JP2015196803A - thermosetting aromatic polyester composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting aromatic polyester composition which is excellent in molding such as transfer molding without increasing viscosity due to the progress of the crosslinking reaction during heating and kneading.SOLUTION: There is provided a thermosetting aromatic polyester composition which comprises the following aromatic polyester (A) and the following crosslinking compound (B), where the aromatic polyester (A) has a softening point lower by 30°C or more than that of the crosslinking compound. The aromatic polyester (A): an aromatic polyester having at least one group or structure selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic cyclic group and a conjugated diene structure at the molecular chain terminal, the crosslinking compound (B): a crosslinking compound having a group or a structure of the aromatic polyester (A) which is a functional group reactive with a hydroxyl group, an acyloxy group, an aromatic cyclic group and a conjugated diene structure and a thermally polymerizable functional group in the molecule.

Description

  The present invention relates to a thermosetting aromatic polyester composition.

  Liquid crystal polymers represented by liquid crystal polyester are excellent in various properties such as heat resistance, moldability, chemical resistance, and mechanical strength, and thus are used in various applications such as electric / electronic parts and automobile parts. In recent years, attention has been focused on a thermosetting liquid crystal polymer material that can form a cured product having extremely high heat resistance by being cured by heating.

  As a method for producing a liquid crystal polyester, a method by transesterification involving acetylation and deacetylation of a monomer is known. As a method for producing a thermosetting liquid crystal polyester, there is known a method in which a curing agent such as a thermosetting agent is added to liquid crystal polyester and melt mixed. Transfer molding is known as a semiconductor sealing technique.

  As a thermosetting liquid crystal polymer material, for example, a material in which a liquid crystal oligomer such as a main chain thermotropic liquid crystal ester is end-capped with a phenylacetylene, phenylmaleimide or nadiimide reactive terminal group is known (see Patent Documents 1 to 3). ). In addition, a material obtained by reacting a thermosetting liquid crystal oligomer having one or more soluble structural units in the main chain and having a thermosetting group at one or more terminals of the main chain with a specific fluorine compound ( A material obtained by reacting the thermosetting liquid crystal oligomer with a nano filler whose surface is substituted with an alkoxide metal compound is known (see Patent Document 5).

  As a thermosetting liquid crystal polymer material, for example, a material in which a crosslinkable group is bonded to a terminal of a liquid crystal polymer via a spacer unit is also known (see Patent Document 6). A material having radically polymerizable groups such as unsubstituted or substituted maleimide, unsubstituted or substituted nadiimide, ethynyl, and benzocyclobutene at both ends of the liquid crystal polyester is also known (see Patent Document 7).

JP-T-2004-509190 US Pat. No. 6,993,940 US Pat. No. 7,507,784 JP 2011-1111619 A JP 2011-084707 A Japanese translation of PCT publication No. 2002-521354 US Pat. No. 5,114,612

  Aromatic polyester is a thermoplastic resin and cannot be used because it deforms in applications where it is exposed to a temperature higher than the molding temperature. Therefore, it is necessary to introduce a thermosetting functional group having crosslinkability into the aromatic polyester to form a thermosetting resin. As a method for obtaining a thermosetting aromatic polyester having a crosslinkable group as described above, a solution method is often used, and productivity is generally poor. In order to obtain a thermosetting aromatic polyester with high productivity, a method (melt mixing) of heating and kneading a compound having an aromatic polyester and a crosslinkable group at a temperature equal to or higher than the melting point of the aromatic polyester is employed. ing. However, aromatic polyesters generally have a very high melting point (for example, 280 ° C. or higher), and the viscosity increases due to the progress of the crosslinking reaction during melt mixing, which may make molding such as transfer molding difficult.

  Accordingly, an object of the present invention is to allow aromatic polyester to be melt-mixed at a relatively low temperature (for example, 200 ° C. or less), the viscosity does not increase due to the progress of the crosslinking reaction during melt-mixing, and the moldability such as transfer molding is improved. It is to provide an excellent thermosetting aromatic polyester composition.

  As a result of intensive studies to solve the above problems, the present inventors have used a specific aromatic polyester in which the softening temperature of the aromatic polyester is lower by 30 ° C. or more than the curing temperature of the compound having a crosslinkable group, It knead | mixed in the comparatively low temperature range (for example, 100-200 degreeC) which a crosslinking reaction does not advance, discovered that a thermosetting aromatic polyester composition could be obtained, and completed this invention.

That is, this invention contains the following aromatic polyester (A) and the following crosslinkable compound (B), and the softening temperature of the said aromatic polyester (A) is 30 degreeC or more rather than the curing temperature of the said crosslinkable compound (B). A thermosetting aromatic polyester composition characterized by being low is provided.
Aromatic polyester (A): aromatic polyester having at least one group or structure selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic cyclic group, and a conjugated diene structure at the molecular chain terminal Crosslinkable compound (B ): A functional group that reacts with a hydroxyl group, an acyloxy group, an aromatic cyclic group, or a conjugated diene structure, a functional group that reacts with the group or structure of the aromatic polyester (A), and a thermally polymerizable functional group. Crosslinkable compound in the molecule

  Furthermore, this invention provides the said thermosetting aromatic polyester composition whose softening temperature of the said aromatic polyester (A) is 40-200 degreeC.

  Furthermore, this invention provides the said thermosetting aromatic polyester composition whose curing temperature of the said crosslinkable compound (B) is 70-250 degreeC.

  Furthermore, this invention provides the said thermosetting aromatic polyester composition whose said crosslinkable compound (B) is a maleimide derivative.

  Furthermore, this invention provides the said thermosetting aromatic polyester composition whose average degree of polymerization of the said aromatic polyester (A) is 3-30.

  Furthermore, the present invention provides the thermosetting aromatic polyester composition, wherein the amount of the crosslinkable compound (B) is 10 to 300 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). provide.

  Since the thermosetting aromatic polyester composition of the present invention has the above-described configuration, the viscosity does not increase due to the progress of the crosslinking reaction during heating and kneading, and the thermosetting aromatic polyester composition has excellent moldability such as transfer molding. Can be obtained. Moreover, since aromatic polyester is included as an essential component, the obtained cured product is excellent in processability, dimensional stability, low linear expansion, high thermal conductivity, low hygroscopicity, and dielectric properties.

[Thermosetting aromatic polyester composition]
The thermosetting aromatic polyester composition of the present invention includes the following aromatic polyester (A) and the following crosslinkable compound (B), and the softening temperature of the aromatic polyester (A) is that of the crosslinkable compound (B). It is characterized by being 30 ° C. lower than the curing temperature. The softening temperature of the aromatic polyester (A) in the present invention means a temperature at which the composition can be prepared by kneading the aromatic polyester (A) and the crosslinkable compound (B). For example, a hot stage is attached. It can be measured by the method described in the examples using a polarizing microscope. The curing temperature of the crosslinkable compound (B) is the exothermic peak temperature by DSC measurement.
Aromatic polyester (A): aromatic polyester having at least one group or structure selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic cyclic group, and a conjugated diene structure at the molecular chain terminal Crosslinkable compound (B ): A functional group that reacts with a hydroxyl group, an acyloxy group, an aromatic cyclic group, or a conjugated diene structure, a functional group that reacts with the group or structure of the aromatic polyester (A), and a thermally polymerizable functional group. Crosslinkable compound in the molecule

[Aromatic polyester (A)]
As described above, the aromatic polyester (A) in the present invention is at least one group or structure selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic cyclic group, and a conjugated diene structure at the molecular chain terminal ( An aromatic polyester having a “reactive functional group (a)”. The aromatic polyester (A) is a polymer (polymer or oligomer) having a polyester structure, and its melt (for example, a melt at 450 ° C. or lower) exhibits a liquid crystal polyester (thermoplastic). Often a tropic liquid crystal polymer).

  When the aromatic polyester (A) has a hydroxyl group at the molecular chain end, it is not particularly limited, but it may have a hydroxyl group only at one end (one end) of the molecular chain, or both ends ( It may have a hydroxyl group at both ends. Moreover, the aromatic polyester (A) may have a hydroxyl group in a portion other than the molecular chain end.

  The hydroxyl group that the aromatic polyester (A) has at the molecular chain terminal may be a phenolic hydroxyl group or an alcoholic hydroxyl group. Among these, from the viewpoint of the heat resistance of the cured product, the hydroxyl group that the aromatic polyester (A) has at the molecular chain terminal is preferably a phenolic hydroxyl group. The “phenolic hydroxyl group” in the present specification includes a hydroxyl group bonded to other aromatic rings (naphthalene ring, anthracene ring, etc.) in addition to a hydroxyl group bonded to a substituted or unsubstituted benzene ring. .

  When the aromatic polyester (A) has an acyloxy group at the molecular chain end, it is not particularly limited. However, the aromatic polyester (A) may have an acyloxy group only at one end (one end) of the molecular chain, or both of the molecular chains. The terminal (both terminals) may have an acyloxy group. In addition, the aromatic polyester (A) may have an acyloxy group in a portion other than the molecular chain end.

