Polymer compounds, compositions and molded articles

Abstract

The present invention addresses the problem of providing: a polymeric compound from which it is possible to obtain a molded article having a low dielectric loss tangent; a composition; and a molded article. The polymeric compound according to the present invention exhibits liquid crystalline properties and has a repeating unit sequentially including: a rigid part formed of a combination between an aromatic part having a six-membered ring and an aromatic part having a five-membered ring; a linker part selected from group 1; a flexible part formed of an alkylene group having 2 or more carbon atoms; and a linker part selected from group 1.　Group 1: A single bond or a divalent linkage group selected from the group consisting of -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH-, -C≡C-, and combinations thereof. R represents a hydrogen atom or an alkyl group.

Description

[Technical Field]

[0001] The present invention relates to a polymeric compound, a composition, and a molded article. [Background technology]

[0002] Liquid crystal polymer films made of polymer liquid crystals (liquid crystal polymers) have been attracting attention as materials for flexible printed circuit (FPC) substrates, etc., due to their excellent electrical properties (low dielectric constant, low dielectric loss) in the high frequency range (GHz band) and low transmission loss in circuits.

[0003] For example, Patent Document 1 describes "a liquid crystal polymer composition containing 100 parts by mass of a liquid crystal polymer and 0.1 to 20 parts by mass of a polyarylate resin, the liquid crystal polymer composition having a melt tension of 3 mN or more and a dielectric loss tangent of 0.0015 or less as measured at 1 GHz using a stick-shaped test piece having a length of 85 mm, a width of 1.75 mm, and a thickness of 1.75 mm" ([Claim 1]). It also describes a liquid crystal polyester containing, as the liquid crystal polymer, repeating units represented by the following formulas (I) to (III): [wherein Ar1 and Ar2 each represent one or more divalent aromatic groups, and p, q, and r each represent the composition ratio (mol %) of each repeating unit in the liquid crystal polyester (A), satisfying the following conditions: 35≦p≦90, 5≦q≦30, and 5≦r≦30] ([Claim 3]). [ka] [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-193261 Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors have studied the liquid crystal polymer described in Patent Document 1 and have found that there is room for improvement in reducing the dielectric loss tangent of molded articles (such as films) made using the polymer.

[0006] Therefore, an object of the present invention is to provide a polymer compound, a composition, and a molded article from which a molded article with a low dielectric loss tangent can be obtained. [Means for solving the problem]

[0007] As a result of intensive research to achieve the above object, the present inventors have found that a molded article with a low dielectric loss tangent can be obtained by using a polymer compound having a repeating unit containing, in this order, a rigid part consisting of a combination of an aromatic part having a 6-membered ring and an aromatic part having a 5-membered ring, a specified linker part, a flexible part consisting of an alkylene group having 2 or more carbon atoms, and the specified linker part, and have completed the present invention. That is, it has been found that the above object can be achieved by the following configuration.

