WO2015151815A1

WO2015151815A1 - Thermosetting aromatic polyester composition and method for producing same

Info

Publication number: WO2015151815A1
Application number: PCT/JP2015/058056
Authority: WO
Inventors: 中谷晃司; 竹内秀一; 坂本勝利; 田口吉昭
Original assignee: 株式会社ダイセル
Priority date: 2014-04-02
Filing date: 2015-03-18
Publication date: 2015-10-08

Abstract

The purpose of the present invention is to provide a production method with which it is possible to easily obtain a uniform thermosetting aromatic polyester composition suitable for molding such as transfer molding, and with which it is possible to suppress an increase in viscosity of the thermosetting aromatic polyester composition by adjusting the order of mixing additives, etc., at the time of melt-mixing an aromatic polyester and a thermosetting agent. This method for producing a thermosetting aromatic polyester composition is a method for producing a thermosetting polyester composition that includes an aromatic polyester and a cross-linking compound, the method comprising: a step (I) for melt-mixing an aromatic polyester (A) and an additive; and a step (II) for adding a cross-linking compound (B) to the mixture obtained at step (I), and melt-mixing the same.

Description

Thermosetting aromatic polyester composition and method for producing the same

The present invention relates to a thermosetting aromatic polyester composition (thermosetting liquid crystal resin composition containing an aromatic polyester) and a method for producing the same. This application claims the priority of Japanese Patent Application Nos. 2014-076513, 2014-076514, and 2014-076518, filed in Japan on April 2, 2014, the contents of which are incorporated herein by reference. .

Liquid crystal polymers typified by liquid crystal polyester are excellent in various properties such as heat resistance, moldability, chemical resistance, and mechanical strength, and are therefore 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 the 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 end 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

However, aromatic polyesters such as liquid crystal polyesters have very poor compatibility with thermosetting agents. Therefore, it is necessary to mix the aromatic polyester and the thermosetting agent in a liquid state at a high temperature for a long time. However, when a thermosetting agent is added to the aromatic polyester and heated and mixed for a long time at a temperature higher than the melting point, the crosslinking reaction of the thermopolymerizable functional group proceeds, so that the viscosity of the thermosetting polyester composition is increased. May rise and become high viscosity. Therefore, molding such as transfer molding may be difficult.

Therefore, the object of the present invention is to suppress the increase in viscosity of the thermosetting aromatic polyester composition by devising the mixing order of additives when the aromatic polyester and the thermosetting agent are melt-mixed. Another object of the present invention is to provide a production method capable of easily obtaining a thermosetting aromatic polyester composition that is uniform and suitable for molding such as transfer molding.

Another object of the present invention is to add a maleimide derivative having a low melting point and / or a large difference between the melting point and the heat generation starting temperature as a thermosetting agent, so that a crosslinking reaction does not proceed (for example, 80 to 200). It is an object of the present invention to provide a method for producing a thermosetting aromatic polyester composition capable of mixing a maleimide derivative with a thermosetting aromatic polyester at a low temperature and uniformly dispersing the mixture.

Furthermore, 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.

Therefore, another object of the present invention is that aromatic polyester can 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 molding such as transfer molding. It is providing the thermosetting aromatic polyester composition excellent in property.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention blended an additive such as an inorganic filler first when an aromatic polyester having a specific structure and a thermosetting agent are melt-mixed, and then the thermosetting agent. When (crosslinkable compound) is blended, the aromatic polyester in the system is diluted, the concentration of the thermosetting aromatic polyester generated after the addition of the thermosetting agent is lowered, and the thermosetting agent and the thermosetting aromatic polyester The inventors have found that a time for heating can be reduced, an increase in viscosity due to a curing reaction (crosslinking reaction) can be suppressed, and a uniform and transfer-moldable thermosetting aromatic polyester composition can be easily produced, thereby completing the present invention. It was.

In addition, as a result of intensive studies to solve the above problems, the present inventors have formulated a thermosetting aromatic polyester having a specific structure and a low melting point and / or a maleimide derivative having a large difference between the melting point and the heat generation start temperature. The aromatic polyester and the maleimide derivative can be mixed in a temperature range where the cross-linking reaction does not proceed (for example, 80 to 200 ° C.), the viscosity increase of the thermosetting aromatic polyester composition can be suppressed, and a uniform composition can be obtained. Discovered and completed the present invention.

Furthermore, as a result of intensive studies to solve the above problems, the present inventors use a specific aromatic polyester in which the softening temperature of the aromatic polyester is 30 ° C. or lower than the curing temperature of the compound having a crosslinkable group. Thus, it was found that a thermosetting aromatic polyester composition can be obtained by kneading in a relatively low temperature range (for example, 100 to 200 ° C.) where the crosslinking reaction does not proceed, and the present invention has been completed.