  Examples of the acyloxy group that the aromatic polyester (A) has at the molecular chain end include an acetyloxy group (acetoxy group), a propionyloxy group, and a butyryloxy group. Especially, it is preferable that the acyloxy group which the aromatic polyester (A) has in the molecular chain terminal from the viewpoint of the versatility and the reactivity of the raw material to be used is an acetoxy group.

  When the aromatic polyester (A) has an aromatic cyclic group at the end of the molecular chain, it is not particularly limited, but it may have an aromatic cyclic group only at one end (one end) of the molecular chain. In addition, an aromatic cyclic group may be present at both ends (both ends) of the molecular chain. In addition, the aromatic polyester (A) may have an aromatic cyclic group at a portion other than the molecular chain end. In addition, the aromatic cyclic group which the aromatic polyester (A) has at the molecular chain end may be bonded with one or more substituents per ring. Examples of the substituent include publicly known or commonly used substituents, and are not particularly limited. Examples thereof include those exemplified as the substituents that the aromatic hydroxycarboxylic acid described later may have.

  When the aromatic polyester (A) has a phenolic hydroxyl group at the molecular chain end, the aromatic polyester (A) is also an aromatic polyester having a hydroxyl group at the molecular chain end and has an aromatic ring at the molecular chain end. It is also an aromatic polyester.

  When the aromatic polyester (A) has a conjugated diene structure at the end of the molecular chain, it is not particularly limited, but it may have a conjugated diene structure only at one end (one end) of the molecular chain, Both ends (both ends) may have a conjugated diene structure. In addition, the aromatic polyester (A) may have a conjugated diene structure in a portion other than the molecular chain end.

  Examples of the conjugated diene structure that the aromatic polyester (A) has at the molecular chain end include a chain conjugated diene structure and a cyclic conjugated diene structure. Examples of the chain conjugated diene structure include structures derived from 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. It is done. Examples of the cyclic conjugated diene structure include structures derived from 1,3-cyclopentadiene, 1,3-cyclohexadiene, furan and derivatives thereof, thiophene and derivatives thereof, and the like.

  The aromatic polyester (A) may have two or more selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic ring, and a conjugated diene structure at the molecular chain terminal. For example, the aromatic polyester (A) may have both a hydroxyl group and an acyloxy group at the molecular chain end. Specifically, the aromatic polyester (A) has a hydroxyl group at one end of the molecular chain and at the other end. It may have an acyloxy group.

  In the aromatic polyester (A), the ratio of hydroxyl groups is 5 to 100%, the ratio of acyloxy groups is 0 to 90%, and the ratio of groups other than hydroxyl groups and acyloxy groups is 0 to 90% with respect to the entire terminal groups at the molecular chain terminals. %, The proportion of hydroxyl groups is 10 to 90%, the proportion of acyloxy groups is 10 to 90%, and the proportion of groups other than hydroxyl groups and acyloxy groups is more preferably 0 to 80%.

  The aromatic polyester (A) includes at least a structural unit (repeating structural unit) derived from at least one aromatic compound selected from the group consisting of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic diol. An aromatic polyester is preferred.

Examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, Examples include 5-hydroxy-1-naphthoic acid, 4′-hydroxy [1,1′-biphenyl] -4-carboxylic acid, and derivatives thereof. Examples of the derivative include compounds in which the aromatic ring (aromatic ring) of the aromatic hydroxycarboxylic acid is substituted with a substituent having 0 to 20 carbon atoms (preferably 0 to 10 carbon atoms). Examples of the substituent include an alkyl group [eg, methyl group, ethyl group, etc.]; alkenyl group [eg, vinyl group, allyl group, etc.]; alkynyl group [eg, ethynyl group, propynyl group, etc.]; halogen atom [ For example, chlorine atom, bromine atom, iodine atom, etc.]; hydroxyl group; alkoxy group [eg, C _1-6 alkoxy group such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isobutyloxy group (preferably Is a C _1-4 alkoxy group, etc.]; an alkenyloxy group [for example, a C _2-6 alkenyloxy group such as an allyloxy group (preferably a C _2-4 alkenyloxy group), etc.]; an aryloxy group [eg, a phenoxy group , tolyloxy group, such as a naphthyloxy group, C _1-4 alkyl groups on the aromatic ring, C _2-4 alkenyl group, a halogen Child, such as good C _6-14 aryloxy group which may have a substituent such as C _1-4 alkoxy group]; aralkyloxy group [for example, benzyloxy group, C _7-18 aralkyloxycarbonyl such as phenethyloxy Group]; acyloxy group [eg, C _1-12 acyloxy group such as acetyloxy group, propionyloxy group, (meth) acryloyloxy group, benzoyloxy group, etc.]; mercapto group; alkylthio group [eg, methylthio group, ethylthio] A C _1-6 alkylthio group such as a group (preferably a C _1-4 alkylthio group)]; an alkenylthio group [eg, a C _2-6 alkenylthio group such as an arylthio group (preferably a C _2-4 alkenylthio group) etc.]; arylthio group [e.g., phenylthio group, tolylthio group, such as a naphthylthio group, C _1-4 alkyl groups on the aromatic ring, C _2-4 alkenyl Group, a halogen atom, C _1-4, etc. Good C _6-14 arylthio group which may have a substituent such as an alkoxy group]; aralkylthio group [for example, benzylthio group, C _7-18 such phenethylthio group Aralkylthio group etc.]; carboxyl group; alkoxycarbonyl group [eg C _1-6 alkoxy-carbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, etc.]; aryloxycarbonyl group [eg, C _6-14 aryloxy-carbonyl group such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc.]; Aralkyloxycarbonyl group [for example, C _7-18 aralkyloxy-carbonyl group such as benzyloxycarbonyl group, etc. ]; Amino group; mono- or dialkylamino [For example, methylamino group, ethylamino group, dimethylamino group, such as mono- or di -C _1-6 alkylamino group such as a diethylamino group]; mono- or diphenylamino group [such as phenylamino group]; an acylamino group [ For example, C _1-11 acylamino group such as acetylamino group, propionylamino group, benzoylamino group, etc.]; Epoxy group-containing group [eg, glycidyl group, glycidyloxy group, 3,4-epoxycyclohexyl group, etc.]; Oxetanyl group containing group [e.g., ethyloxetanyl group]; an acyl group [e.g., an acetyl group, a propionyl group, a benzoyl group]; these two or more optionally C _1-6 alkylene group; oxo group; isocyanate group And a group bonded via each other. In addition, aromatic polyester (A) may have 1 type of the structural unit derived from aromatic hydroxycarboxylic acid, and may have 2 or more types.

  Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, [1,1′-biphenyl] -4,4′-dicarboxylic acid. Examples include acid, 4,4′-oxybis (benzoic acid), 4,4′-thiobis (benzoic acid), 4- [2- (4-carboxyphenoxy) ethoxy] benzoic acid, and derivatives thereof. Examples of the derivatives include compounds in which the aromatic ring of the aromatic dicarboxylic acid is substituted with a substituent having 0 to 20 carbon atoms (preferably 0 to 10 carbon atoms). As said substituent, the thing similar to the substituent in aromatic hydroxycarboxylic acid is illustrated. In addition, aromatic polyester (A) may have 1 type of the structural unit derived from aromatic dicarboxylic acid, and may have 2 or more types.

  Examples of the aromatic diol include 4,4′-dihydroxybiphenyl, hydroquinone, resorcinol, 2,6-naphthalenediol, 1,5-naphthalenediol, [1,1′-biphenyl] -4,4′-diol. 4,4′-dihydroxydiphenyl ether, bis (4-hydroxyphenyl) methanone, bisphenol A, bisphenol F, bisphenol S, (phenylsulfonyl) benzene, [1,1′-biphenyl] -2,5-diol, and these And derivatives thereof. Examples of the derivative include compounds in which the aromatic ring of the aromatic diol is substituted with a substituent having 0 to 20 carbon atoms (preferably 0 to 10 carbon atoms). As said substituent, the thing similar to the substituent in aromatic hydroxycarboxylic acid is illustrated. In addition, aromatic polyester (A) may have 1 type of the structural unit derived from aromatic diol, and may have 2 or more types.

  The aromatic polyester (A) is an aromatic polyester containing a structural unit U derived from at least one aromatic compound selected from the group consisting of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic diol, The ratio of the structural unit U to the total structural units constituting the aromatic polyester skeleton (when the structural unit is two or more, the ratio of the total amount thereof) is preferably 60% by weight or more, and 80% by weight or more. Is more preferable, and 90% by weight or more is more preferable. In particular, it is preferable that the aromatic polyester (A) is substantially composed only of structural units derived from the above-mentioned aromatic compounds (aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol). When the ratio is in the above range, the aromatic polyester (A) is less susceptible to chemical changes due to the structural units derived from other monomers introduced, and the cured product has heat resistance and moisture resistance (hydrolysis resistance). ) Is less likely to occur.

