resin according to the present disclosure.

[0023] 1) Compound (1) 1-1) Method for producing compound (1) Compound (1) can be synthesized safely, stably, and at low cost using a production method comprising the following first and second steps. The starting materials are commercially available or can be synthesized by combining known methods in general organic synthetic chemistry. Organic synthetic chemistry is described in, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart; Organic Syntheses, John Wiley & Sons, Inc.; Organic Reactions, John Wiley & Sons, Inc.; Comprehensive Organic Synthesis, Pergamon Press; and New Experimental Chemistry Lectures (Maruzen).

[0024] The reaction scheme for the first step is as follows: JPEG0007782745000006.jpg1291 In Compound (1A) and Compound (1B), n is an integer between 2 and 12, and X is a halogen (fluorine, chlorine, bromine, iodine, or astatine). Compound (1B) can be obtained in high yield by stirring a mixture of Compound (1A), a solvent, a peroxide, and titanium silicalite-1 (TS-1) as a catalyst at a temperature between 0 and 60°C for several hours to several days. The starting material, compound (1A), is commercially available or can be prepared by common synthetic organic chemistry techniques. The solvent may be methanol, isopropanol, ethyl acetate, acetonitrile, or a mixture thereof, with a mixture of methanol and ethyl acetate being preferred. The peroxide may be hydrogen peroxide or peracetic acid, with hydrogen peroxide being more preferred from the standpoint of cost. The amount of the catalyst may be 1 to 100 wt % based on the compound (1A), and the larger the amount of the catalyst, the faster the reaction rate. From the viewpoint of cost, the amount of the catalyst is preferably 3 to 50 wt %. The amount of peroxide may be such that the molar ratio of compound (1A) to peroxide is 1:1.0 to 5.0, and from the standpoints of the reaction rate of the reactant, ease of post-treatment, and cost, the molar ratio is preferably 1:1.1 to 2.0. The reaction temperature is preferably 0 to 40° C. Within this temperature range, the reaction rate is particularly fast, and the reaction selectivity to compound (1B) is improved.

[0025] The reaction scheme for the second step is as follows: JPEG0007782745000007.jpg49132 In compound (1C) and compound (1), R m is alkyl or alkoxy having 1 to 4 carbon atoms, s is an integer of 0 to 4, p is 0 or 1, and n is an integer of 2 to 12. When s is 2 or more, R m may be the same or different. Compound (1) can be obtained with high reaction selectivity by stirring a mixture of compound (1C), compound (1B), a base, and a solvent at a temperature ranging from 0 to 100°C for several hours to several days. The starting material compound (1C) is commercially available or can be prepared by general synthetic organic chemistry techniques. The base may be potassium carbonate, cesium carbonate, potassium phosphate (particularly tripotassium phosphate), or sodium phosphate. In terms of reaction selectivity, potassium phosphate is preferred. The solvent may be methanol, ethanol, isopropanol, butanol, tetrahydrofuran (THF), N,N'-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), dimethoxymethyl ether, or a mixture thereof, with methanol, ethanol, tetrahydrofuran (THF), and N,N'-dimethylformamide being more preferred in terms of solubility. If necessary, a catalyst such as a quaternary ammonium halide salt, such as tetrabutylammonium bromide, or a cyclic ether, such as a crown ether, may be added. The amount of base may be such that the molar ratio of compound (1C) to base is 1:2.1 to 5.0, and from the standpoints of the reaction rate of the reactant, ease of post-treatment, and cost, the molar ratio is preferably 1:2.1 to 3.0. The reaction temperature may be 0 to 40° C., and is preferably 20 to 40° C. Within this temperature range, the compatibility of the reaction system is high, the reaction rate is fast, and the reaction selectivity is improved.

[0026] 1-2) Characteristics of compound (1) The polymerizable liquid crystal compound (1) (also referred to as compound (1)) obtained by the production method according to the present disclosure has a liquid crystal skeleton (rod-shaped mesogenic skeleton) and a polymerizable group, and preferably has few conjugated or polar groups, high molecular linearity and symmetry, high polymerization reactivity, a wide liquid crystal phase temperature range, good miscibility, etc. This compound (1) is likely to become homogeneous when mixed with other liquid crystal compounds or polymerizable compounds. In addition, compound (1) has low polarity throughout the molecule and exhibits low dielectric constant and low dielectric loss. Therefore, a polymer molded product obtained by curing a low dielectric constant resin-forming composition using compound (1) with heat or ultraviolet light can be used as a suitable material for applications requiring low dielectric loss, such as low dielectric constant resin insulating films, low dielectric constant resin films, and low dielectric constant resin sheets. The melting point of compound (1) is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower, from the viewpoint of molding and curing temperatures. Alternatively, the transition temperature of compound (1) from a nematic phase to a liquid is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower, from the viewpoint of molding and curing temperatures.

[0027] Compound (1) is composed of a ring structure, a side group, a bonding group, and a terminal polymerizable group. m ), bonding group (-(CH2) nBy appropriately selecting n, physical properties such as the liquid crystal phase manifestation region can be adjusted as desired. n is an integer of 0 to 12. The effects of the types of terminal group, ring structure, side group, and bonding group on the physical properties of compound (1), as well as preferred examples thereof, are described below. The ring structure, bonding group, and terminal group are referred to as "ring structure A," "bonding group Z," and "terminal group R," respectively. 1 " is sometimes referred to collectively.

[0028] <Ring structure A> The ring structures of compound (1) are independently 1,4-phenylene, and in this 1,4-phenylene ring, at least one hydrogen may be replaced by alkyl or alkoxy having 1 to 4 carbon atoms. In compound (1), "at least one hydrogen atom on the 1,4-phenylene ring may be replaced by an alkyl having 1 to 4 carbon atoms," and preferred examples of the alkyl having 1 to 4 carbon atoms are methyl and ethyl. Compound (1) has a low melting point, high solubility, a low relative permittivity due to a small molecular polarizability, a low dielectric loss due to suppressed molecular motion, and a large orientational order parameter and magnetic anisotropy. When at least two rings are 1,4-phenylene or the above-mentioned substituted 1,4-phenylene, compound (1) has a wide temperature range of the liquid crystal phase and a high clearing point. When the ring structure of compound (1) is 1,4-phenylene or 3,5-dimethyl-phenylene, it is preferable in terms of cost in producing compound (1).

[0029] Preferred examples of the ring structure of compound (1) are 1,4-phenylene, 2-methyl-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 2,5-dimethyl-1,4-phenylene, and 2,6-dimethyl-1,4-phenylene. More preferred examples are 1,4-phenylene, 2-methyl-1,4-phenylene, and 3,5-dimethyl-1,4-phenylene. 2-Methyl-1,4-phenylene and 3-methyl-1,4-phenylene are structurally identical, so the latter is not exemplified. This rule also applies to the relationship between 2,5-dimethyl-1,4-phenylene and 3,6-dimethyl-1,4-phenylene.