[0008] [1] A rigid part consisting of a combination of an aromatic part having a 6-membered ring and an aromatic part having a 5-membered ring; A linker part selected from the following Group 1; a flexible part consisting of an alkylene group having two or more carbon atoms; A polymer compound exhibiting liquid crystallinity, having a repeating unit containing, in this order: Group 1: a single bond or a divalent linking group selected from the group consisting of -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH-, -C≡C-, and combinations thereof, wherein R represents a hydrogen atom or an alkyl group. However, the rigid part is composed of an aromatic part having two or more of the above-mentioned six-membered rings and an aromatic part having one or more of the above-mentioned five-membered rings, and has a structure in which the aromatic parts having two or more of the above-mentioned six-membered rings are not adjacent to each other. In the flexible part, one or more -CH2- groups constituting the alkylene group other than the terminal group may be substituted with -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH- or -C≡C-. R represents a hydrogen atom or an alkyl group. [2] The polymer compound according to [1], wherein the aromatic moiety having a 6-membered ring is represented by the formula (1) or (2) described below. [3] The polymer compound according to [1] or [2], wherein the aromatic moiety having a five-membered ring is represented by the formula (3) or (4) described below. [4] a rigid part consisting of a combination of an aromatic part having a 6-membered ring and an aromatic part having a 5-membered ring; A linker part selected from the following Group 1; a flexible part consisting of an alkylene group having two or more carbon atoms; A polymer compound having a repeating unit containing, in this order, a linker part selected from the following Group 1: the aromatic moiety having a 6-membered ring is a 1,3-phenylene group or a 1,4-phenylene group; A polymer compound in which the aromatic moiety having the five-membered ring is a 1,2,4-oxadiazole-3,5-diyl group. Group 1: a single bond or a divalent linking group selected from the group consisting of -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH-, -C≡C-, and combinations thereof, wherein R represents a hydrogen atom or an alkyl group. However, the rigid part is composed of an aromatic part having two or more of the above-mentioned six-membered rings and an aromatic part having one or more of the above-mentioned five-membered rings, and has a structure in which the aromatic parts having two or more of the above-mentioned six-membered rings are not adjacent to each other. In the flexible part, one or more -CH2- groups constituting the alkylene group other than the terminal group may be substituted with -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH- or -C≡C-. R represents a hydrogen atom or an alkyl group. [5] A composition containing the polymer compound according to any one of [1] to [4]. [6] A molded article obtained by processing the polymer compound according to any one of [1] to [4] or the composition according to [5]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a polymer compound, a composition, and a molded article that can give a molded article with a low dielectric loss tangent. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The following description of the components may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0011] In this specification, each component may be a single substance corresponding to the component, or two or more substances may be used in combination. When two or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination, unless otherwise specified. In addition, the bonding direction of the divalent group (e.g., —O—CO—) described in this specification is not particularly limited. 1 -L 2 -L 3 In the bond of L 2 When is -O-CO-, L 1 The position where it is bonded to the side is *1, L 3 If the position bonded to the side is *2, then L 2 may be *1-O-CO-*2 or *1-CO-O-*2.