  The aromatic polyester (A) is composed of structural units other than the structural units described above (structural units derived from aromatic hydroxycarboxylic acids, structural units derived from aromatic dicarboxylic acids, structural units derived from aromatic diols) ("other structural units"). The other structural unit may be, for example, a structural unit derived from an aromatic diamine, a structural unit derived from an aromatic amine or aromatic amide having a phenolic hydroxyl group, and the like. Is mentioned.

  Examples of the aromatic diamine include 1,4-benzenediamine, 1,3-benzenediamine, 4-methyl-1,3-benzenediamine, 4- (4-aminobenzyl) phenylamine, 4- (4- Aminophenoxy) phenylamine, 3- (4-aminophenoxy) phenylamine, 4′-amino-3,3′-dimethyl [1,1′-biphenyl] -4-ylamine, 4′-amino-3,3 ′ -Bis (trifluoromethyl) [1,1'-biphenyl] -4-ylamine, 4-amino-N- (4-aminophenyl) benzamide, 4-[(4-aminophenyl) sulfonyl] phenylamine, bis ( 4-aminophenyl) methanone, and derivatives thereof. Examples of the derivative include compounds in which the aromatic ring of the aromatic diamine is substituted with a substituent having 0 to 20 carbon atoms (preferably 0 to 10 carbon atoms). As said substituent, the thing similar to the substituent in aromatic hydroxycarboxylic acid is illustrated. In addition, aromatic polyester (A) may have 1 type of the structural unit derived from aromatic diamine, and may have 2 or more types.

  Examples of the aromatic amine or aromatic amide having a phenolic hydroxyl group include 4-aminophenol, 4-acetamidophenol, 3-aminophenol, 3-acetamidophenol, 6-amino-2-naphthol, and 5-amino- Examples thereof include 1-naphthol, 4′-hydroxy- [1,1′-biphenyl] -4-amine, 4-amino-4′-hydroxydiphenylmethane, and derivatives thereof. Examples of the derivative include compounds in which the aromatic ring of the aromatic amine having the phenolic hydroxyl group is substituted with a substituent having 0 to 20 carbon atoms (preferably 0 to 10 carbon atoms). As said substituent, the thing similar to the substituent in aromatic hydroxycarboxylic acid is illustrated. In addition, aromatic polyester (A) may have 1 type of the structural unit derived from the aromatic amine or aromatic amide which has a phenolic hydroxyl group, and may have 2 or more types. .

  Ratio of the above-mentioned aromatic compound (aromatic diamine, aromatic amine or aromatic amide having a phenolic hydroxyl group) to all structural units constituting the aromatic polyester (A) (when the number of the structural units is two or more) The ratio of the total amount thereof is not particularly limited, but is preferably 30% by weight or less (for example, 0 to 30% by weight), more preferably 10% by weight or less, and still more preferably 5% by weight or less. When the ratio is 30% by weight or less, the hygroscopic resistance (hydrolysis resistance) of the cured product is difficult to decrease.

  The aromatic polyester (A) can be produced by polymerizing the above aromatic compound (monomer) by a known or conventional method, and the production method is not particularly limited. Specifically, for example, the above-mentioned aromatic hydroxycarboxylic acid, aromatic diol, aromatic amine having a phenolic hydroxyl group, an aromatic compound having a hydroxyl group or an amino group, such as an aromatic diamine, an excess amount of fatty acid anhydride It can be produced by reacting the acylated product obtained by the reaction with an aromatic compound having a carboxyl group such as aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid (transesterification reaction, amide exchange reaction). More specifically, for example, it can be produced by the method described in JP-A-2007-119610. Moreover, as aromatic polyester (A), a commercial item can also be used.

  As a method for producing an aromatic polyester (A) having a hydroxyl group at the molecular chain end, for example, a method of controlling the monomer composition so that the hydroxyl group becomes excessive (for example, excess aromatic diol as a monomer component) Etc.) and the like. Specifically, in the monomer constituting the aromatic polyester (A) used for producing the aromatic polyester (A), a hydroxyl group and a functional group that undergoes a condensation reaction with the hydroxyl group (derived from a carboxyl group or a carboxyl group). The ratio of the hydroxyl group to the group (ester group, acid anhydride group, acid halide group, etc.), amino group, etc.) is not particularly limited. 02 mol or more (for example, 1.02 to 100 mol) is preferable, 1.05 mol or more is more preferable, and 1.10 mol or more is more preferable. When the hydroxyl group is 1.02 mol or more, the molecular weight does not become too high, and the time required for the thermosetting reaction can be suppressed. More specifically, the ratio of the aromatic diol to the total amount (100 mol%) of the monomer constituting the aromatic polyester (A) is not particularly limited, but is preferably 3 to 25 mol%, and preferably 4 to 25 mol. % Is more preferable.

  Moreover, as a method for producing an aromatic polyester (A) having an acyloxy group at the molecular chain terminal, for example, the hydroxyl group of the aromatic polyester (A) having a hydroxyl group at the molecular chain terminal is converted to a known or conventional acylating agent ( For example, a method of acylating using a fatty acid anhydride such as acetic anhydride, an acid halide, or the like.

  As a method for producing an aromatic polyester (A) having an aromatic cyclic group at the molecular chain end, for example, a substantially aromatic compound (for example, the above-mentioned aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid as a monomer) can be used. Acid, aromatic diol, etc.) and aromatic compounds with respect to the reactive functional group at the end of the aromatic polyester having a reactive functional group such as hydroxyl group or carboxyl group at the molecular chain end. Examples thereof include a method of forming an aromatic ring at the molecular chain terminal by reaction (for example, addition reaction).

  As a method for producing an aromatic polyester (A) having a conjugated diene structure at the molecular chain terminal, for example, for the reactive functional group of the aromatic polyester having a reactive functional group such as a hydroxyl group or a carboxyl group at the terminal A compound having a conjugated diene structure and capable of reacting (for example, addition reaction) with the reactive functional group (for example, (1-methyl-2,4-cyclopentadien-1-yl) methanol) ) And the like.

  Although the average degree of polymerization of aromatic polyester (A) is not specifically limited, 3-30 are preferable, 3-25 are more preferable, and 3-20 are more preferable. When the average degree of polymerization is in the above range, the softening temperature is easily adjusted appropriately. The average degree of polymerization of the aromatic polyester (A) can be determined, for example, by the amine decomposition HPLC method described in JP-A No. 5-271394.

  The molecular weight of the aromatic polyester (A) is not particularly limited, but is preferably 500 to 20000, more preferably 500 to 10,000, and further preferably 500 to 5000. When the molecular weight is in the above range, the curing reactivity is unlikely to decrease, and the softening temperature can be easily adjusted appropriately. In addition, the molecular weight of aromatic polyester (A) can be calculated | required by GPC measurement, for example.

  Although the glass transition temperature (Tg) of aromatic polyester (A) is not specifically limited, 30-150 degreeC is preferable, 40-120 degreeC is more preferable, 50-100 degreeC is further more preferable. When the glass transition temperature is in the above range, the cured product is hardly inferior in heat resistance, and the aromatic polyester (A) and the crosslinkable compound (B) are melt-mixed at a relatively low temperature (for example, 200 ° C. or lower). Can do. In addition, the glass transition temperature of aromatic polyester (A) can be measured by thermal analysis and dynamic viscoelasticity measurement, such as DSC and TGA.

  The melting point (Tm) of the aromatic polyester (A) may or may not be a clearly measurable melting point, and is not particularly limited, but is preferably 250 ° C. or lower (for example, 80 to 250 ° C.), and 220 ° C. or lower. Is more preferable, 200 ° C. or lower is further preferable, and 180 ° C. or lower is particularly preferable. When the melting point is 250 ° C. or less, the aromatic polyester (A) and the crosslinkable compound (B) can be melt-mixed at a relatively low temperature (for example, 200 ° C. or less), and the viscosity is rapidly decreased by the crosslinking reaction. It is hard to cause. In addition, melting | fusing point of aromatic polyester (A) can be measured by thermal analysis and dynamic viscoelasticity measurement, such as DSC and TGA, for example.

  Although the softening temperature of aromatic polyester (A) is not specifically limited, 40-200 degreeC is preferable, 50-180 degreeC is more preferable, 80-160 degreeC is further more preferable. When the softening temperature is in the above range, the aromatic polyester (A) and the crosslinkable compound (B) can be melt-mixed at a relatively low temperature (for example, 200 ° C. or less), and the crosslinkable compound ( The crosslinking reaction of B) does not occur easily. The softening temperature of the aromatic polyester (A) is a temperature at which the composition can be prepared by kneading the aromatic polyester (A) and the crosslinkable compound (B). For example, a polarizing microscope equipped with a hot stage is used. And can be measured by the method described in the examples.