[0030] <Binding group Z:-(CH2) n -> In the methylene group, when n is small, the rigidity of the molecule increases, so that compound (1) has high liquid crystallinity, low viscosity, and low dielectric loss tangent. When n is large, the molecular length increases, so that compound (1) has a low melting point and high solubility in organic solvents. n is an integer of 2 to 12.

[0031] p is 0 or 1. When p is 0, i.e., when compound (1) has two rings, compound (1) has a low viscosity, and when p is 1 or more, i.e., when compound (1) has three or more rings, compound (1) has a high clearing point.

[0032] As described above, a compound having desired physical properties can be obtained by appropriately selecting the types of ring structure A and bonding group Z. Specific examples of preferred compound (1) include compounds represented by formulae (1-1-1) to (1-1-6) and formulae (1-2-1) to (1-2-6). JPEG0007782745000008.jpg114110 JPEG0007782745000009.jpg121125 In the formulas (1-1-1) to (1-1-6) and (1-2-1) to (1-2-6), R m are independently alkyl or alkoxy having 1 to 4 carbon atoms, s is an integer of 0 to 4, and when s is 2 or more, R m may be the same or different, and n is an integer of 2 to 12.

[0033] 2) Polymer (1) The compound (1) obtained by the production method according to the present disclosure has a polymerizable group and can be easily polymerized. The polymer (1) is at least one type of polymer obtained by polymerizing the compound (1). In the composition (1) described in the next section, the polymer (1) formed in combination with at least one other component may be an oligomer of the compound (1). This oligomer refers to a low polymer having a low number (degree of polymerization) of constitutional units of the compound (1) that constitute the polymer (1). Depending on the number of constitutional units, the oligomer may be called a dimer, trimer, tetramer, or the like.

[0034] 3) Composition (1) The composition (1) according to the present disclosure is a composition containing at least one compound (1). That is, the composition (1) may be composed of two or more compounds (1), or may be composed of a combination of at least one compound (1) and at least one other component other than the compound (1), including a polymer (1). The at least one other component is not particularly limited, but examples thereof include polymer (1), polymerizable compounds other than the compound (1) (hereinafter also referred to as "other polymerizable compounds"), polymerization initiators, organic solvents, non-polymerizable liquid crystal compounds, inorganic fillers, and fibrous reinforcing agents. Preferred compositions (1) include compositions composed of at least one compound (1) and polymer (1), compositions composed of at least one compound (1) and other polymerizable compounds, and compositions composed of at least one compound (1), polymer (1), and other polymerizable compounds.

[0035] 4) Other polymerizable compounds Composition (1) according to the present disclosure may contain a polymerizable compound (other polymerizable compound) other than compound (1). The polymerizable compound other than compound (1) is composed of at least one of the following polymerizable liquid crystal compounds other than compound (1) (hereinafter also referred to as "other polymerizable liquid crystal compounds") and at least one of the following polymerizable non-liquid crystal compounds.

[0036] 4-1) Other polymerizable liquid crystal compounds Composition (1) according to the present disclosure may contain at least one polymerizable liquid crystal compound other than compound (1). From the viewpoints of the development of a liquid crystal phase in composition (1), which is a polymerizable liquid crystal composition, and compatibility with compound (1) and organic solvents, etc., compounds represented by formula (M1), (M2), or (M3) (excluding compound (1)) are preferred as the polymerizable liquid crystal compound.

[0037] JPEG0007782745000010.jpg54159

[0038] In formulas (M1), (M2) and (M3), A M are independently any 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, and fluorene-2,7-diyl, in which at least one hydrogen may be replaced by fluorine, chlorine, cyano, hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, alkoxycarbonyl having 2 to 5 carbon atoms, or alkanoyl having 2 to 5 carbon atoms; Z M are independently a single bond, -OCH2-, -CHO-, -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 is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or alkoxycarbonyl having 2 to 20 carbon atoms; Y M are independently a single bond, -O-, -COO-, -OCO-, or -OCOO-; Q M is a single bond, -O-, -COO-, or -OCO-; q is an integer from 1 to 6; c and d are independently integers of 0 to 3 and satisfy the relationship 1≦c+d≦6; a is an integer from 0 to 20; P 3 ~P 5 are independently groups selected from the polymerizable groups represented by formulae (PG-1) to (PG-13). JPEG0007782745000011.jpg1939 JPEG0007782745000012.jpg48129

[0039] 4-2) Polymerizable non-liquid crystal compound The composition (1) according to the present disclosure may contain at least one polymerizable non-liquid crystal compound as a constituent element. Such a polymerizable non-liquid crystal compound is preferably a compound that does not reduce film-forming properties and mechanical strength. This polymerizable non-liquid crystal compound is classified as a compound that does not have liquid crystallinity. Examples of polymerizable non-liquid crystal compounds that do not have liquid crystallinity include derivatives such as vinyl derivatives, styrene derivatives, (meth)acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, and itaconic acid derivatives; modified polyimide oligomers, modified maleimide oligomers, modified polyphenylene ether oligomers, modified polyphenylene sulfide oligomers, and modified polybutadiene elastomers; and modified engineering plastic oligomers, i.e., macromers, which refer to high-molecular-weight compounds having polymerizable functional groups. Preferred examples of these derivatives are shown below.

[0040] In the text, "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylic acid" means acrylic acid or methacrylic acid.

[0041] Preferred vinyl derivatives include 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, vinyl pt-butylbenzoate, 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.

[0042] Preferred styrene derivatives include styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, and α-methylstyrene.

[0043] Preferred (meth)acrylic acid derivatives include 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-adduct triacrylate, pentaerythritol triacrylate, tris(meth)acryloyloxyethyl phosphate, bisphenol A EO-adduct diacrylate, bisphenol A glycidyl diacrylate (trade name: "Biscoat 700" manufactured by Osaka Organic Chemical Industry Ltd.), and polyethylene glycol diacrylate dimethyl itaconate.

[0044] Preferred sorbic acid derivatives include 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 propargyl sorbate.

[0045] Preferred fumaric acid derivatives include dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclopentyl fumarate, and dicyclohexyl fumarate.

[0046] Preferred itaconic acid derivatives include diethyl itaconate, dibutyl itaconate, and diisopropyl itaconate. In addition to these, many polymerizable non-liquid crystal compounds such as butadiene, isoprene, and maleimide can also be used.

[0047] 5) Polymerization initiator The composition (1) according to the present disclosure may contain a polymerization initiator as a constituent element. The polymerization initiator may be a thermal radical polymerization initiator, a photoradical polymerization initiator, a photocationic polymerization initiator, or the like, depending on the curing method (polymerization method) of the composition (1). When the polymerizable compound used in the present disclosure is composited with an inorganic filler to increase thermal conductivity, the inorganic filler absorbs light, so it is preferable to use a thermal radical polymerization initiator. When a composite material with an inorganic filler is used as a thin film with a thickness of several micrometers, it is also possible to increase the amount of polymerization initiator or use a strong polymerization initiator to cure by photopolymerization.