[0012] In addition, in this specification, the phrase "optionally having a substituent" includes not only embodiments in which no substituent is present, but also embodiments in which one or more substituents are present. Here, examples of the substituent include those described in the following Substituent Group A. <Substituent group A> The substituent group A is a halogen atom (for example, a fluorine atom, a chlorine atom, or a bromine atom, preferably a chlorine atom or a fluorine atom, more preferably a fluorine atom), an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 1- norbornyl group, 1-adamantyl group), alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably an alkenyl group having 2 to 18 carbon atoms, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, for example, a phenyl group, a naphthyl group), heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably a heterocyclic group having 1 to 18 carbon atoms, for example, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, a 1-pyrazolyl group, a benzotriazol-1-yl group), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably a silyl group having 3 to 18 carbon atoms, for example, a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, a t-hexyldimethylsilyl group), a hydroxy group, a cyano group, a nitro group, an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably an alkoxy group having 1 to 24 carbon atoms, for example, a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxy group, group, a cycloalkyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group), an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, for example, a phenoxy group, a 1-naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, for example, a 1-phenyltetrazole-5-oxy group, a 2-tetrahydropyranyloxy group), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably a silyloxy group having 1 to 18 carbon atoms, for example,trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably an acyloxy group having 2 to 24 carbon atoms, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably an alkoxycarbonyloxy group having 2 to 24 carbon atoms, for example, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, a cycloalkyloxycarbonyloxy group, an oxy group, for example, a cyclohexyloxycarbonyloxy group; an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, for example, a phenoxycarbonyloxy group); a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably a carbamoyloxy group having 1 to 24 carbon atoms, for example, an N,N-dimethylcarbamoyloxy group, an N-butylcarbamoyloxy group, an N-phenylcarbamoyloxy group, an N-ethyl-N-phenylcarbamoyloxy group, a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably a sulfamoyloxy group having 1 to 24 carbon atoms, for example, an N,N-diethylsulfamoyloxy group, an N-propylsulfamoyloxy group), an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably an alkylsulfonyloxy group having 1 to 24 carbon atoms, for example, a methylsulfonyloxy group, a hexadecylsulfonyloxy group, or a cyclohexylsulfonyloxy group), an arylsulfonyloxy group (preferably a group having 6 to 32 carbon atoms, more preferably a an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group; an acyl group (preferably an acyl group having 1 to 48 carbon atoms, more preferably an acyl group having 1 to 24 carbon atoms, such as a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group, or a cyclohexanoyl group); an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 24 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, or a cyclohexyloxycarbonyl group);2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group), carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably a carbamoyl group having 1 to 24 carbon atoms, such as a carbamoyl group, N,N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N,N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, an amino group (preferably an amino group having 32 or less carbon atoms, more preferably an amino group having 24 or less carbon atoms, for example, amino, methylamino, N,N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably an anilino group having 6 to 24 carbon atoms, for example, an anilino group, N-methylanilino), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably an heterocyclic amino group having 1 to 18 carbon atoms, for example, an amino group, methylamino, N,N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), an amino group, for example, a 4-pyridylamino group; a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an acetamido group, a benzamido group, a tetradecanamido group, a pivaloylamido group, or a cyclohexanamido group); a ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably a ureido group having 1 to 24 carbon atoms, for example, a ureido group, an N,N-dimethylureido group, or an N-phenylureido group); an imido group (preferably an imido group having 36 or less carbon atoms, more preferably a carbon atom having 24 or less carbon atoms, for example, an N-succinimido group); an N-phthalimido group, an N-phthalimido group), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, or a cyclohexyloxycarbonylamino group), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably an aryloxycarbonylamino group having 7 to 24 carbon atoms, for example, a phenoxycarbonylamino group),sulfonamido groups (preferably sulfonamido groups having 1 to 48 carbon atoms, more preferably sulfonamido groups having 1 to 24 carbon atoms, for example, methanesulfonamido groups, butanesulfonamido groups, benzenesulfonamido groups, hexadecanesulfonamido groups, and cyclohexanesulfonamido groups), sulfamoylamino groups (preferably sulfamoylamino groups having 1 to 48 carbon atoms, more preferably sulfamoylamino groups having 1 to 24 carbon atoms, for example, N,N-dipropylsulfamoylamino groups and N-ethyl-N-dodecylsulfamoylamino groups), azo groups (preferably having 1 to 32 carbon atoms, more preferably azo groups having 1 to 24 carbon atoms, for example, a phenylazo group, a 3-pyrazolylazo group), alkylthio groups (preferably alkylthio groups having 1 to 48 carbon atoms, more preferably alkylthio groups having 1 to 24 carbon atoms, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group), arylthio groups (preferably arylthio groups having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, a phenylthio group), heterocyclic thio groups (preferably heterocyclic thio groups having 1 to 32 carbon atoms, more preferably heterocyclic thio groups having 1 to 18 carbon atoms, for example, a 2-benzothiazolylthio group, a 2-pyridylthio group, a 1-benzothiazolyl ... -phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, a dodecanesulfinyl group), arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably an arylsulfinyl group having 6 to 24 carbon atoms, for example, a phenylsulfinyl group), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, for example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, a phenylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, an octylsulfonyl group, a cyclohexylsulfonyl group), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably an arylsulfonyl group having 6 to 24 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably an sulfamoyl group having 24 or less carbon atoms, such as a sulfamoyl group, an N,N-dipropylsulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group,N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl, N-(2-ethylhexyl)sulfamoyl), phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably a phosphonyl group having 1 to 24 carbon atoms, for example, a phenoxyphosphonyl group, an octyloxyphosphonyl group, a phenylphosphonyl group), phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably a phosphinoylamino group having 1 to 24 carbon atoms, for example, a diethoxyphosphinoylamino group, a dioctyloxyphosphinoylamino group), epoxy group, (meth)acrylolyl group, -NHCOCH3, -SON2NHC2H4OCH3, -NHSO2CH3,