  The softening temperature of the aromatic polyester (A) can be controlled by changing the composition and degree of polymerization of the aromatic polyester. As the composition of the aromatic polyester, among the above aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, and aromatic diols, the higher the ratio of the aromatic diol, the lower the softening temperature and the higher the ratio of the aromatic dicarboxylic acid. Then, the softening temperature tends to increase. Moreover, when the ratio of polycyclic aromatic rings such as naphthalene and anthracene in the aromatic polyester skeleton increases, the softening temperature tends to increase. As the degree of polymerization of the aromatic polyester, the softening temperature tends to increase as the degree of polymerization increases. For example, the softening temperature in the case of a pentamer is 90 to 100 ° C., and the softening temperature in the case of a 10-mer. Is 140-150 degreeC, and the softening temperature in the case of a 20-mer is 170-180 degreeC.

[Crosslinking Compound (B)]
The crosslinkable compound (B) constituting the thermosetting aromatic polyester composition of the present invention functions as a thermosetting agent, and the aromatic polyester (A) is a molecule in the molecule (in one molecule) as described above. A reactive functional group (a) (at least one selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic cyclic group, and a conjugated diene structure) having a functional group at the chain end (“reactive functional group ( b) ") and a thermopolymerizable functional group (thermosetting functional group).

  The reactive functional group (b) is not particularly limited as long as it is a functional group capable of reacting with the reactive functional group (a) of the aromatic polyester (A), but from the viewpoint of the temperature at which the reaction proceeds. For example, an α, β-unsaturated carbonyl group (eg, a ketone group having a carbon-carbon unsaturated bond between the α-position and the β-position of the carbonyl carbon, and a carbon-carbon between the α-position and the β-position of the carbonyl carbon. An ester group having an unsaturated bond, an amide group having a carbon-carbon unsaturated bond between the α-position and the β-position of the carbonyl carbon, and an imide having a carbon-carbon unsaturated bond between the α-position and the β-position of the carbonyl carbon Group, etc.); epoxy group; maleimide group; ester group; acid anhydride group (for example, maleic anhydride group); carboxyl group, acid chloride and the like. In addition, a crosslinkable compound (B) may have 1 type of the said reactive functional group (b), and may have 2 or more types.

  Of the reactive functional groups (b) exemplified above, α, β-unsaturated carbonyl group, epoxy group, maleimide group, ester group, acid anhydride group, and carboxyl group are reactive functional groups that react with hydroxyl groups. Group (functional group reactive with hydroxyl group). Moreover, among the reactive functional groups (b) exemplified above, the carboxyl group is a reactive functional group that reacts with an acyloxy group (against an acyloxy group reactive functional group). Furthermore, among the reactive functional groups (b) exemplified above, a maleimide group and an acid anhydride group (particularly a maleic anhydride group) react with an aromatic ring (cycloaddition reaction). And / or a reactive functional group that reacts with a conjugated diene structure (cycloaddition reaction).

  The number of reactive functional groups (b) in the crosslinkable compound (B) may be one or more and is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5.

  The thermopolymerizable functional group is not particularly limited as long as it is a functional group that can be polymerized by heating, but in terms of the temperature at which the polymerization reaction proceeds, for example, a maleimide group, a nadiimide group, a phthalimide group, a cyanate group, Nitrile group, phthalonitrile group, styryl group, ethynyl group, propargyl ether group, benzocyclobutene group, biphenylene group, epoxy group, benzoxazine group, isocyanate group, benzopyran group, 3-phenylmaleimide group, phenylethynyl group, and these Or a substituted or derivative thereof. In addition, as said substituted body or derivative | guide_body, the thermopolymerizable functional group etc. which the substituent (For example, the substituent in the above-mentioned aromatic hydroxycarboxylic acid etc.) couple | bonded with the said thermopolymerizable functional group are mentioned. Among them, a maleimide group is preferable in that part or all of the structure functions also as the reactive functional group (b). In addition, the crosslinkable compound (B) may have one of the above thermopolymerizable functional groups, or may have two or more.

  The number of the thermally polymerizable functional groups in the crosslinkable compound (B) is not particularly limited as long as it is 1 or more, but 1 to 10 is preferable, and 1 to 5 is more preferable.

  The crosslinkable compound (B) needs to have at least one reactive functional group (b) and at least one thermopolymerizable functional group. For example, when the crosslinkable compound (B) has a maleimide group that functions as both a reactive functional group (b) and a thermopolymerizable functional group, it is necessary to have two or more maleimide groups. The α carbon-β carbon double bond in the maleimide group disappears by reacting with the hydroxyl group, aromatic cyclic group, or conjugated diene structure of the aromatic polyester (A), and no longer functions as a thermopolymerizable functional group. It is because it becomes impossible.

Examples of the crosslinkable compound (B) include one or more reactive functional groups (b) and one or more thermopolymerizable functional groups in the molecule, and a carbon number of 100 or less (preferably 10 to 50). ). Examples of such a crosslinkable compound (B) include a hydrocarbon group, a heterocyclic group, or two or more of these bonded via one or more of a linking group (a divalent group having one or more atoms). And compounds formed by the above groups. Examples of the hydrocarbon group, the heterocyclic group, and a group in which two or more of these are bonded via one or more of the linking groups include, for example, groups exemplified as X ¹ and X ² in the following formula (i) (organic groups) ) And the like.

Specifically, as the crosslinkable compound (B), a compound represented by the following formula (i) (α, β-unsaturated carbonyl group (when the unsaturated group is a double bond)) and a thermally polymerizable functional group Compound).

X ¹ and X ² in the above formula (i) are the same or different and represent an organic group. The organic group is not particularly limited, but includes a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted heterocyclic group, a group in which two or more of these groups are bonded via one or more linking groups, and the like. Can be mentioned.

Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and a corresponding divalent or higher group. Examples of the alkyl group include C _1-20 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group (preferably C _{1 -10} alkyl group, more preferably C _1-4 alkyl group). Examples of the alkenyl group include vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, and 2-pentenyl groups. C _2-20 alkenyl groups (preferably C _2-10 alkenyl groups, more preferably C _2-4 alkenyl groups) such as 3-pentenyl group, 4-pentenyl group, and 5-hexenyl group. Examples of the alkynyl group include C _2-20 alkynyl groups such as ethynyl group and propynyl group (preferably C _2-10 alkynyl group, more preferably C _2-4 alkynyl group).

Examples of the alicyclic hydrocarbon group include a C _3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group, and a corresponding divalent or higher group; a cyclohexenyl group. C _3-12 cycloalkenyl groups and corresponding divalent or higher groups; bicycloheptanyl groups, bicycloheptenyl groups, and corresponding divalent or higher divalent groups such as C _4-15 bridged cyclic carbonization A hydrogen group etc. are mentioned.

Examples of the aromatic hydrocarbon group include a C _6-14 aryl group (particularly a C _6-10 aryl group) such as a phenyl group and a naphthyl group, and a corresponding divalent or higher group.

Examples of the hydrocarbon group include a group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group such as a cyclohexylmethyl group, a methylcyclohexyl group, and a corresponding divalent or higher valent group are bonded; C _7-18 aralkyl groups such as benzyl and phenethyl groups (especially C _7-10 aralkyl groups), C _6-10 aryl-C _2-6 alkenyl groups such as cinnamyl groups, C _1-4 alkyls such as tolyl groups Examples thereof include a C _2-4 alkenyl-substituted aryl group such as a substituted aryl group and a styryl group, and a group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group such as a corresponding divalent or higher valent group are bonded. As a substituent which the said hydrocarbon group may have, the group similar to the substituent in the above-mentioned aromatic hydroxycarboxylic acid is mentioned, for example.

  Examples of the heterocyclic group include a pyridyl group, a furyl group, a thienyl group, and a bivalent or higher group corresponding to these. As a substituent which the said heterocyclic group may have, the group similar to the substituent in the above-mentioned aromatic hydroxycarboxylic acid is mentioned, for example.

Examples of the hydrocarbon group include two or more hydrocarbon groups having one or more linking groups [a divalent group having one or more atoms; for example, an ester bond, an ether bond, a carbonate bond, an amide bond, a thioether bond, Examples include a group linked by a thioester bond, —NR— (wherein R represents a hydroxyl group or an alkyl group), an imide bond, a group in which two or more of these are bonded, and the like. Examples of the heterocyclic group also include a group in which two or more heterocyclic groups are directly bonded. The organic group (X ¹ , X ² ) is a group in which one or more of the hydrocarbon groups and one or more of the heterocyclic groups are bonded directly and / or through one or more linking groups. May be.

X ¹ and X ² in the above formula (i) may be bonded to each other to form a ring together with the three carbon atoms shown in the formula. Specifically, examples of the ring structure formed by X ¹ and X ² and the three carbon atoms shown in the formula include a cycloalkenone ring, a cycloalkenedione ring, a flange-on ring (maleic anhydride ring). ), A pyrrole dione ring (maleimide ring), a lactone ring having a carbon-carbon unsaturated bond between the α-position and the β-position of the carbonyl carbon, and a carbon-carbon unsaturated bond between the α-position and the β-position of the carbonyl carbon. And a lactam ring.