[0048] Preferred thermal radical polymerization initiators include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide (DTBPO), t-butyl peroxydiisobutyrate, lauroyl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), and dimethyl 2,2'-azobis(isobutyrate). Commercially available peroxide initiators include benzoyl peroxide, available from various companies, as well as "Dicumyl Peroxide" (trade name, manufactured by Tokyo Chemical Industry Co., Ltd.), and "Percumyl D, Niper BMT, and Perhexa 25Z" (trade names, manufactured by NOF Corporation). Azo polymerization initiators include AIBN, available from various companies, as well as "V-40, V-50, V-59, V-65, V-70, V-501, and V-601" (trade names, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Generally, azo polymerization initiators can be suitably used for both thermal radical polymerization and photoradical polymerization.

[0049] The photoradical polymerization initiator is not particularly limited, and known initiators can be used, such as 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, and benzophenone / methyltriethanolamine mixture. Commercially available products include those manufactured by Ciba Specialty Chemicals (now BASF Japan Ltd.) under the trade names "Darocur Series 1173, 4265" and those manufactured by Ciba Specialty Chemicals (now BASF Japan Ltd.) under the trade names "Irgacure Series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, 2959."

[0050] The photocationic polymerization initiator is not particularly limited, and known ones can be used, and examples thereof include commercially available products such as "Cyracure UVI-6990, 6974" manufactured by UCC Corporation, "ADEKA Optomer SP-150, 152, 170, 172" manufactured by ADEKA Corporation, "Photoinitiator 2074" manufactured by Rhodia, "Irgacure 250" manufactured by Ciba Specialty Chemicals (now BASF Japan Ltd.), and "DTS-102" manufactured by Midori Chemical Industry Co., Ltd.

[0051] Preferred initiators for anionic polymerization, coordination polymerization and living polymerization include alkali metal alkyl compounds such as n-C4H9Li and t-C4H9Li-R3Al, aluminum compounds, transition metal compounds and the like.

[0052] 6) Hardener When the composition (1) according to the present disclosure contains a cyclic ether, which is a cyclic compound having an ether bond, as a constituent element, the composition (1) may contain a curing agent as a constituent element. Preferred examples of the curing agent are shown below.

[0053] Amine 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, norbornene diamine, 1,2 -diaminocyclohexane, 3,9-dipropanamine-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, polyoxypropylenediamine, polyoxypropylenetriamine, polycyclohexylpolyamine, N-aminoethylpiperazine, and the like.

[0054] Examples of acid anhydride 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 bisanhydrotrimethylate, glycerin bis(anhydrotrimellitate) monoacetate, dedecenylsuccinic anhydride, and chlorendic anhydride.

[0055] Examples of phenol-based 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 JP-A Nos. 2004-256687 and 2002-226550 can also be used.

[0056] The active ester curing agent is not particularly limited, and known active ester curing agents can be used, and examples thereof include commercially available products such as "EPICLON (registered trademark) HPC-8000-65T" manufactured by DIC Corporation as an active ester compound containing a dicyclopentadiene-type diphenol structure, "EXB-8150-65T" manufactured by DIC Corporation as an active ester compound containing a naphthalene structure, "DC808" manufactured by Mitsubishi Chemical Corporation as an active ester compound containing an acetylated product of phenol novolac, and "YLH1026" manufactured by Mitsubishi Chemical Corporation as an active ester compound containing a benzoylated product of phenol novolac, and "DC808" manufactured by Mitsubishi Chemical Corporation as an active ester curing agent which is an acetylated product of phenol novolac, and "YLH1026" manufactured by Mitsubishi Chemical Corporation as an active ester curing agent which is a benzoylated product of phenol novolac.

[0057] Further, examples of the curing accelerator include 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 the cycloamidine compounds, when used in combination with maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, and 2,3-dimethoxy-5-methylbenzoquinone. quinone compounds such as phenyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and the like, compounds having intramolecular polarization obtained by adding compounds having a π bond such as diazophenylmethane and phenolic resins; tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the tertiary amine compounds; 2-methylimidazole, 2-phenylimidazole, 2-phenylimidazole, and the like. 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 a compound having a π bond such as maleic anhydride, the above-mentioned quinone compounds, diazophenylmethane, or a phenol resin 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 the tetraphenylboron salts with phosphine compounds such as triphenylphosphonium-triphenylborane and N-methylmorpholine tetraphenylphosphonium-tetraphenylborate.

[0058] 7) Organic Solvents Composition (1) may contain an organic solvent. Composition (1) may be cured in an organic solvent or without a solvent. For example, composition (1) containing an organic solvent may be applied to a substrate by spin coating or the like, and then the organic solvent may be removed before photocuring. After photocuring, the composition may be heated to an appropriate temperature for post-treatment by thermal curing.

[0059] Preferred organic solvents include benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran (THF), methyl ethyl ketone (MEK), γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide, cyclohexane, methylcyclohexane, cyclopentanone, cyclohexanone, 2-methoxy-1-methylethyl acetate (propylene glycol methyl ether acetate: PGMEA), etc. The above organic solvents may be used alone or in combination of two or more. It is not particularly meaningful to limit the proportion of the organic solvent used during curing, and the proportion may be determined for each individual case, taking into consideration the curing efficiency, solvent cost, energy cost, etc.

[0060] The composition (1) according to the present disclosure preferably contains 70 wt% or less of an organic solvent based on the total weight, and is particularly preferably a solvent-free composition. A solvent-free composition is a composition that maintains fluidity at room temperature without the use of an organic solvent, or can be prepared into a varnish-like form that exhibits high fluidity when melted. By using a composition containing 70 wt% or less of an organic solvent based on the total weight, or a solvent-free composition, the concentration of the cured product is increased, allowing the functionality of the cured product to be effectively expressed. Composition (1) before curing is in a liquid state at around room temperature and retains fluidity, and can be used as a varnish without solvent or containing 70 wt% or less of an organic solvent based on the total weight. In other words, it can be used as is for applications such as coating or adhesion, and does not require a process of volatilizing the solvent at high temperature. In addition, examples of organic solvents that can be used here include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N,N-dimethylformamide, methanol, ethanol, etc., which are relatively low in toxicity from the viewpoint of environmental impact. Composition (1) of the present disclosure is capable of forming a resin with high heat resistance and a high low dielectric constant in a non-organic solvent system, and therefore can provide insulating materials for various electronic components, such as laminates for printed wiring boards, interlayer insulating materials for substrates, adhesive films, semiconductor encapsulants, and conductive adhesives.

[0061] 8) Non-polymerizable liquid crystal compounds The composition (1) according to the present disclosure may contain a liquid crystal compound without a polymerizable group as a constituent element. Examples of such non-polymerizable liquid crystal compounds are described in LiqCryst (LCI Publisher GmbH, Hamburg, Germany), a database of liquid crystal compounds. By curing the composition (1) containing the non-polymerizable liquid crystal compound, a composite material containing a polymer of the compound (1) and the liquid crystal compound can be obtained. In such a composite material, for example, the non-polymerizable liquid crystal compound exists in a polymer network, such as a polymer-dispersed liquid crystal.