[0013] [High molecular compound] The polymer compound according to the first aspect of the present invention (hereinafter also simply referred to as "the polymer compound of the present invention") comprises: a rigid part consisting of a combination of an aromatic part having a 6-membered ring and an aromatic part having a 5-membered ring; A linker part selected from the following Group 1; a flexible part consisting of an alkylene group having two or more carbon atoms; A linker part selected from the following Group 1; The polymer compound has a repeating unit containing the above in this order (hereinafter also simply referred to as "specific repeating unit") and exhibits liquid crystallinity. Group 1: a single bond or a divalent linking group selected from the group consisting of -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH-, -C≡C-, and combinations thereof, wherein R represents a hydrogen atom or an alkyl group. However, the rigid part is composed of an aromatic part having two or more of the above-mentioned six-membered rings and an aromatic part having one or more of the above-mentioned five-membered rings, and has a structure in which the aromatic parts having two or more of the above-mentioned six-membered rings are not adjacent to each other. In the flexible part, one or more -CH2- groups constituting the alkylene group other than the terminal group may be substituted with -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH- or -C≡C-. R represents a hydrogen atom or an alkyl group. Here, "exhibiting liquid crystallinity" means that a liquid crystal state is expressed when the polymer compound is kept alone at room temperature, when it is heated, or when it is cooled after heating, or that a liquid crystal state is expressed when the polymer compound is dissolved alone in a solvent.

[0014] In the present invention, as described above, by using a polymer compound having a specific repeating unit, a molded article having a low dielectric loss tangent can be obtained. Although the details of this are not clear, the present inventors speculate as follows. That is, in the polymer compound of the present invention, it is believed that the linker part (e.g., -CO-O-) adjacent to the rigid part exists on the same plane as the rigid part and is maintained in a state where it is difficult to move, making it difficult for dielectric relaxation to occur, and as a result, it is believed that a molded product with a low dielectric dissipation factor can be obtained. The specific repeating units contained in the polymer compound of the present invention will be described in detail below.

[0015] [Specific repeating unit] As described above, the specific repeating unit contained in the polymer compound of the present invention is a repeating unit containing a rigid part, a linker part, a flexible part, and a linker part in this order.

[0016] <Rigid part> The rigid part contained in the specific repeating unit is a part consisting of a combination of an aromatic part having a 6-membered ring and an aromatic part having a 5-membered ring, and is a part that has a structure in which the aromatic parts having two or more of the 6-membered rings and the aromatic part having one or more of the 5-membered rings are not adjacent to each other. Here, examples of the aromatic ring constituting the aromatic part having the six-membered ring include a benzene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, and a tetrazine ring. Furthermore, examples of the aromatic ring constituting the aromatic part having the above-mentioned five-membered ring include a thiophene ring, a furan ring, a pyrrole ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a triazole ring, and an oxadiazole ring. In the present invention, a fused ring containing a 6-membered ring (e.g., a naphthalene ring, a benzofuran ring, etc.) corresponds to an "aromatic part having a 6-membered ring", and a fused ring containing a 5-membered ring but not a 6-membered ring (e.g., a pyrrolopyrrole ring, etc.) corresponds to an "aromatic part having a 5-membered ring". The aromatic ring may have a substituent, and the substituent may be bonded to another group to form a condensed ring. Examples of the substituent include those described in the above-mentioned substituent group A.

[0017] In the present invention, the aromatic part having the six-membered ring preferably has a structure represented by the following formula (1) or (2) because a molded article having a lower dielectric loss tangent can be obtained, and more preferably has a structure represented by the following formula (2) because a molded article having an even lower dielectric loss tangent can be obtained. [ka]

[0018] In the above formulas (1) and (2), * represents a bonding position. In the above formula (1), A 11 , A 12 , A 13 and A 14 each independently represents a methine group or a nitrogen atom. In the above formula (2), A 21 , A 22 , A 23 and A 24 each independently represents a methine group or a nitrogen atom.

[0019] Examples of the structure represented by the above formula (1) include a 1,4-phenylene group, a pyridine-2,5-diyl group, and a pyrazine-2,5-diyl group. Examples of the structure represented by the above formula (2) include a 1,3-phenylene group, a pyridine-2,6-diyl group, and a pyrazine-2,6-diyl group.