R ¹ and R ² in the above formula (i) are the same or different and represent a hydrogen atom or an alkyl group which may have a substituent. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group. And a linear or branched alkyl group having 1 to 20 carbon atoms. Examples of the substituent that the alkyl group may have include the same groups as the substituent in the above-described aromatic hydroxycarboxylic acid (excluding the alkyl group).

Y ¹ and Y ² in the above formula (i) are the same or different and represent a thermally polymerizable functional group. Examples of the thermally polymerizable functional group include the above-described thermally polymerizable functional groups. Further, n1 and n2 in the above formula (i) are the same or different and represent an integer of 0 or more. However, the sum of n1 and n2 (n1 + n2) represents an integer of 1 or more (that is, the compound represented by the formula (i) has one or more thermopolymerizable functional groups in the molecule). As a total of n1 and n2, for example, an integer of 1 to 10 (more preferably an integer of 1 to 5) is preferable. Further, the bonding positions of Y ¹ and Y ² with respect to X ¹ and X ² are not particularly limited. In the case n1 (or n2) is an integer of 2 or more, plural Y ¹ (or Y ²⁾ may be the same or different.

Further, as the crosslinkable compound (B), a compound represented by the following formula (ii) (a compound having an α, β-unsaturated carbonyl group (when the unsaturated group is a triple bond) and a thermally polymerizable functional group) Is mentioned.

X ³ and X ⁴ in the above formula (ii) are the same or different and represent an organic group. Examples of the organic group include the same organic groups as those exemplified as X ¹ and X ^{2 in} formula (i). Similarly to X ¹ and X ² in the above formula (i), X ³ and X ⁴ in the above formula (ii) are bonded to each other to form a ring together with the three carbon atoms shown in the formula. It may be.

Y ³ and Y ⁴ in the above formula (ii) are the same or different and represent a thermally polymerizable functional group. Examples of the thermally polymerizable functional group include the above-described thermally polymerizable functional groups. Moreover, n3 and n4 in the above formula (ii) are the same or different and represent an integer of 0 or more. However, the sum of n3 and n4 (n3 + n4) represents an integer of 1 or more (that is, the compound represented by the above formula (ii) has one or more thermopolymerizable functional groups in the molecule). As a total of n3 and n4, for example, an integer of 1 to 10 (more preferably an integer of 1 to 5) is preferable. Further, the bonding positions of Y ³ and Y ⁴ to X ³ and X ⁴ are not particularly limited. In the case n3 (or n4) is an integer of 2 or more, plural Y ³ (or Y ⁴⁾ may be the same or different.

Moreover, as a crosslinkable compound (B), the compound (The carboxylic acid which has a thermopolymerizable functional group, or its derivative (s)) represented by following formula (iii) is mentioned.

R ^a in the above formula (iii) represents a hydroxyl group (—OH), an alkoxy group, a halogen atom, or an acyloxy group. As said alkoxy group, C1-C20 alkoxy groups, such as a methoxy group, an ethoxy group, a propoxy group, its derivative (s), etc. are mentioned, for example. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, a butyryloxy group, and a group represented by the following formula. X ⁵ , Y ⁵ and n5 in the following formula are the same as those in the above formula (iii).

X ⁵ in the above formula (iii) represents an organic group. Examples of the organic group include the same organic groups as those exemplified as X ¹ and X ^{2 in} formula (i). Y ⁵ in the above formula (iii) represents a thermally polymerizable functional group. Examples of the thermally polymerizable functional group include the above-described thermally polymerizable functional groups. Moreover, n5 in the said formula (iii) shows an integer greater than or equal to 1. For example, n5 is preferably an integer of 1 to 10 (more preferably an integer of 1 to 5). Further, the bonding position of Y ⁵ to X ⁵ is not particularly limited. In the case n5 is an integer of 2 or more, the plurality of Y ^5, may be the same or may be different.

Moreover, as a crosslinkable compound (B), the compound (epoxy compound which has a thermopolymerizable functional group) represented by a following formula (iv) is mentioned.

X ⁶ in the above formula (iv) represents an organic group. Examples of the organic group include the same organic groups as those exemplified as X ¹ and X ^{2 in} formula (i). Y ⁶ in the above formula (iv) represents a thermally polymerizable functional group. Examples of the thermally polymerizable functional group include the above-described thermally polymerizable functional groups. N6 in the above formula (iv) represents an integer of 1 or more. For example, n6 is preferably an integer of 1 to 10 (more preferably an integer of 1 to 5). Further, the bonding position of Y ⁶ to X ⁶ is not particularly limited. In the case n6 is an integer of 2 or more, plural Y ⁶ may be the same or different.

R < ³ > -R < ⁵ > in the said formula (iv) is the same or different, and shows the alkyl group which may have a hydrogen atom or a substituent. Examples of the alkyl group that may have a substituent include the same groups as those exemplified as R ¹ and R ² in the above formula (i).

  Although it does not restrict | limit especially as a crosslinkable compound (B), A maleimide derivative is preferable.

［式（１）中のＲ¹は、炭素数１〜２０の直鎖状又は分岐鎖状アルキレン基、炭素数３〜８のシクロアルキレン基、炭素数６〜１５のアリーレン基又はこれらが２以上、連結基を介して、又は介することなく結合した基を表す］ Examples of the maleimide derivative include compounds having 100 or less (preferably 10 to 50) carbon atoms. Among them, the maleimide derivative is not particularly limited, but a compound that is a compound represented by the following formula (1) is preferable from the viewpoint of compatibility with the aromatic polyester (A).

[R ¹ in Formula (1) is a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, an arylene group having 6 to 15 carbon atoms, or two or more thereof. Represents a group bonded via or without a linking group.]

The linking group is not particularly limited, but is an ether bond (—O—), a thioether bond (—S—), a sulfonyl bond (—SO ₂ —), an amide bond (—NHCO—), an ester bond (—COO—). ), An acyl bond (—CO—) and the like. The alkylene group in the formula (1) preferably has 1 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. The cycloalkylene group in the formula (1) preferably has 4 to 6 carbon atoms. The arylene group in the formula (1) preferably has 6 carbon atoms (phenylene group).

  Specific examples of the maleimide derivative include 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane as an aromatic bismaleimide compound containing three or more aromatic rings (phenylene groups) in one molecule. , Bis [4-maleimide (4-phenoxyphenyl)] sulfone, 1,1 ′-[1,4-phenylenebis (oxy-4,1-phenylene)] bismaleimide, 1,1 ′-[sulfonylbis (4 , 1-phenyleneoxy-3,1-phenylene)] bismaleimide, bis [4- (3-maleimidophenoxy) phenyl] ketone, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3 -Maleimidophenoxy) benzene, 1,1 '-[oxybis (4,1-phenylenethio-4,1-phenylene)] bismaleimide, 1,1'-[ 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluoro [1,1′-biphenyl] -4,4′-diyl) bis (oxy-3,1-phenylene)] bis And maleimide. Among them, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis [4-maleimido (4-phenoxyphenyl)] sulfone, 1,3-bis (4-maleimidophenoxy) benzene, 1,3 -Bis (3-maleimidophenoxy) benzene is preferred.

  Specifically, as the maleimide derivative, as an aromatic bismaleimide compound containing two aromatic rings (phenylene groups) in one molecule, 4,4′-diphenylmethane bismaleimide, N, N ′-(4, 4′-biphenylene) bismaleimide, N, N ′-(sulfonyldi-p-phenylene) bismaleimide, N, N ′-(oxydi-p-phenylene) bismaleimide, N, N ′-(3,3′- Dimethyl-4,4′-biphenylylene) bismaleimide, N, N ′-(benzylidenedi-p-phenylene) bismaleimide, 3,3′-dichloro-4,4′-diphenylmethane bismaleimide, 3,3′-dimethyl -4,4'-diphenylmethane bismaleimide, 3,3'-dimethoxy-4,4'-diphenylmethane bismaleimide, 4,4'-diphenyl Sulfide bismaleimide, 4,4′-diphenyl ether bismaleimide, 3,3′-benzophenone bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 1,1′- And [1,4-butanediylbis (oxy-p-phenylene)] bismaleimide. Among these, 4,4′-diphenylmethane bismaleimide, 4,4′-diphenyl sulfide bismaleimide, and 4,4′-diphenyl ether bismaleimide are preferable.

  Specific examples of the maleimide derivative include 4-methyl-1,3-phenylenebismaleimide and 1,3-phenylene as aromatic bismaleimide compounds containing one aromatic ring (phenylene group) in one molecule. Examples thereof include bismaleimide, 1,4-phenylene bismaleimide, 1,2-phenylene bismaleimide, naphthalene-1,5-dimaleimide, and 4-chloro-1,3-phenylene bismaleimide.