[0062] 9) Inorganic fillers and fibrous reinforcing agents An inorganic filler can be added to the composition (1) to improve thermal conductivity, improve mechanical strength, adjust viscosity, etc. In this specification, the inorganic filler may be referred to as inorganic filler. To suppress dielectric loss, the material may be a silicon compound such as spherical silica, pulverized silica, hollow silica, or fumed silica, a metal oxide such as magnesium oxide, zinc oxide, or titanium oxide, or a metal salt such as potassium titanate. Spherical silica, hollow silica, magnesium oxide, or potassium titanate is preferred, and hollow silica is more preferred. A fibrous reinforcing agent can be used as a fibrous or whisker-like filler for increasing the strength of substrates and resin parts. Preferred examples include inorganic fibers such as glass cloth, low-dielectric glass cloth, carbon fibers, and carbon nanotubes, and inorganic whiskers such as silicate whiskers, alumina whiskers, magnesium oxide whiskers, zinc oxide whiskers, and aluminum nitride whiskers, and more preferred examples are low-dielectric glass cloth, aluminum oxide whiskers, aluminum nitride whiskers, and carbon nanotubes.

[0063] To increase mechanical strength, a larger amount of filler is preferable, but if there is too much, the resin may not be able to fill the gaps between the fillers. Also, if there is too much resin, the effect of increasing mechanical strength may not be achieved. Furthermore, increasing the filler content tends to increase the dielectric constant and decrease the dielectric dissipation factor, so it is preferable to determine the composition while balancing these two factors. In addition to inorganic fibers, organic fibers can also be used as fibrous heat-dissipating fillers. Examples of organic fibers with high mechanical strength include polyamide fibers, aramid fibers, polyparaphenylene benzobisoxazole fibers, liquid crystalline polyester fibers, and cellulose nanofibers. Compared to inorganic fibers, organic fibers are lighter and are therefore preferred for substrates of portable devices.

[0064] Fillers with high thermal conductivity include powdered 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 and mullite; and metal fillers such as gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, and stainless steel. Boron nitride and silicon oxide, which have low dielectric constants, are preferred, and hexagonal boron nitride (h-BN) is particularly preferred due to its low dielectric constant and high thermal conductivity. While the thermal conductivity increases with increasing inorganic filler content, inorganic fillers generally have a higher relative dielectric constant and a smaller dielectric dissipation factor than resin components, so increasing the filler content increases the dielectric constant. Therefore, it is preferable to fill the required amount within a range that does not exceed the desired dielectric constant. When heat resistance is not required, the use of cellulose nanofibers is preferable because they have a slightly higher dielectric constant but are lightweight and have high thermal conductivity.

[0065] Composition (1) is highly transparent and has low dielectric constant. When used as a low refractive optical material, the refractive index can be adjusted by adding powders such as hollow silica, spherical silica, titanium oxide, and zirconium oxide.

[0066] The shape of the filler may be spherical, amorphous, fibrous, whisker-like, cylindrical, plate-like, etc. The type, shape, size, and amount of filler added can be appropriately selected depending on the purpose. When the resulting polymer molded article requires insulation, a conductive filler may be used as long as the desired insulation properties, mechanical strength, relative dielectric constant, dielectric loss tangent, and dielectric loss are maintained.

[0067] The average particle size of the spherical or irregularly shaped filler is preferably 0.1 to 200 μm, more preferably 1 to 100 μm. A diameter of 0.1 μm or more provides good thermal conductivity, while a diameter of 200 μm or less allows for a high filling rate. Regarding fibrous fillers, the longer the fiber length, the higher the tensile strength, but this may make kneading or dispersion difficult, so it is preferable to select the length depending on the application. When dispersed, the average particle size of the fibrous filler is preferably 0.01 to 200 μm, more preferably 0.1 to 100 μm. A diameter of 0.01 μm or more provides good thermal conductivity, while a diameter of 200 μm or less allows for increased mechanical strength. The amount of filler is preferably 20 to 95 wt% in the polymer molded body after curing, more preferably 50 to 95 wt%. A filler content of 20 wt% or more is preferred because it increases thermal conductivity. A filler content of 95 wt% or less is preferred because it prevents the polymer molded body from becoming brittle.

[0068] As the filler, commercially available products that have been surface-treated, such as affinity-treated, adhesion-facilitating-treated, dispersion-treated, or waterproof-treated, may be used as they are, or the commercially available products from which the surface treatment agents have been removed may be used. Alternatively, untreated fillers may be used after being treated with a silane coupling agent, affinity agent, surface tension adjuster, anti-settling agent, anti-aggregation agent, etc.

[0069] 10) Other additives Since the compound (1) and composition (1) obtained by the production method according to the present disclosure have high polymerizability, a stabilizer may be added to composition (1) to facilitate handling. Known stabilizers can be used without limitation as such stabilizers, and examples thereof include hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT). In applications requiring a low dielectric tangent (low tanδ) and a high glass transition temperature, it is preferable to add a crosslinking agent, which preferably chemically bonds with the polymerizable groups of the compound (1) used in the present disclosure and has polymerizable groups at both ends to form a three-dimensional crosslink.

[0070] To adjust the properties of the cured product, composition (1) may contain other resins that do not react with compound (1). Examples of such resins include polyphenylene ether resins (PPE resins), polystyrene resins, polycarbonate resins, polyimide resins, polyamide resins, polyester resins, polybutadiene copolymers, polyvinyl acetal resins, natural rubber, synthetic rubber, synthetic elastomers, epoxy resins with a different liquid crystal skeleton from that of compound (1) used in the present disclosure, oxetane resins, acrylic resins, methacrylic resins, maleimide resins, oxazine resins, and oxazoline resins. When dielectric properties are particularly important, polyphenylene ether resins (PPE resins), polystyrene resins, and polycarbonate resins are preferred. These resins contain unreacted sites that may react with compound (1) used in the present disclosure. In such cases, a crosslinked structure is formed, which is expected to result in improved properties compared to when the reaction is complete.

[0071] 11) Low dielectric constant resin The low dielectric constant resin of another embodiment is a cured product of the composition (1) and therefore has a low dielectric constant, and is also excellent in thermal conductivity, heat resistance, rigidity, elasticity, molding flowability, chemical resistance, dimensional stability, and the like.

[0072] 11-1) Polymerizable group When a low-dielectric-constant resin-forming composition containing compound (1) obtained by the manufacturing method of the present disclosure is cured without the addition of an inorganic filler, the dielectric constant and dielectric dissipation factor of the cured product are measured. Compound (1) is an epoxy compound, and conjugation and electron imbalance between the ring structure and surrounding atoms are likely to occur. Its dielectric properties, particularly in the high-frequency range of 1 GHz to 50 GHz, are as follows: a dielectric constant of 2.8 to 2.0 and a dielectric dissipation factor of 0.02 to 0.001. The liquid crystal skeleton and linker moieties are preferably molecularly designed to achieve a dielectric constant of 2.8 to 2.0 and a dielectric dissipation factor of 0.01 to 0.001, more preferably a dielectric constant of 2.6 to 2.0 and a dielectric dissipation factor of 0.008 to 0.001, and even more preferably a dielectric constant of 2.5 to 2.0 and a dielectric dissipation factor of 0.006 to 0.001. Furthermore, compounds containing maleimide residues can be used to form resins with superior dielectric properties compared to polymerizing monomers such as maleimide-styryl resins. Furthermore, when short-time curing using photocuring or patterning is required, compound (1) can also be used in combination with an appropriate photopolymerization initiator or curing catalyst.