[0020] In the present invention, the aromatic part having the above-mentioned five-membered ring is preferably a structure represented by the following formula (3) or (4) because it is possible to obtain a molded product having a lower dielectric tangent, and more preferably a structure represented by the following formula (4) because it is easy to synthesize. [ka]

[0021] In the above formulas (3) and (4), * represents a bonding position. In the above formula (3), A 31 and A 32 each independently represents a methine group or a nitrogen atom. In the above formula (3), X 1 represents an oxygen atom, a sulfur atom, or —NR. R represents a hydrogen atom or an alkyl group. In the above formula (4), A 41 and A 42 each independently represents a methine group or a nitrogen atom. In the above formula (4), X 2 represents an oxygen atom, a sulfur atom, or —NR. R represents a hydrogen atom or an alkyl group.

[0022] Examples of the structure represented by the above formula (3) include a thiophene-2,5-diyl group, a furan-2,5-diyl group, an oxazole-2,5-diyl group, and a 1,3,4-oxadiazole-2,5-diyl group. Examples of the structure represented by the above formula (4) include a thiophene-2,4-diyl group, an oxazole-2,4-diyl group, an oxazole-2,4-diyl group, and a 1,2,4-oxadiazole-3,5-diyl group.

[0023] The rigid part contained in the specific repeating unit can be synthesized by referring to the method for synthesizing the compound represented by general formula (1) or (1a) described in JP-A-2010-244038, for example.

[0024] <Linker part> The linker part contained in the specific repeating unit is a part selected from Group 1 below. Group 1: a single bond or a divalent linking group selected from the group consisting of -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH-, -C≡C-, and combinations thereof, wherein R represents a hydrogen atom or an alkyl group.

[0025] Specific examples of the divalent linking group in Group 1 include -O-, -S-, -CO-, -CO-O-, and -NR 1 -, -CH=CH-, -C≡C-, -SO2-O-, -CO-NR 2 -, etc. 1 and R 2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. In the present invention, the linker part is preferably a single bond, *-CO-O-, or *-CO-NR because it can provide a molded article with a lower dielectric tangent. 2 - is preferable. In addition, * indicates the bonding position with the rigid part.

[0026] <Flexible Part> The flexible part contained in the specific repeating unit is a part consisting of an alkylene group having 2 or more carbon atoms, and one or more -CH2- constituting the alkylene group other than the terminal may be substituted with -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH- or -C≡C-. R represents a hydrogen atom or an alkyl group.

[0027] Examples of alkylene groups having 2 or more carbon atoms include linear, branched, or cyclic alkylene groups having 2 to 12 carbon atoms. Specific examples thereof include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, a heptylene group, and a cyclohexane-1,4-diyl group.

[0028] [Other repeating units] The polymer compound of the present invention is not particularly limited as long as it has the above-mentioned specific repeating unit and is a polymer that exhibits liquid crystallinity, and may have other repeating units in addition to the above-mentioned specific repeating unit. When the polymer compound of the present invention has other repeating units, the content of the specific repeating units is preferably 80 mol % or more, more preferably 85 mol % or more, and even more preferably 90 to 99 mol % in terms of molar ratio.

[0029] [Molecular weight] The weight average molecular weight (Mw) of the polymer compound of the present invention is not particularly limited, but is preferably from 1,000 to 500,000, more preferably from 2,000 to 300,000, for the reason that handling becomes easier. Here, the weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

[0030] [Liquid Crystallinity] The liquid crystal phase exhibited by the polymer compound of the present invention may be any of a nematic phase, a discotic nematic phase, a smectic phase and a columnar phase, but preferably exhibits at least a nematic phase or a discotic nematic phase. The temperature range in which the liquid crystal phase is exhibited is preferably 0°C to 450°C, and from the viewpoint of ease of handling and suitability for production, it is preferably 30°C to 400°C.