  Specific examples of the maleimide derivative include aliphatic bismaleimide compounds such as 1,6-bismaleimide- (2,2,4-trimethyl) hexane and 1,6-bismaleimide- (2,4,4- Trimethyl) hexane, N, N′-decamethylene bismaleimide, N, N′-decamethylene bismaleimide, N, N′-octamethylene bismaleimide, N, N′-heptamethylene bismaleimide, N, N′-hexa Methylene bismaleimide, N, N′-pentamethylene bismaleimide, N, N′-tetramethylene bismaleimide, N, N′-trimethylene bismaleimide, N, N′-ethylene bismaleimide, N, N ′-(oxy Dimethylene) bismaleimide, 1,13-bismaleimide-4,7,10-trioxatridecane, 1,11-bis Maleimide) 3,6,9-such as the trio key sound decane. Of these, 1,6-bismaleimide- (2,2,4-trimethyl) hexane and N, N′-hexamethylene bismaleimide, which are compounds represented by the following formula (ii), are preferable.

  In addition to the above, polyphenylmethane maleimide, which is a compound represented by the following formula (2), may be mentioned. These maleimide derivatives can be used singly or in combination of two or more.

  As the maleimide derivative, a commercially available product can be used, and the product name “BMI-2000”, the product name “BMI-2300”, the product name “BMI-TMH” (manufactured by Daiwa Kasei Co., Ltd.), the product The name “BMI-3000”, the product name “BMI-689”, the product name “BMI-1500” (the above-mentioned, manufactured by Air Brown Co., Ltd.).

［上記式（２）中のｎは、０〜１０の整数を表す］

In particular, polyphenylmethanemaleimide, which is a compound represented by the following formula (2), and a compound represented by the following formula (3) from the viewpoint of low melting point and easy melting and mixing with the aromatic polyester (A) at a low temperature. Certain 1,6-bismaleimide- (2,2,4-trimethyl) hexane is preferred.

[N in the above formula (2) represents an integer of 0 to 10]

  N in the above formula (2) is preferably an integer of 0 to 5 in terms of melt fluidity. Maleimide derivatives having different values of n may be used, and maleimide derivatives having a distribution in the value of n may be used.

  The molecular weight of the maleimide derivative is not particularly limited, but is preferably 200 to 10000, more preferably 200 to 8000, and still more preferably 250 to 6000. When the molecular weight is within the above range, it is easy to melt and mix with the aromatic polyester (A) at a low temperature, and to mix uniformly.

  The melting point (Tm) of the maleimide derivative is preferably 200 ° C. or lower (for example, 60 to 200 ° C.), more preferably 180 ° C. or lower, and further preferably 160 ° C. or lower. When the melting point is 200 ° C. or less, it can be melt-mixed in a temperature region where the crosslinking reaction does not proceed, and a uniform composition can be obtained. In addition, the said melting | fusing point shows the endothermic peak temperature of DSC measurement.

  The exothermic start temperature of the maleimide derivative is not particularly limited, but is preferably 250 ° C. or lower (eg, 90 to 250 ° C.), more preferably 230 ° C. or lower, and further preferably 210 ° C. or lower. When the exothermic start temperature is 250 ° C. or less, the exothermic start temperature of the thermosetting aromatic polyester composition obtained by melt mixing with the aromatic polyester (A) is relatively low, and the curing temperature (curing temperature) is high. Not too much. The heat generation start temperature indicates a temperature at which the curve starts to rise from the baseline in DSC measurement.

  The curing temperature of the maleimide derivative is not particularly limited, but is preferably 70 to 250 ° C, more preferably 80 to 240 ° C, and further preferably 90 to 230 ° C. When the curing temperature of the maleimide derivative is within the above range, it is difficult for the viscosity to increase due to a crosslinking reaction during melt mixing. The curing temperature of the maleimide derivative can be measured from the exothermic peak temperature of DSC measurement.

  The curing temperature of the maleimide derivative is 240 ° C. in the case of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane as an aromatic bismaleimide compound containing three or more aromatic rings in one molecule. In the case of 4,4′-diphenylmethane bismaleimide as an aromatic bismaleimide compound containing two aromatic rings, the temperature is 202 ° C., and as an aromatic bismaleimide compound containing one aromatic ring, 4-methyl-1,3 In the case of -phenylene bismaleimide, it is 210 ° C., and in the case of polyphenylmethane maleimide, which is a compound represented by the above formula (2), it is 226 ° C. and is a compound represented by the above formula (3). In the case of 1,6-bismaleimide- (2,2,4-trimethyl) hexane, it is 285 ° C.

  The curing temperature of the crosslinkable compound (B) including the maleimide derivative tends to increase as the proportion of the aromatic cyclic group in the molecule increases. In particular, the proportion of polycyclic aromatic rings such as naphthalene and anthracene is increased. If it increases, the curing temperature tends to increase. In addition, the curing temperature tends to decrease when the proportion of an aliphatic hydrocarbon chain such as an alkyl group increases in the molecule, and particularly when the proportion of a long-chain aliphatic hydrocarbon chain having 6 or more carbon atoms increases, the curing temperature decreases. A compound having a long aliphatic chain such as the above formula (3) tends to increase the curing temperature.

  The blending amount (blending ratio) of the maleimide derivative is not particularly limited, but is preferably 10 to 300 parts by weight, more preferably 10 to 250 parts by weight, with respect to 100 parts by weight of the aromatic polyester (A). Part by weight is more preferred. When the blending amount of the maleimide derivative is within the above range, the curability of the thermosetting aromatic polyester composition is hardly lowered, and the cured compound does not have a large amount of the crosslinkable compound (B) remaining in the composition. It is difficult to adversely affect the physical properties.

  The curing temperature of the crosslinkable compound (B) is not particularly limited, but is preferably 70 to 250 ° C, more preferably 80 to 240 ° C, and further preferably 90 to 230 ° C. When the curing temperature of the crosslinkable compound (B) is in the above range, it is difficult for the viscosity to increase due to a crosslinking reaction during melt mixing. The curing temperature of the crosslinkable compound (B) is DSC (Differential Scanning Calorimeter, “DSC6200”, manufactured by Seiko Instruments Inc.) under a temperature rising condition of 20 ° C./min (under a nitrogen stream). The exothermic peak top temperature can be measured.

  In particular, the thermosetting aromatic polyester composition of the present invention is characterized in that the softening temperature of the aromatic polyester (A) is 30 ° C. or lower than the curing temperature of the crosslinkable compound (B). The softening temperature is preferably 40 ° C. or more lower than the curing temperature, more preferably 50 ° C. or more lower. Since the softening temperature is 30 ° C. or more lower than the curing temperature, it is difficult for the viscosity to increase due to a crosslinking reaction during melt mixing. The difference between the softening temperature and the curing temperature is not particularly limited. However, the softening temperature of the aromatic polyester (A) is 140 to 150 ° C., and the curing temperature of the crosslinkable compound (B) is 200 to 250 ° C. It is preferable.

  The blending amount (blending ratio) of the aromatic polyester (A) and the crosslinkable compound (B) varies depending on the types of the aromatic polyester (A) and the crosslinkable compound (B) and is not particularly limited. The amount of the crosslinkable compound (B) is preferably 10 to 300 parts by weight, more preferably 15 to 250 parts by weight, and still more preferably 20 to 200 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). When the blending amount of the crosslinkable compound (B) is within the above range, the curability of the thermosetting aromatic polyester composition is hardly lowered, and a large amount of the crosslinkable compound (B) may remain in the composition. There is no adverse effect on the physical properties of the cured product.

[Additive]
The thermosetting aromatic polyester composition of the present invention reduces the concentration of the aromatic polyester (A) to suppress the curing reaction at the time of adjusting the composition, and the performance of the cured product according to the purpose (use). Therefore, it contains additives such as inorganic fillers. Among these, an inorganic filler is preferably used as the additive.

  As the inorganic filler, known or conventional inorganic fillers can be used, and are not particularly limited. For example, silica (for example, natural silica, synthetic silica), aluminum oxide (for example, α-alumina), oxidation, etc. Oxides such as titanium, zirconium oxide, magnesium oxide, cerium oxide, yttrium oxide, calcium oxide, zinc oxide and iron oxide; carbonates such as calcium carbonate and magnesium carbonate; sulfates such as barium sulfate, aluminum sulfate and calcium sulfate; Nitride such as aluminum nitride, silicon nitride, titanium nitride, boron nitride; hydroxide such as calcium hydroxide, aluminum hydroxide, magnesium hydroxide; mica, talc, kaolin, kaolin clay, kaolinite, halloysite, pyrophyllite , Montmorillonai , Sericite, Amesite, Bentonite, Asbestos, Wollastonite, Sepiolite, Zonolite, Zeolite, Hydrotalcite, Fly Ash, Dehydrated Sludge, Glass Beads, Glass Fiber, Diatomaceous Earth, Silica Sand, Carbon Black, Sendust, Alnico Magnets, magnetic powders such as various ferrites, hydrated gypsum, alum, antimony trioxide, magnesium oxysulfate, silicon carbide, potassium titanate, calcium silicate, magnesium silicate, aluminum silicate, magnesium phosphate, copper, iron, etc. Is mentioned. The inorganic filler may have any structure such as a solid structure, a hollow structure, and a porous structure. Moreover, the said inorganic filler may be surface-treated with well-known surface treating agents, such as organosilicon compounds, such as organohalosilane, organoalkoxysilane, and organosilazane, for example. In addition, in the manufacturing method of the thermosetting aromatic polyester composition of this invention, an inorganic filler can also be used individually by 1 type, and can also be used in combination of 2 or more type. Especially, when using the thermosetting aromatic polyester composition of this invention for semiconductor sealing materials, it is preferable to use a silica (silica filler) etc., and heat conductivity and heat dissipation characteristic of hardened | cured material When adjusting the above, it is preferable to use alumina (alumina fine particles) or the like.