[0073] 11-2) Selection of main skeleton When the ring structure is phenylene, as in compound (1) obtained by the production method according to the present disclosure, compound (1) has high molecular chain rigidity and crystallinity, excellent thermal conductivity, heat resistance, and high flame retardancy. Furthermore, by introducing a side chain such as methyl into the phenylene ring, the affinity of compound (1) with solvents and with other resins can be controlled. When heat dissipation is important, compound (1) preferably has no side chains, as in the compound represented by formula (1-1-1), or, if it does have side chains, preferably has alkyl or alkoxy side chains having 1 to 4 carbon atoms, arranged symmetrically with respect to the axis of molecular vibration, as in the compound represented by formula (1-1-4) or formula (1-1-6).

[0074] 11-3) Molecular Orientation When low-dielectric resins exhibit liquid crystallinity, molecular orientation can be controlled by orientation treatment before curing. The relative dielectric constant and thermal conductivity exhibit anisotropy depending on the molecular orientation direction. When designing the dielectric constant and thermal design of electronic boards, more advanced material design becomes possible, such as designing the area directly below the heat-generating IC to have high thermal conductivity in the thickness direction, and orienting the area other than directly below the IC in the horizontal direction to spread the heat over a wide area. The orientation method can be controlled using the following methods. Methods for controlling the alignment of the mesogenic portion of liquid crystal molecules in a low-dielectric-constant resin-forming composition include treating the surface of an inorganic filler with a silane coupling agent or alignment agent that has alignment ability, and aligning using the self-alignment force of the composition itself. These methods may be used alone or in combination. Examples of alignment states controlled by such alignment control methods include homogeneous, twisted, homeotropic, hybrid, bend, and spray alignment, and the alignment state can be determined appropriately depending on the application and alignment control method. Furthermore, during film formation or molding, physical alignment can also be achieved by applying shear stress to the liquid crystal state before curing.

[0075] The orientation temperature is preferably in the range of room temperature to 250°C, more preferably room temperature to 200°C, and even more preferably room temperature to 180°C. The heat treatment time is preferably in the range of 5 seconds to 2 hours, more preferably 10 seconds to 60 minutes, and even more preferably 20 seconds to 30 minutes. If the heat treatment time is longer than the lower limit of the above range, the temperature of the layer made of composition (1) can be raised to a predetermined temperature, while if it is shorter than the upper limit of the above range, productivity is improved. Note that the above heat treatment conditions vary depending on the types and compositional ratios of the components used in composition (1), the presence and content of a polymerization initiator, etc., and therefore only indicate approximate ranges. In particular, if the temperature is higher than the polymerization initiation temperature of the polymerizable component used in composition (1), the composition will harden before orientation occurs, making it impossible to obtain a low-dielectric-constant resin with molecular chains oriented in a specific direction.

[0076] Methods for curing (polymerizing) composition (1) include radical polymerization of polymerizable groups (polymerizable components), anionic polymerization, cationic polymerization, and coordination polymerization. However, to fix the molecular alignment or helical structure, thermal polymerization and photopolymerization using light or heat, such as electron beams, ultraviolet light, visible light, or infrared light (heat rays), are suitable. Thermal polymerization is preferably carried out in the presence of a radical polymerization initiator, while photopolymerization is preferably carried out in the presence of a photoradical polymerization initiator. For example, a polymer with a fixed alignment of liquid crystal molecules can be obtained by polymerization using ultraviolet light or an electron beam in the presence of a photoradical polymerization initiator. The resulting polymer may be a homopolymer, random copolymer, alternating copolymer, block copolymer, or graft copolymer, and the type can be selected appropriately depending on the application.

[0077] When the orientation of composition (1) is fixed by photopolymerization, ultraviolet or visible light is usually used. The wavelength of the light used for light irradiation is preferably in the range of 150 to 500 nm, more preferably 250 to 450 nm, and even more preferably 300 to 400 nm. Examples of light sources for light irradiation include low-pressure mercury lamps (germicidal lamps, fluorescent chemical lamps, black lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), short-arc discharge lamps (ultra-high-pressure mercury lamps, xenon lamps, mercury-xenon lamps), and ultraviolet light-emitting diodes. Of these, metal halide lamps, xenon lamps, ultraviolet light-emitting diodes, and high-pressure mercury lamps are preferred.

[0078] The wavelength range of the irradiation light source may be selected by placing a filter or the like between the light source and the composition (1) to allow only a specific wavelength range to pass through. The amount of light irradiated from the light source is preferably 2 to 5000 mJ / cm . 2 , more preferably 10 to 3000 mJ / cm 2 , and more preferably 100 to 2000 mJ / cm 2 The temperature conditions during light irradiation are preferably set to the same range as the heat treatment temperature described above.

[0079] Conditions for fixing the orientation of composition (1) by thermal polymerization include a thermosetting temperature preferably in the range of room temperature to 350°C, more preferably room temperature to 250°C, and even more preferably 50°C to 200°C, and a curing time preferably in the range of 5 seconds to 10 hours, more preferably 1 minute to 5 hours, and even more preferably 5 minutes to 1 hour. After curing, it is preferable to slowly cool the composition to suppress stress distortion. Furthermore, a reheating treatment may be performed to relieve distortion.

[0080] The orientation-controlled cured product or the composition in the curing process may be further oriented in any direction by a mechanical operation such as stretching. The isolated polymer (1) may be dissolved in an organic solvent and mixed with other components to form a composition, which may then be aligned and cured on an alignment-treated substrate to form a film or other product. In this case, two polymers may be mixed and processed, or multiple polymers may be laminated. Preferred organic solvents include N-methyl-2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide dimethyl acetal, tetrahydrofuran, chloroform, 1,4-dioxane, bis(methoxyethyl)ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, hexafluoro-2-propanol, 2-methoxyethyl acetate, methyl ethyl ketone, cyclopentanone, and cyclohexanone. These solvents may also be mixed with a small amount of a common organic solvent, such as acetone, benzene, toluene, heptane, or methylene chloride.

[0081] When a highly linear, low-dielectric-constant resin-forming composition exhibits a liquid crystal phase over a very narrow range and exhibits high crystallinity, it forms domains with axes aligned in a certain direction, resulting in higher thermal conductivity than polymerizable compounds such as bisphenol A. Orientation and crystallinity can also be controlled by slowly curing the resin from an isotropic liquid state with the surface of a polymer sheet with aligned orientation or a crystalline resin filler present as a core for crystal growth. However, excessive crystallinity tends to reduce flexibility, so it is necessary to use a composition with appropriate crystallinity.