That is, this invention is a manufacturing method of the thermosetting polyester composition containing aromatic polyester and a crosslinkable compound, Comprising: The process I which melt-mixes the following aromatic polyester (A) and an additive, and the said Provided is a method for producing a thermosetting aromatic polyester composition comprising a step II in which the following crosslinkable compound (B) is added to the mixture obtained in the step I and melt mixed.
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

Further, according to the present invention, the amount of the additive is 10 to 4000 parts by weight and the amount of the crosslinkable compound (B) is 10 to 400 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). A method for producing the thermosetting aromatic polyester composition is provided.

Further, the present invention provides the production of the thermosetting aromatic polyester composition, wherein the mixing temperature when the aromatic polyester (A) and the additive are melt-mixed in the step I is 80 to 300 ° C. Provide a method.

Further, the present invention provides the thermosetting aromatic compound according to the step II, wherein the crosslinking temperature (80) is 200 to 200 ° C. and the mixing time is 30 to 600 minutes when the crosslinkable compound (B) is added and melt mixed. A method for producing a polyester composition is provided.

Furthermore, the present invention provides a method for producing the thermosetting aromatic polyester composition, wherein the additive is an inorganic filler.

Furthermore, the present invention provides a method for producing the thermosetting aromatic polyester composition, wherein the inorganic filler is a silica filler.

Moreover, this invention provides the manufacturing method of the thermosetting aromatic polyester composition characterized by including the process of adding the following maleimide derivative (B ') to the following aromatic polyester (A), and mixing.
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 end Maleimide derivative (B ′ ): Melting point of 150 ° C. or less and / or difference in heat generation start temperature between the melting point and the maleimide derivative is 30 ° C. or more, and a maleimide group that reacts with the aromatic polyester (A) in the molecule and a thermopolymerizable functional group Maleimide derivative having a maleimide group as a group

Further, the present invention provides the above thermosetting aromatic polyester composition, wherein the blended amount of the maleimide derivative (B ′) is 10 to 400 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). Provide a method.

Furthermore, the present invention relates to the thermosetting resin, wherein the maleimide derivative (B ′) is added to the aromatic polyester (A) and the mixing temperature is 80 to 200 ° C. and the mixing time is 30 to 600 minutes. A method for producing an aromatic polyester composition is provided.

Furthermore, the present invention provides the thermosetting, wherein the maleimide derivative (B ′) is at least one compound selected from a compound represented by the following formula (i) and a compound represented by the formula (ii): A method for producing a conductive polyester composition is provided.

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

Further, in the present invention, the aromatic polyester (A) is 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 (A) (the ratio of the total amount when there are two or more structural units) is 60 to 100 Provided is a method for producing the thermosetting aromatic polyester composition, which is in weight percent.

Furthermore, this invention provides the manufacturing method of the said thermosetting aromatic polyester composition whose melting | fusing point of the said aromatic polyester (A) is 250 degrees C or less.

Furthermore, the present invention provides a method for producing the thermosetting aromatic polyester composition, wherein the aromatic polyester (A) has a molecular weight of 300 to 20000.

Further, in the present invention, the ratio of the hydroxyl group is 5 to 100% and the ratio of the acyloxy group is 0 to 90% with respect to the entire terminal group at the molecular chain end of the aromatic polyester (A). Provided is a method for producing the thermosetting aromatic polyester composition, wherein the ratio of groups other than the hydroxyl group and the acyloxy group is 0 to 90%.

The present invention also provides a thermosetting aromatic polyester composition obtained by the above-described method for producing a thermosetting aromatic polyester composition.

Moreover, 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 from the hardening 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, the present invention provides the thermosetting aromatic polyester composition described above, wherein the aromatic polyester (A) has a softening temperature of 40 to 200 ° C.

Furthermore, the present invention provides the thermosetting aromatic polyester composition, wherein the curing temperature of the crosslinkable compound (B) is 70 to 250 ° C.

Furthermore, the present invention provides the thermosetting aromatic polyester composition, wherein the aromatic polyester (A) has an average degree of polymerization of 3 to 30.

Furthermore, the present invention provides the thermosetting aromatic polyester composition, wherein the crosslinkable compound (B) is a maleimide derivative.

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.

The present invention also provides a cured product obtained by curing the thermosetting aromatic polyester composition.

Furthermore, in the present invention, the 5% weight reduction rate measured at a temperature rising rate of 10 ° C./min (in air) is 350 ° C. or higher, and the activation energy of the thermal decomposition reaction in air is 150 kJ / mol or higher. The cured product is provided.