  The content of the inorganic filler is not particularly limited, but with respect to 100 parts by weight of the total amount (total amount) of the aromatic polyester (A) and the crosslinkable compound (B) constituting the thermosetting aromatic polyester composition, 0-500 weight part is preferable, More preferably, it is 0-300 weight part.

  The additive other than the inorganic filler is not particularly limited, and examples thereof include diamino compounds [for example, diaminodiphenylmethane], diallyl compounds [for example, diallyl bisphenol A], triazines [for example, 1,3,5-tri-2 -Propenyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (2-methyl-2-propenyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc.].

  As additives other than the above inorganic filler, other known or commonly used additives can be used as long as the effects of the present invention are not impaired. For example, organic resins such as silicone resins, epoxy resins, fluororesins; solvents; Stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.); flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants, etc.); flame retardant aids; reinforcing materials Nucleating agent; Coupling agent; Lubricant; Wax; Plasticizer; Release agent; Impact resistance improver; Hue improver; Fluidity improver; Colorant (dye, pigment, etc.); Dispersant; Defoaming agents; antibacterial agents; antiseptics; viscosity modifiers; thickeners can be used. In addition, the said additive can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The thermosetting aromatic polyester composition of the present invention may contain additives for accelerating and controlling the curing reaction. The additive is not particularly limited, and examples thereof include diamino compounds [for example, diaminodiphenylmethane], diallyl compounds [for example, diallyl bisphenol A], and triazines [for example, 1,3,5-tri-2-propenyl-1]. , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (2-methyl-2-propenyl) -1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione, 1,3,5-tris (2,3-epoxypropyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Etc.]. In addition, the said additive can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The content (blending amount) of the additive (other than the inorganic filler) is not particularly limited, but is 0 to 30 weights with respect to 100 parts by weight of the total amount of the aromatic polyester (A) and the crosslinkable compound (B). Parts are preferred, more preferably 1 to 20 parts by weight.

  The above additives (including the inorganic filler) are blended together when preparing the thermosetting aromatic polyester composition of the present invention (when the aromatic polyester (A) and the crosslinkable compound (B) are melt-mixed). It can also be blended after the thermosetting aromatic polyester composition of the present invention is once prepared.

  The thermosetting aromatic polyester composition of the present invention is not particularly limited as long as it contains the aromatic polyester (A) and the crosslinkable compound (B), but the aromatic polyester (A), the crosslinkable compound (B), and other additives are added. It is preferable to add the agent and melt and mix.

  The mixing temperature when the aromatic polyester (A) and the crosslinkable compound (B) are melt-mixed is a temperature at which the aromatic polyester (A) and the crosslinkable compound (B) can be melted (in particular, the aromatic polyester ( The melting point of A) is not particularly limited, but is preferably 200 ° C. or lower (for example, 80 to 200 ° C.), more preferably 190 ° C. or lower, and further preferably 180 ° C. or lower. When the temperature of the melt mixing is 200 ° C. or less, the polymerization reaction of the thermally polymerizable functional group derived from the crosslinkable compound (B) can be suppressed, and a rapid increase in viscosity can be suppressed. In addition, the temperature at the time of melt mixing can be controlled so as to be constant during the melt mixing, or can be controlled so as to fluctuate stepwise or continuously.

  Although the time which melt-mixes with aromatic polyester (A) and a crosslinkable compound (B) is not specifically limited, 3 to 600 minutes are preferable, More preferably, it is 4 to 400 minutes, More preferably, it is 5 to 200 minutes. is there. When the melt mixing time is within the above range, the productivity of the cured product does not decrease, and the reaction between the aromatic polyester (A) and the crosslinkable compound (B) can proceed.

  The melt viscosity (initial complex viscosity) of the thermosetting aromatic polyester composition of the present invention is preferably 1000 Pa · s or less, more preferably 500 Pa · s or less, and 200 Pa · s or less at 200 ° C. or less (for example, 180 ° C.). The following is more preferable, and 100 Pa · s or less is particularly preferable. When the initial complex viscosity is 1000 Pa · s or less, molding such as transfer molding is facilitated. The melt viscosity (initial complex viscosity) can be measured using a rheometer (viscoelasticity measuring device) (trade name “MCR-302”, manufactured by Anton Paar).

  The melt mixing can be carried out using a known or conventional apparatus (melt mixing apparatus). Although it does not specifically limit as said melt mixing apparatus, Extruders, such as a single screw extruder and a twin screw extruder; Mixers, such as a paddle mixer, a high-speed flow-type mixer, a ribbon mixer, a Banbury mixer, a Haake mixer, a static mixer; Kneader Is mentioned.

  The thermosetting aromatic polyester composition of the present invention has a reactive functional group at the end of the molecular chain of the aromatic polyester (A) in that higher performance (heat resistance, mechanical properties, etc.) can be obtained when it is cured. It is preferable that an adduct formed by reacting (a) and the reactive functional group (b) of the crosslinkable compound (B) at the time of melt mixing is included as a part of the composition. The adduct is obtained by bonding one or more aromatic polyesters (A) and one or more crosslinkable compounds (B) by the above-described reaction (for example, addition reaction).

  As described above, the thermosetting aromatic polyester composition of the present invention has a crosslinkable compound (B) because the softening temperature of the aromatic polyester (A) is 30 ° C. or more lower than the curing temperature of the crosslinkable compound (B). The aromatic polyester (A) and the crosslinkable compound (B) can be melt-mixed at a temperature at which the crosslinking reaction does not proceed. Therefore, the thermosetting aromatic polyester composition can suppress an increase in viscosity and is excellent in moldability such as transfer molding.

[Cured product]
A cured product (sometimes referred to as “cured product of the present invention”) is obtained by curing the thermosetting aromatic polyester composition of the present invention by heating (advancing the curing reaction). The reaction (polymerization reaction) between the thermally polymerizable functional groups mainly resulting from the compound (B) proceeds by heating, and a cured product is formed. As heating means, known or conventional means can be used, and there is no particular limitation.

  The heating temperature (curing temperature) for curing the thermosetting aromatic polyester composition of the present invention is not particularly limited, but is preferably 70 to 250 ° C, more preferably 100 to 250 ° C, and further 150 to 250 ° C. preferable. When the curing temperature is in the above range, productivity does not decrease, the curing reaction proceeds sufficiently, and a cured product with good physical properties can be obtained. The curing temperature can be controlled to be constant during curing, or can be controlled to vary stepwise or continuously.

  The heating time (curing time) for curing the thermosetting aromatic polyester composition of the present invention is not particularly limited, but is preferably 3 to 600 minutes, more preferably 5 to 480 minutes, and further more preferably 5 to 360 minutes. preferable. When the curing time is within the above range, the productivity of the cured product does not decrease, the curing reaction proceeds sufficiently, and the physical properties of the cured product are unlikely to decrease.

  Curing of the thermosetting aromatic polyester composition of the present invention can be performed under normal pressure, or can be performed under reduced pressure or under pressure. Moreover, the said hardening can also be performed in one step, and can also be performed by dividing into two or more steps.

The 5% weight loss temperature (T _d5 ) of the cured product of the present invention measured at a temperature rising rate of 10 ° C./min (in air) is not particularly limited, but is 350 ° C. or higher (for example, 350 to 500 ° C.). It is preferably 380 ° C. or higher, more preferably 400 ° C. or higher. If the 5% weight loss temperature is less than 350 ° C., the heat resistance may be insufficient depending on the application. The 5% weight loss temperature can be measured by, for example, TG / DTA (simultaneous measurement of differential heat and thermogravimetry).

  The activation energy of the thermal decomposition reaction in the air of the cured product of the present invention is not particularly limited, but is preferably 150 kJ / mol or more (for example, 150 to 350 kJ / mol), more preferably 180 kJ / mol or more, and 200 kJ / mol. The above is more preferable. If the activation energy is less than 150 kJ / mol, the heat resistance may be insufficient depending on the application. The activation energy can be calculated by, for example, the Ozawa method. The Ozawa method is a method in which TG measurement (thermogravimetry) is performed at three or more types of temperature increase rates, and the activation energy of the thermal decomposition reaction is calculated from the obtained thermogravimetric reduction data.

  Since the cured product of the present invention is a cured product obtained by curing the thermosetting aromatic polyester composition of the present invention, it has excellent heat resistance, and excellent workability, dimensional stability, It has low linear expansion, high thermal conductivity, low moisture absorption, and dielectric properties. Furthermore, since the cured product of the present invention is obtained by heating the thermosetting aromatic polyester composition of the present invention at a relatively low temperature of 250 ° C. or less, it is excellent in productivity.