[0031] The polymer compound according to the second aspect of the present invention is a rigid part consisting of a combination of an aromatic part having a 6-membered ring and an aromatic part having a 5-membered ring; A linker part selected from the following Group 1; a flexible part consisting of an alkylene group having two or more carbon atoms; A polymer compound having a repeating unit containing, in this order, a linker part selected from the following Group 1: the aromatic moiety having a 6-membered ring is a 1,3-phenylene group or a 1,4-phenylene group; The polymer compound is one in which the aromatic moiety having the five-membered ring is a 1,2,4-oxadiazole-3,5-diyl group. Group 1: a single bond or a divalent linking group selected from the group consisting of -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH-, -C≡C-, and combinations thereof, wherein R represents a hydrogen atom or an alkyl group. However, the rigid part is composed of an aromatic part having two or more of the above-mentioned six-membered rings and an aromatic part having one or more of the above-mentioned five-membered rings, and has a structure in which the aromatic parts having two or more of the above-mentioned six-membered rings are not adjacent to each other. In the flexible part, one or more -CH2- groups constituting the alkylene group other than the terminal group may be substituted with -O-, -S-, -CO-, -SO2-, -NR-, -CH=CH- or -C≡C-. R represents a hydrogen atom or an alkyl group.

[0032] That is, the polymer compound according to the second aspect of the present invention is a polymer in which, among the polymer compounds according to the first aspect of the present invention described above, the aromatic moiety having a 6-membered ring is limited to a 1,3-phenylene group or a 1,4-phenylene group, and the aromatic moiety having a 5-membered ring is limited to a 1,2,4-oxadiazole-3,5-diyl group, with respect to the rigid moiety contained in the specific repeating unit. The polymer compound according to the second aspect of the present invention is a polymer that is not limited to the requirement of "exhibiting liquid crystallinity" as defined for the polymer compound according to the first aspect of the present invention. The polymer compound according to the second aspect of the present invention is preferably a polymer compound that exhibits liquid crystallinity, similar to the polymer compound according to the first aspect of the present invention.

[0033] [Manufacturing method] The method for producing the polymer compounds according to the first and second aspects of the present invention is not particularly limited, and the polymer compounds can be obtained by subjecting polymerizable monomers to a known polycondensation method (e.g., melt acidolysis, slurry polymerization, etc.) that forms an ester bond or an amide bond. An example of the production method is shown in the following formula: In the formula, Rig represents the rigid part, and Fle represents the flexible part. [ka]

[0034] Specific examples of the polymer compounds according to the first and second aspects of the present invention are shown below. [ka] JPEG0007789746000006.jpg43109JPEG0007789746000007.jpg43109JPEG0007789746000008.jpg43108JPEG0007789746000009.jpg44108JPE G0007789746000010.jpg43108JPEG0007789746000011.jpg43108JPEG0007789746000012.jpg43108JPEG0007789746000013.jpg44105JPEG000 7789746000014.jpg43116JPEG0007789746000015.jpg43112JPEG0007789746000016.jpg43106JPEG0007789746000017.jpg43111JPEG000778 9746000018.jpg43124JPEG0007789746000019.jpg43107JPEG0007789746000020.jpg4398JPEG0007789746000021.jpg44126JPEG00077897460 00022.jpg45129JPEG0007789746000023.jpg43116JPEG0007789746000024.jpg45135JPEG0007789746000025.jpg43147JPEG00077897460000 26.jpg44147JPEG0007789746000027.jpg45135JPEG0007789746000028.jpg45135JPEG0007789746000029.jpg43136JPEG0007789746000030.j pg44141JPEG0007789746000031.jpg45133JPEG0007789746000032.jpg45133JPEG0007789746000033.jpg43128JPEG0007789746000034.jpg4 2147JPEG0007789746000035.jpg42147JPEG0007789746000036.jpg42105JPEG0007789746000037.jpg42105JPEG0007789746000038.jpg42104

[0035] [Components] The composition of the present invention is a composition containing the polymer compound according to the first or second aspect of the present invention. Here, the content of the polymer compound is preferably 10 to 97% by mass, more preferably 40 to 95% by mass, and even more preferably 60 to 95% by mass, based on the total solid content (100% by mass) of the composition.