[0082] 12) Low-dielectric-constant resin insulating film, low-dielectric-constant resin film, and low-dielectric-constant resin sheet The polymer molded article according to the present disclosure is a molded article of a low dielectric constant resin, which is a cured product of a low dielectric constant resin-forming composition comprising the above-mentioned composition (1), and can be used as a thin film low dielectric constant resin insulating film, as well as a film-, sheet-, plate-, fiber-, or three-dimensionally shaped part (insulating part of a connector), or can be used as a coating agent, adhesive, or filler as it is. When used in the form of a thin film, film, sheet, plate, fiber, or three-dimensional molded product, the preferred shapes are films and thin films. Films and thin films can be obtained by curing composition (1) in a state where it is applied to a substrate or a release film, or sandwiched between flat plates such as substrates and molds. Alternatively, composition (1) containing an organic solvent can be applied to an orientation-treated substrate and then the organic solvent removed. Furthermore, films can be obtained by press-molding the cured product. In this specification, the thickness of a sheet is 1 mm or more, the thickness of a film is 5 μm or more but less than 1 mm, preferably 10 to 500 μm, and more preferably 20 to 300 μm, and the thickness of a thin film is less than 5 μm.

[0083] Hereinafter, a method for producing a film as a polymer molded article using the composition (1) containing an organic solvent will be specifically described. First, composition (1) is applied to a release-treated substrate, and the organic solvent is dried and removed to form a coating layer with a uniform thickness. Coating methods include spin coating, roll coating, curtain coating, flow coating, printing, microgravure coating, gravure coating, wire bar coating, dip coating, spray coating, and meniscus coating.

[0084] The organic solvent can be removed by drying at room temperature, drying on a hot plate, drying in a drying oven, or by blowing warm or hot air. The conditions for removing the organic solvent are not particularly limited; drying can be performed until the organic solvent is mostly removed and the coating layer loses its fluidity. Depending on the type and composition of the compounds used in composition (1), the liquid crystal molecules in the coating layer may be completely aligned during the drying process. In such cases, the coating layer that has undergone the drying process can be subjected to the polymerization process (curing process) without undergoing the heat treatment process described above. However, to achieve a more uniform alignment of the liquid crystal molecules in the coating layer, it is preferable to heat the coating layer that has undergone the drying process to a liquid crystal phase expression temperature to align them in the liquid crystal state, and then fix the alignment by photopolymerization or thermal polymerization.

[0085] Furthermore, when composition (1) is used as a low-dielectric-constant resin insulating film, it is also preferable to perform an alignment treatment on the substrate surface before application. Alignment treatment methods include simply forming an alignment film on the substrate, forming an alignment film on the substrate and then rubbing it with a rayon cloth, directly rubbing the substrate with a rayon cloth, oblique deposition of silicon oxide, and rubbing-free alignment using a stretched film, a photoalignment film, or an ion beam. In some cases, the desired alignment state can be achieved without treating the substrate surface. While surface treatments such as rubbing are often not performed when forming homeotropic alignment, rubbing may be performed to achieve higher alignment.

[0086] The alignment film is not particularly limited as long as it can control the alignment of the composition (1), and known alignment films can be used, such as polyimide, polyamide, polyvinyl alcohol, alkylsilane, alkylamine, or lecithin-based alignment films. For vertical alignment, a silane coupling agent is also suitable.

[0087] Any method can be used for the rubbing treatment. Usually, a method is used in which a rubbing cloth made of a material such as rayon, cotton, or polyamide is wrapped around a metal roll or the like, and the roll is moved while rotating in contact with the substrate or the alignment film, or a method is used in which the substrate side is moved while the roll is fixed.

[0088] In order to obtain a more uniform alignment, an alignment control additive may be added to the composition (1). Examples of such alignment control additives include imidazoline, quaternary ammonium salt, alkylamine oxide, polyamine derivative, polyoxyethylene-polyoxypropylene condensate, polyethylene glycol and its ester, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl amine sulfates, alkyl-substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid-formaldehyde condensates, laurylamidopropyl betaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkylethylene oxide adducts, perfluoroalkyltrimethylammonium salts, oligomers having a perfluoroalkyl and a hydrophilic group, oligomers having a perfluoroalkyl and a lipophilic group, urethanes having a perfluoroalkyl, and organosilicon compounds having a primary amino group (alkoxysilane-type, linear siloxane-type, and three-dimensionally condensed silsesquioxane-type organosilicon compounds).

[0089] Examples of the substrate 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, triacetyl cellulose or its partially saponified product, epoxy resin, phenol resin, and 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.

[0090] The film substrate may be a uniaxially stretched film or a biaxially stretched film. The film substrate may be previously subjected to a surface treatment such as saponification, corona treatment, or plasma treatment. A protective layer may be formed on the film substrate to prevent the film from being corroded by the organic solvent contained in the composition (1). An example of a material used for the protective layer is polyvinyl alcohol. Furthermore, an anchor coat layer may be formed to enhance adhesion between the protective layer and the substrate. Such an anchor coat layer may be made of either an inorganic or organic material, as long as it enhances adhesion between the protective layer and the substrate.

[0091] 13) Low-dielectric resin parts and electronic devices The low dielectric constant resin-forming composition according to the present disclosure can be used as low dielectric constant resin parts such as low dielectric constant resin insulating films, low dielectric constant resin films, low dielectric constant resin sheets, etc. Furthermore, it is useful for applications in various electronic devices such as low dielectric constant resin substrates, low dielectric constant resin coatings, low dielectric constant resin adhesives, and low dielectric constant resin molded products.

[0092] [Manufacturing method] Hereinafter, a method for producing a low dielectric constant resin-forming composition according to the present disclosure and a method for producing a low dielectric constant resin part from the composition will be specifically described.

[0093] The low-dielectric-constant resin-forming composition according to the present disclosure can be used as a liquid resin raw material in a temperature range where a liquid crystal phase or an isotropic phase is exhibited. Alternatively, it can be dissolved in an organic solvent and used as a solution. The low-dielectric-constant resin-forming composition is prepared by adding compound (1), which is a polymerizable liquid crystal compound (1), an organic solvent, an inorganic filler, and the various additives described above, as needed, and then stirring and degassing the mixture using a stirrer until the composition is uniform. For example, a rotation-revolution mixer is used to stir the mixture at 2000 rpm for 10 minutes, followed by degassing at 2200 rpm for 10 minutes. In addition to the rotation-revolution mixer, the components of the low-dielectric-constant resin-forming composition can be dispersed using a stirring motor, a crusher, a three-roll mill, a ball mill, a rotation-revolution mill, a planetary mill, a bead mill, a jet mill, or the like.