That is, the present invention relates to the following.
[1] A method for producing a thermosetting polyester composition containing an aromatic polyester and a crosslinkable compound, which is obtained in Step I in which the aromatic polyester (A) and an additive are melt-mixed, and in Step I above. A method for producing a thermosetting aromatic polyester composition, comprising the step II of adding the crosslinkable compound (B) to the obtained mixture and melt-mixing the mixture.
[2] The amount of the additive is 10 to 4000 parts by weight and the amount of the crosslinkable compound (B) is 10 to 400 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). The manufacturing method of the thermosetting aromatic polyester composition as described in [1].
[3] The thermosetting aromatic according to [1] or [2], wherein in the step I, the mixing temperature when the aromatic polyester (A) and the additive are melt-mixed is 80 to 300 ° C. A method for producing a polyester composition.
[4] Any one of [1] to [3], wherein in the step II, the mixing temperature is 80 to 200 ° C. and the mixing time is 30 to 600 minutes when the crosslinkable compound (B) is added and melt mixed. The manufacturing method of the thermosetting aromatic polyester composition of 1 item | term.
[5] The method for producing a thermosetting aromatic polyester composition according to any one of [1] to [4], wherein the additive is an inorganic filler.
[6] The method for producing a thermosetting aromatic polyester composition according to [5], wherein the inorganic filler is a silica filler.
[7] In the step II, the melt viscosity (initial complex viscosity) of the thermosetting aromatic polyester composition after the crosslinkable compound (B) is added and melt mixed is 200 Pa or less at 1000 Pa · s or less. The method for producing a thermosetting aromatic polyester composition according to any one of [1] to [6].
[8] A method for producing a thermosetting aromatic polyester composition comprising a step of adding and mixing a maleimide derivative (B ′) to the aromatic polyester (A).
[9] The thermosetting aromatic polyester composition according to [8], wherein the amount of the maleimide derivative (B ′) is 10 to 400 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). Production method.
[10] In [8] or [9], when the maleimide derivative (B ′) is added to the aromatic polyester (A) and mixed, the mixing temperature is 80 to 200 ° C. and the mixing time is 30 to 600 minutes. The manufacturing method of the thermosetting aromatic polyester composition of description.
[11] The maleimide derivative (B ′) is at least one compound selected from the compound represented by the formula (i) and the compound represented by the formula (ii). The manufacturing method of the thermosetting polyester composition of any one.
[12] The method for producing a thermosetting polyester composition according to any one of [8] to [11], wherein the maleimide derivative (B ′) has a molecular weight of 200 to 1,000.
[13] The method for producing a thermosetting polyester composition according to any one of [8] to [12], wherein the maleimide derivative (B ′) has a melting point of 150 ° C. or lower.
[14] The method for producing a thermosetting polyester composition according to any one of [8] to [13], wherein the maleimide derivative (B ′) has an exothermic starting temperature of 250 ° C. or lower.
[15] The aromatic polyester (A) includes 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 (A) (the ratio of the total amount when there are two or more structural units) is 60 to 100% by weight. The method for producing a thermosetting aromatic polyester composition according to any one of [1] to [14].
[16] The process for producing a thermosetting aromatic polyester composition according to any one of [1] to [15], wherein the aromatic polyester (A) has a melting point of 250 ° C. or lower.
[17] The method for producing a thermosetting aromatic polyester composition according to any one of [1] to [16], wherein the aromatic polyester (A) has a molecular weight of 300 to 20000.
[18] The ratio of the hydroxyl group is 5 to 100% and the ratio of the acyloxy group is 0 to 90% with respect to the entire terminal group at the molecular chain end of the aromatic polyester (A). The method for producing a thermosetting aromatic polyester composition according to any one of [1] to [17], wherein the ratio of groups other than the acyloxy group is 0 to 90%.
[19] A thermosetting aromatic polyester composition obtained by the method for producing a thermosetting aromatic polyester composition according to any one of [1] to [18].
[20] It includes an aromatic polyester (A) and a crosslinkable compound (B), and the softening temperature of the aromatic polyester (A) is 30 ° C. or lower than the curing temperature of the crosslinkable compound (B). A thermosetting aromatic polyester composition.
[21] The thermosetting aromatic polyester composition according to [20], wherein the aromatic polyester (A) has a softening temperature of 40 to 200 ° C.
[22] The thermosetting aromatic polyester composition according to [20] or [21], wherein the curing temperature of the crosslinkable compound (B) is 70 to 250 ° C.
[23] The thermosetting aromatic polyester composition according to any one of [20] to [22], wherein the average degree of polymerization of the aromatic polyester (A) is 3 to 30.
[24] The thermosetting aromatic polyester composition according to any one of [20] to [23], wherein the crosslinkable compound (B) is a maleimide derivative.
[25] 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), according to any one of [20] to [24] Thermosetting aromatic polyester composition.
[26] A cured product obtained by curing the thermosetting aromatic polyester composition according to any one of [19] to [25].
[27] The 5% weight loss rate measured at a heating rate of 10 ° C./min (in air) is 350 ° C. or more, and the activation energy of the thermal decomposition reaction in air is 150 kJ / mol or more [26]. The cured product described in 1.