[0036] [Resin component] The composition of the present invention preferably contains a resin component. Examples of the resin component include epoxy resin, polyacrylate resin, phenol resin, and polyimide resin, and among these, it is preferable that the resin contains epoxy resin or polyacrylate resin.

[0037] Specific examples of epoxy resins include bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol novolac-type epoxy resins, phenol novolac-type epoxy resins, tert-butyl-catechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, cresol novolac-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and halogenated epoxy resins.

[0038] Polyarylate resins are resins whose constituent units are aromatic dicarboxylic acids or derivatives thereof and dihydric phenols or derivatives thereof, and can be produced by methods such as solution polymerization, melt polymerization, and interfacial polymerization. Examples of aromatic dicarboxylic acids constituting the polyarylate resin include terephthalic acid and isophthalic acid, but a mixture of the two is preferable from the viewpoints of melt processability and overall performance. The blending ratio of terephthalic acid and isophthalic acid in the mixture is not limited, but a mass ratio of terephthalic acid / isophthalic acid of 9 / 1 to 1 / 9 is preferred. Considering the balance between melt processability and performance, a blending ratio of 7 / 3 to 3 / 7 is preferred, with 1 / 1 being particularly preferred. Examples of dihydric phenols that constitute polyarylate resins include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydrodiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl, and hydroquinone. 2,2-bis(4-hydroxyphenyl)propane [bisphenol A] is preferred. These may be used alone or in combination. Furthermore, small amounts of ethylene glycol, propylene glycol, etc. may be used in combination with these dihydric phenols.

[0039] [Curing agent] When the composition of the present invention contains an epoxy resin, it preferably contains a curing agent together with the epoxy resin. The curing agent is not particularly limited, and examples thereof include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. The curing agent may be used alone or in combination of two or more kinds in any ratio.

[0040] [Filling material] The compositions of the present invention may contain fillers. The filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. The filler may be used alone or in combination of two or more kinds in any ratio.

[0041] [Other additives] The composition of the present invention may contain other additives, such as flame retardants; organic fillers; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; thickeners; antifoaming agents; leveling agents; adhesion promoters; and colorants.

[0042] The composition of the present invention can provide a cured product that has a low dielectric loss tangent and good adhesion to a conductor layer. Therefore, the composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and can be more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for an interlayer insulating layer of a printed wiring board). Furthermore, the composition of the present invention can be used in a wide range of applications requiring a resin composition, such as adhesive films, sheet-like laminate materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, and component embedding resins.

[0043] The method for preparing the composition of the present invention is not particularly limited, and examples thereof include a method in which the ingredients are mixed and dispersed using a rotary mixer or the like, with the addition of a solvent or the like as necessary.

[0044] [Molded products] The molded article of the present invention is a molded article obtained by processing the polymer compound according to the first or second aspect of the present invention described above, or the composition of the present invention described above. Examples of such molded articles include those formed in the various uses of the composition of the present invention described above. [Example]

[0045] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0046] [Example 1] The following rigid monomer 1 was synthesized with reference to Comparative Example 1 of JP-A-2010-244038. The obtained rigid monomer 1 (5 g) was mixed with an equimolar amount of propanediol, and 0.1% by mass of paratoluenesulfonic acid was added under a nitrogen atmosphere. The mixture was heated at 250°C for 3 hours and then heated under reduced pressure at 250°C for 10 hours to obtain the target product, LCP1 shown below. The obtained LCP1 was confirmed to exhibit liquid crystallinity under a polarizing microscope. The obtained LCP1 was melt-cast into a film having a thickness of 100 μm. The dielectric loss tangent (25°C, 15 GHz) of the prepared film was 0.0005.

[0047] Rigid Monomer 1 [ka]

[0048] LCP1 [ka]

[0049] [Comparative Example 1] The following acrylate monomer A was synthesized with reference to Example 1 of JP-A-2007-204705.