[0094] As the application method, a wet coating method is preferably used to uniformly coat the low dielectric constant resin-forming composition. Among wet coating methods, spin coating, which allows for simple and uniform film formation, is preferred when producing a small number of low dielectric constant resin parts. When productivity is important, 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 printing, flexographic printing, screen printing, rod coating, etc. are preferred. The wet coating method can be appropriately selected from these methods depending on the required film thickness, viscosity, curing conditions, etc.

[0095] When producing a sheet, a cast molding method is used in which the composition is coated onto a release-treated substrate using the method described above and then peeled off, and when producing a structure, a mold is used as needed, and resin molding methods such as press molding, injection molding, and various 3D printer molding methods (ejection lamination methods) can be used. After molding, the mold can be removed and the mold can be fully cured, or the molded product can be fully cured while still in the mold, or in the case of a molding method that does not use a mold, the molded product can be fully cured as is.

[0096] Composition (1) containing polymerizable liquid crystal compound (1) is a composition for forming a low dielectric constant resin that exhibits high heat resistance and dielectric properties such as a low dielectric constant and a low dielectric loss tangent in the high frequency range after curing, and can be prepared into a varnish-like form using no solvent or a small amount of organic solvent.In addition to the above properties, this composition for forming a low dielectric constant resin also exhibits high transparency and high heat dissipation. The cured product obtained by curing the composition not only has low dielectric properties, but also has high heat dissipation properties, transparency, and excellent properties in at least one of the following characteristics: chemical stability, heat resistance, hardness, and mechanical strength. Therefore, it is suitable for a variety of applications, such as low-dielectric circuit boards, low-dielectric antenna substrates, low-dielectric coatings, low-dielectric adhesives, and next-generation communication equipment and radar in the high-frequency range.

[0097] As described above, by using the production method according to the present disclosure, compound (1) can be obtained safely and stably in high yield and high purity, with little environmental impact, and at low cost. The composition containing the polymerizable liquid crystal compound (1) obtained by the production method according to the present disclosure is a composition for forming a low dielectric constant resin that exhibits high heat resistance and dielectric properties of a low dielectric constant and a low dielectric loss tangent in the high frequency range after curing, and further exhibits high transparency or high heat dissipation properties in addition to the above properties. The cured product obtained by the production method according to the present disclosure has, in addition to low dielectric properties, high heat dissipation and transparency, and excellent properties in at least one of characteristics such as chemical stability, heat resistance, hardness, and mechanical strength. Therefore, for example, it is suitable for various applications such as low dielectric circuit boards, low dielectric antenna substrates, low dielectric coatings, low dielectric adhesives, next-generation communication devices in the high-frequency region, and radars.

Examples

[0098] The present disclosure will be described in more detail by way of examples (including production examples of compounds, compositions, polymers, low dielectric constant resins, etc.). However, the present invention is not limited by these examples.

[0099] Using the method for producing the compound (1) according to the present disclosure, the compound was synthesized according to the procedure shown in the examples. Unless otherwise specified, the reaction was carried out under a nitrogen atmosphere. The synthesized compound was identified by methods such as NMR analysis. The properties of the compound (1) were measured by the following methods.

[0100] <NMR Analysis> For the measurement, JNM-ECZR manufactured by JEOL Ltd. was used. 1 In 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. 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.

[0101] <Gas Chromatographic Analysis> For the measurement, a GC-2014 type gas chromatograph manufactured by Shimadzu Corporation was used. For the column, 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. (currently: Keysight Technologies Inc.) was used. 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, adjusted to a 1 wt% solution, and 1 μl of the resulting solution was injected into the sample vaporization chamber. For the recorder, a GCSolution system manufactured by Shimadzu Corporation or the like was used.

[0102] <HPLC Analysis> For the measurement, a Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. For the column, a YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle size 5 μm) manufactured by WMC Co., Ltd. was used. The eluent was appropriately mixed with methanol / water or acetonitrile / water and used. 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 210 - 254 nm. The sample was dissolved in methanol or 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.

[0103] <Ultraviolet-Visible Spectrophotometric Analysis> For the measurement, a PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was set from 190 nm to 700 nm. The sample was dissolved in acetonitrile, prepared into a 0.01 mmol / L solution, placed in a quartz cell (optical path length 1 cm), and measured.

[0104] <Measurement Sample> When measuring the transition temperature (clear point, melting point, polymerization initiation temperature, etc.) and, when the compound has a liquid crystal phase, the phase structure and transition temperature, the compound itself was used as the sample.

[0105] (1) Transition temperature (℃) Measurements were performed using a high-sensitivity differential scanning calorimeter, X-DSC7000, manufactured by Hitachi High-Tech Science Corporation (formerly SII Nanotechnology Corporation). The sample was heated and cooled at a rate of 3–5°C / min, and the onset of the endothermic or exothermic peak associated with the phase change of the sample was extrapolated to determine the transition temperature. The melting point and polymerization onset temperature of the compound were also measured using this instrument. When a compound has a liquid crystalline phase, the temperature at which it transitions from a solid to a liquid crystalline phase such as a smectic or nematic phase is sometimes abbreviated as the "lower limit temperature of the liquid crystalline phase." The temperature at which a compound transitions from a crystal to a liquid is sometimes abbreviated as the "clearing point."

[0106] Crystals were represented by C. When the type of crystal could be distinguished, they were represented by C1, C2, etc. When a liquid crystal phase was present, the smectic phase was represented by S and the nematic phase by N. When the smectic phase could be distinguished into smectic A, smectic B, smectic C, or smectic F, they were represented by SA, SB, SC, or SF, respectively. Liquids (isotropic phases) were represented by I. Transition temperatures were represented, for example, as "C 50.0 N 100.0 I." This indicates that the transition temperature from the crystal to the nematic phase is 50.0°C, and the transition temperature from the nematic phase to the liquid is 100.0°C.

[0107] (2) Phase structure If the compound had a liquid crystal phase, the sample was placed on a hot plate (Mettler-Toledo FP-52 hot stage) of a melting point measurement apparatus equipped with a polarizing microscope. The sample was heated at a rate of 3°C / min, and the phase state and its changes were observed under the polarizing microscope to identify the type of phase.

[0108] [Example 1] Synthesis Example 1 of Compound (1-1-1s, n=4) ·1st stage Under a nitrogen atmosphere, TS-1 (5 wt%, 2.50 g), 6-bromo-1-hexene (50.0 g, 306.6 mmol), ethyl acetate (9 volumes, 450 mL), and methanol (1 volume, 50 mL) were added to a reaction vessel at room temperature and stirred. After ice cooling, hydrogen peroxide (34 wt%, 36.80 g, 368.0 mmol) was added dropwise and stirred at 0 °C for 6 hours. After completion of the reaction, the reaction was quenched by adding 10 wt% aqueous sodium thiosulfate solution dropwise. The quenched mixture was filtered through Celite, and the organic layer was washed once with water and twice with saturated brine, then concentrated under reduced pressure at 40 °C. The product was isolated by silica gel column chromatography (solvent: toluene) to give 2-(4-bromobutyl)oxirane (47.3 g, 264.4 mmol). The selectivity of this reaction was 98%, and the yield was 86%.