  The cured product of the present invention can be used for various applications such as various members and various structural materials. In particular, since it is excellent in the above-mentioned various properties, it can be preferably used for applications such as films, prepregs, printed wiring boards, and semiconductor encapsulants. That is, the thermosetting aromatic polyester composition of the present invention is, in particular, a thermosetting composition for films, a thermosetting composition for prepregs, a thermosetting composition for printed wiring boards, and a thermosetting for semiconductor sealing materials. It can be preferably used as a composition.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Synthesis example 1
[Synthesis of Aromatic Polyester E (Decamer)]
In a 500 mL flask equipped with a condenser and a stirrer, 94.3 g (0.682 mol) of 4-hydroxybenzoic acid, 102.7 g (0.546 mol) of 6-hydroxy-2-naphthoic acid, 25,4'-dihydroxybiphenyl 25 .4 g (0.136 mol), acetic anhydride 156.3 g (1.53 mol), and potassium acetate 10.0 mg (0.10 mol) were added, and the temperature was gradually raised to 140 ° C. under a nitrogen atmosphere. The acetylation reaction was completed by reacting for 3 hours while maintaining. Subsequently, acetic acid and unreacted acetic anhydride were distilled off while heating up to 340 ° C. at a rate of 0.8 ° C./min. Thereafter, the inside of the flask is gradually depressurized to 1 Torr to distill off the volatile components, whereby an aromatic polyester E having hydroxyl groups at both ends of a molecular chain consisting only of aromatic units (constituent units derived from aromatic compounds). Got. Table 1 shows the thermal analysis results [glass transition temperature (Tg), melting point (Tm)] and softening temperature of the obtained aromatic polyester E. In addition, as a result of calculation of the number of terminals of the aromatic polyester E and GPC measurement, the obtained aromatic polyester E was estimated to be a monomer 10-mer.

Synthesis example 2
[Synthesis of Aromatic Polyester F (Pentamer)]
The amount of 4-hydroxybenzoic acid used was 81.4 g (0.589 mol), the amount of 6-hydroxy-2-naphthoic acid used was 88.9 g (0.472 mol), and the amount of 4,4′-dihydroxybiphenyl used was The same operation as in Synthesis Example 1 except that 49.4 g (0.265 mol), the amount of acetic anhydride used was 165.8 g (1.62 mol), and the amount of potassium acetate used was 10.0 mg (0.10 mol). The aromatic polyester F which has a hydroxyl group in the both ends of the molecular chain which consists only of an aromatic unit (constituent unit derived from an aromatic compound) was obtained. The thermal analysis results and softening temperature of the obtained aromatic polyester F were as shown in Table 1. The obtained aromatic polyester F was estimated to be a monomeric pentamer as a result of calculation of the number of terminals of the aromatic polyester F and GPC measurement.

Synthesis example 3
[Synthesis of Aromatic Polyester G (20mer)]
As shown in Table 1, the amount of 4-hydroxybenzoic acid used was 100.9 g (0.731 mol), the amount of 6-hydroxy-2-naphthoic acid used was 110.0 g (0.585 mol), 4,4 ′. -The amount of dihydroxybiphenyl used was 12.9 g (0.069 mol), the amount of acetic anhydride used was 151.4 g (1.48 mol), and the amount of potassium acetate used was 10.0 mg (0.10 mol). Operation similar to the synthesis example 1 was performed, and the aromatic polyester G which has a hydroxyl group in the both ends of the molecular chain which consists only of an aromatic unit (structural unit derived from an aromatic compound) was obtained. The thermal analysis results and softening temperature of the obtained aromatic polyester G were as shown in Table 1. The obtained aromatic polyester G was estimated to be a monomeric 20mer as a result of calculation of the number of terminals of the aromatic polyester G and GPC measurement.

Synthesis example 4
[Synthesis of Aromatic Polyester H (100-mer)]
As shown in Table 1, the amount of 4-hydroxybenzoic acid used was 106.5 g (0.771 mol), the amount of 6-hydroxy-2-naphthoic acid used was 118.7 g (0.631 mol), and acetic anhydride was used. The same procedure as in Synthesis Example 1 was conducted except that the amount was 146.0 g (1.43 mol) and the amount of potassium acetate used was 10.0 mg (0.10 mol), and the aromatic unit (derived from the aromatic compound) was obtained. Aromatic polyester H having hydroxyl groups at both ends of the molecular chain consisting only of the structural unit was obtained. The thermal analysis results and softening temperature of the obtained aromatic polyester H were as shown in Table 1. In addition, as a result of calculation of the number of terminals of the aromatic polyester H and GPC measurement, the obtained aromatic polyester H was estimated to be a monomer 100-mer.

The meanings of the abbreviations in Table 1 are as follows.
HBA: 4-hydroxybenzoic acid HNA: 6-hydroxy-2-naphthoic acid BP: 4,4′-dihydroxybiphenyl

[Production of thermosetting aromatic polyester composition]
Example 1
29.1 g of the aromatic polyester E obtained in Synthesis Example 1 was melted at 150 ° C., and melted for 4 hours with 43.8 g of polyphenylmethane maleimide (trade name “BMI-2300” manufactured by Daiwa Kasei Co., Ltd.) as a maleimide derivative. Mixing was performed to obtain a melt (thermosetting aromatic polyester composition).

Example 2
44.0 g of the aromatic polyester G synthesized in Synthesis Example 3 was melted at 170 ° C. and melt-mixed with 30.5 g of polyphenylmethane maleimide (trade name “BMI-2300” manufactured by Daiwa Kasei Co., Ltd.) as a maleimide derivative for 1 hour. As a result, a melt (thermosetting aromatic polyester composition) was obtained.

Comparative Example 1
44.0 g of aromatic polyester H was melted at 265 ° C., and melted and mixed with 30.1 g of polyphenylmethane maleimide (trade name “BMI-2300” manufactured by Daiwa Kasei Co., Ltd.) as a maleimide derivative for 1 hour. A curable aromatic polyester composition) was obtained. The obtained melt was non-uniform and the maleimide derivative alone cured significantly.

[Softening temperature]
Using a polarizing microscope (trade name “Leica DM4000B”, manufactured by Leica) equipped with a hot stage (trade name “METTLER TOLEDO FP82HT”, manufactured by METTLER TOLEDO), a dried powder sample (10 mg) was placed on a slide glass 2 The sheet was placed on a hot stage and heated at 10 ° C./min. The sample was observed with crossed Nicols, and the temperature at which light was visible in the dark field (the temperature at which liquid crystallinity was manifested) was defined as the softening temperature.

[Initial complex viscosity]
Using a rheometer (viscoelasticity measuring device) (trade name “MCR-302”, manufactured by Anton Paar), the sample was melted while being heated at a heating temperature of 20 ° C./min. The viscosity [Pa · s] was measured.

[5% weight loss temperature of cured product (T _d5 )]
The 5% weight reduction temperature (T _d5 ) of the cured product obtained in the above example was 10 ° C./min. Temperature increase using TG / DTA (“TG / DTA6300”, manufactured by Seiko Instruments Inc.). The measurement was performed under conditions (in a nitrogen atmosphere).

  As shown in Table 2, the thermosetting aromatic polyester composition obtained in the examples can be melt-mixed at a relatively low temperature, has a low initial complex viscosity, and is a thermosetting aromatic polyester composition. An increase in viscosity could be suppressed. Moreover, the obtained cured product had a high 5% weight loss temperature and had very excellent heat resistance.

Claims (6)

The following aromatic polyester (A) and the following crosslinkable compound (B) are included, and the softening temperature of the aromatic polyester (A) is 30 ° C. or lower than the curing temperature of the crosslinkable compound (B). Thermosetting aromatic polyester composition.
Aromatic polyester (A): aromatic polyester having at least one group or structure selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic cyclic group, and a conjugated diene structure at the molecular chain terminal Crosslinkable compound (B ): A functional group that reacts with a hydroxyl group, an acyloxy group, an aromatic cyclic group, or a conjugated diene structure, a functional group that reacts with the group or structure of the aromatic polyester (A), and a thermally polymerizable functional group. Crosslinkable compound in the molecule   The thermosetting aromatic polyester composition according to claim 1, wherein the softening temperature of the aromatic polyester (A) is 40 to 200 ° C.   The thermosetting aromatic polyester composition according to claim 1 or 2, wherein the curing temperature of the crosslinkable compound (B) is 70 to 250 ° C.   The thermosetting aromatic polyester composition according to any one of claims 1 to 3, wherein the crosslinkable compound (B) is a maleimide derivative.   The thermosetting aromatic polyester composition according to any one of claims 1 to 4, wherein the aromatic polyester (A) has an average degree of polymerization of 3 to 30.   The thermosetting fragrance according to any one of claims 1 to 5, wherein the amount of the crosslinkable compound (B) is 10 to 300 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). Group polyester composition.