[0050] Acrylate Monomer A [ka]

[0051] To the obtained acrylate monomer (20 g), 0.1 mass % of a polymerization initiator IRGACURE819 (manufactured by BASF) was added, and the mixture was heated to 90° C. and kneaded. The resulting mixture was melt-formed into a film having a thickness of 100 μm at 90° C., then cooled to 72° C., and irradiated with ultraviolet light having a wavelength of 365 nm (5 J) in a nitrogen atmosphere to produce a film. The dielectric loss tangent (25°C, 15 GHz) of the prepared film was 0.01.

Claims

1. a rigid part consisting of a combination of an aromatic part having a 6-membered ring and an aromatic part having a 5-membered ring; A linker part selected from Group 1 below; a flexible part consisting of an alkylene group having two or more carbon atoms; A polymer compound exhibiting liquid crystallinity, having a repeating unit containing, in this order: Group 1: a single bond, or —O—, —S—, —CO—, or —SO ２ A divalent linking group selected from the group consisting of -, -NR-, -CH=CH-, -C≡C-, and combinations thereof, where R represents a hydrogen atom or an alkyl group. However, the rigid part is composed of an aromatic part having two or more of the six-membered rings and an aromatic part having one or more of the five-membered rings, and has a structure in which the aromatic parts having two or more of the six-membered rings are not adjacent to each other. The flexible part is a —CH group other than the terminal of the alkylene group. ２ At least one of - is -O-, -S-, -CO-, or -SO ２ It may be substituted with -, -NR-, -CH=CH- or -C≡C-, and R represents a hydrogen atom or an alkyl group.

2. The polymer compound according to claim 1 , wherein the aromatic moiety having a 6-membered ring is represented by the following formula (1) or (2): 【Chemistry 1】 Here, in the formulas (1) and (2), * indicates the bond position. A １１ , A １２ , A １３ and A １４ each independently represents a methine group or a nitrogen atom. A ２１ , A ２２ , A ２３ and A ２４ each independently represents a methine group or a nitrogen atom.

3. The polymer compound according to claim 1 or 2, wherein the aromatic moiety having a five-membered ring is represented by the following formula (3) or (4): 【Chemistry 2】 Here, in the formulas (3) and (4), * indicates the bond position. A ３１ and A ３２ each independently represents a methine group or a nitrogen atom. X １ represents an oxygen atom, a sulfur atom, or —NR, where R represents a hydrogen atom or an alkyl group. A ４１ and A ４２ each independently represents a methine group or a nitrogen atom. X ２ represents an oxygen atom, a sulfur atom, or —NR, where R represents a hydrogen atom or an alkyl group.

4. a rigid part consisting of a combination of an aromatic part having a 6-membered ring and an aromatic part having a 5-membered ring; A linker part selected from Group 1 below; a flexible part consisting of an alkylene group having two or more carbon atoms; A polymer compound having a repeating unit containing, in this order, a linker part selected from the following Group 1: the aromatic moiety having a 6-membered ring is a 1,3-phenylene group, A polymer compound, wherein the aromatic moiety having a five-membered ring is a 1,2,4-oxadiazole-3,5-diyl group. Group 1: a single bond, or —O—, —S—, —CO—, or —SO ２ A divalent linking group selected from the group consisting of -, -NR-, -CH=CH-, -C≡C-, and combinations thereof, where R represents a hydrogen atom or an alkyl group. However, the rigid part is composed of an aromatic part having two or more of the six-membered rings and an aromatic part having one or more of the five-membered rings, and has a structure in which the aromatic parts having two or more of the six-membered rings are not adjacent to each other. The flexible part is a —CH group other than the terminal of the alkylene group. ２ At least one of - is -O-, -S-, -CO-, or -SO ２ It may be substituted with -, -NR-, -CH=CH- or -C≡C-, and R represents a hydrogen atom or an alkyl group.

5. A composition comprising the polymer compound according to any one of claims 1 to 4.

6. A molded article obtained by processing the polymer compound according to any one of claims 1 to 4 or the composition according to claim 5.

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