[0109] ·Second stage Under a nitrogen atmosphere, 4,4'-dihydroxybiphenyl (18.0 g, 96.7 mmol), tripotassium phosphate (51.3 g, 241.7 mmol), and N,N'-dimethylformamide (130 ml) were added to a reaction vessel and stirred at 40 °C for 30 minutes. 2-(4-bromobutyl)oxirane (42.0 g, 203.0 mmol) synthesized in the first step was added dropwise, and the mixture was stirred at 40 °C for 8 hours. After the reaction was complete, the mixture was poured into water and dissolved in toluene. The resulting organic layer was washed twice with saturated brine and concentrated under reduced pressure at 50 °C. The product was isolated by silica gel column chromatography (solvent ratio: toluene / ethyl acetate = 9 / 1) and recrystallized (solvent ratio: toluene / ethyl acetate / tetrahydrofuran = 6 / 6 / 1) to obtain the compound (32.6 g, 74.3 mmol). The purity of the purified product was 99.9% by HPLC, and no impurities were detected. The total isolated yield of the first and second steps was 66.1%. The transition temperature of this compound (1-1-1s, n=4) was C 109.9 I (°C). Compound (1-1-1s, n=4) 1 The H-NMR signals were as follows: δ(ppm;CDCl3):7.47-7.44(m,4H), 6.95-6.92(m,4H), 4.02-3.99(t,4H), 2.97-2.93( m,2H), 2.78-2.76(dd,2H), 2.51-2.49(dd,2H), 1.90-1.83(m,4H), 1.73-1.56(m,8H)

[0110] [Example 2] Synthesis Example 1 of Compound (1-1-6s, n=4) 2-(4-Bromobutyl)oxirane was obtained in the same manner as in the first step of Example 1. Next, in the second step of Example 1, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl was used instead of 4,4'-dihydroxybiphenyl, potassium carbonate was used instead of tripotassium phosphate as the base, and the reaction temperature was set at 30°C to obtain compound (1-1-6s, n=4). The purity by HPLC was 96.9%, and the impurity content was 3.0%. The transition temperature of this compound (1-1-6s, n=4) was C 99.2 I (°C). Compound (1-1-6s, n=4) 1 The H-NMR signals were as follows: δ(ppm;CDCl3):7.18(s,4H), 3.81-3.79(t,4H), 2.99-2.96(m,2H), 2.80-2.78(dd ,2H), 2-2.51(dd,2H), 2.32(s,12H), 1.92-1.86(m,4H), 1.76-1.60(m,8H) from 2.5.

[0111] [Example 3] Synthesis Example 2 of Compound (1-1-1s, n=4) In the second step of Example 1, potassium carbonate was used as the base instead of tripotassium phosphate, and the reaction temperature was set at 30° C. Compound (1-1-1s, n=4) was obtained from compound (1B). After purification, the purity by HPLC was 99.3%, and the impurity content was 0.70%.

[0112] [Example 4] Synthesis Example 3 of Compound (1-1-1s, n=4) In the second step of Example 1, potassium carbonate was used as the base instead of tripotassium phosphate, and the reaction temperature was set at 50° C. to obtain compound (1-1-1s, n=4) from compound (1B). After purification, the purity by HPLC was 92.7%, and the impurity content was 7.3%.

[0113] [Example 5] Synthesis Example 2 of Compound (1-1-6s, n=4) In the second step of Example 2, the reaction temperature was set to 50° C. to obtain compound (1-1-6s, n=4) from compound (1B). After purification, the purity by HPLC was 85.0%, and the impurity content was 15.0%.

[0114] [Examples 6 to 16] In the first step of Example 1, the reaction selectivity from compound (1A) to compound (1B) under each reaction condition was as shown in the table below. [Table 1]

[0115] As can be seen from the above examples, by using the production method according to the present disclosure, it has become possible to safely and stably produce compound (1) in high yield and high purity, i.e., without using an expensive organic peracetic acid such as mCPBA or a chlorine-based solvent, with little impurity generation and little impurity content in the final target product. [Industrial Applicability]

[0116] By producing compound (1) using the production method according to the present disclosure, compound (1) can be obtained safely and stably, with little environmental impact, and at low cost, and therefore compound (1) and a composition for forming a low dielectric constant resin containing compound (1) can be stably supplied. The low dielectric constant resin-forming composition according to the present disclosure can be used for various electronic components, such as electronic substrates for high-frequency devices, semiconductor package components, and high-frequency antenna components, which require low dielectric loss. It can be particularly suitable for use around semiconductor components that generate a lot of heat and require heat dissipation. It can also be used as a heat dissipation component in low-frequency devices that do not require low dielectric loss. Furthermore, various electronic components obtained using the low dielectric constant resin-forming composition are useful for various electronic device applications. [Explanation of symbols]

[0117] 11 Polyimide film with release agent (150mm x 150mm x 0.05mm) 12 Heat-resistant polyimide adhesive tape (80mm x 12mm x 0.05mm)

Claims

1. A method for producing the following polymerizable liquid crystal compound (1), A first step of obtaining the following compound (1B) from the following compound (1A); a second step of obtaining the polymerizable liquid crystal compound (1) from the following compound (1C) and the compound (1B): In compound (1A) and compound (1B), n is an integer from 2 to 12, X is a halogen; In the compound (1C) and the polymerizable liquid crystal compound (1), R ｍ are independently alkyl or alkoxy having 1 to 4 carbon atoms; s is independently an integer of 0 to 4, and when s is 2 or more, R ｍ may be the same or different, n is an integer from 2 to 12, p is 0 or 1; In the second step, the polymerizable liquid crystal compound (1) is obtained from the compound (1C) using the compound (1B), a base, and a solvent; the base comprises potassium carbonate, cesium carbonate, or tripotassium phosphate; In the second step, the reaction temperature is 0 to 40°C. A method for producing a polymerizable liquid crystal compound.

2. In the first step, compound (1B) is obtained from compound (1A) using a peroxide and a catalyst. The method of claim 1.

3. the peroxide includes hydrogen peroxide or peracetic acid; The catalyst comprises titanium silicalite-1 (TS-1), The method of claim 2.

4. In the first step, the solvent used includes ethyl acetate, methanol, or acetonitrile. The method of claim 2.

5. In the first step, the reaction temperature is 0 to 40°C. The method of claim 4.

6. In the first step, X is bromine. The method of claim 1.

7. The base comprises tripotassium phosphate; The method of claim 1.

8. The polymerizable liquid crystal compound (1) is a compound selected from the following compounds (1-1-1) to (1-1-6), Among compounds (1-1-1) to (1-1-6), R ｍ is independently methyl or methoxy; n is an integer from 2 to 12; The method of claim 1.

9. The polymerizable liquid crystal compound (1) is a compound selected from the following compounds (1-2-1) to (1-2-6), Among compounds (1-2-1) to (1-2-6), R ｍ is independently methyl or methoxy; s is an integer of 0 to 4, and when s is 2 or more, R ｍ may be the same or different, n is an integer from 2 to 12; The method of claim 1.

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