Since the 1st manufacturing method has the above-mentioned composition, it can control the viscosity rise of the thermosetting aromatic polyester composition by progress of hardening reaction of aromatic polyester and a thermosetting agent (crosslinkable compound), and is uniform. A simple thermosetting aromatic polyester composition can be obtained.

Since the second production method has the above-described configuration, it can be mixed in a temperature range (for example, 80 to 200 ° C.) where the crosslinking reaction does not proceed, and the increase in viscosity of the thermosetting aromatic polyester composition is suppressed and uniform. Composition is obtained.

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.

[Method for producing thermosetting aromatic polyester composition]
The method for producing the thermosetting aromatic polyester composition of the present invention (sometimes referred to as “the production method of the present invention”) is “the first production method” or “the second production method”. The first production method and the second production method are independent production methods, but the increase in the viscosity of the thermosetting aromatic polyester composition can be suppressed, and a uniform composition can be obtained. Has a common effect.

A 1st manufacturing method is a manufacturing method of the thermosetting polyester composition containing an aromatic polyester, a crosslinkable compound, and an additive, Comprising: The process of melt-mixing the following aromatic polyester (A) and an additive I and a step II in which the following crosslinkable compound (B) is added to the mixture obtained in the step I and melt mixed.
Aromatic polyester (A): 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 (particularly, a hydroxyl group and / or an acyloxy group) Aromatic polyester having a crosslinkable compound (B): a functional group that reacts with a hydroxyl group, an acyloxy group, an aromatic ring, or a conjugated diene structure (particularly a functional group that reacts with a hydroxyl group and / or an acyloxy group), A crosslinkable compound having a functional group that reacts with the group or structure of the aromatic polyester (A) and a thermopolymerizable functional group in the molecule. Note that the above-mentioned “hydroxyl group and / or acyloxy group” means “hydroxyl group and acyloxy group” It means “one or both” and the same applies to the other.

The second production method includes a step of adding and mixing the following maleimide derivative (B ′) to the aromatic polyester (A).
Maleimide derivative (B ′): a maleimide group having a melting point of 150 ° C. or less and / or a difference in heat generation starting temperature between the melting point and the maleimide derivative of 30 ° C. or more and reacting with the aromatic polyester (A) in the molecule And a maleimide derivative having a maleimide group which is a thermopolymerizable functional group.
The above “the melting point is 150 ° C. or less and / or the difference between the melting point and the exothermic starting temperature of the maleimide derivative is 30 ° C. or more” may be that the melting point of the maleimide derivative is only 150 ° C. or less. This means that the difference in the heat generation start temperature may be only 30 ° C. or more, the melting point may be 150 ° C. or less, and the difference between the melting point and the heat generation start temperature may be 30 ° C. or more.

[Aromatic polyester (A)]
As described above, the aromatic polyester (A) has 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 (“reactivity”). It is an aromatic polyester having a functional group (sometimes referred to as “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 end 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 end. 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 proportion of hydroxyl groups is 5 to 100%, the proportion of acyloxy groups is 0 to 90%, and the proportion 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. %, More preferably 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 thereof 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. And 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 (A) (when the structural unit is two or more, the ratio of the total amount thereof) is preferably 60 to 100% by weight, Is more preferably from 100 to 100% by weight, still more preferably from 90 to 100% by weight. 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) does not easily exhibit liquid crystallinity in the molten state due to the structural units derived from other monomers to be introduced, and the heat resistance and moisture resistance of the cured product The resistance (hydrolysis resistance) is not easily lowered.

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, 5-amino- Examples thereof include 1-naphthol, 4′-hydroxy- [1,1′-biphenyl] -4-amine, 4-amino-4′-hydroxydiphenylmethane, and derivatives thereof. Examples of the derivatives include compounds in which an aromatic ring of the aromatic amine having a 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 (eg, 0 to 30% by weight), more preferably 10% by weight or less, and further 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-mentioned 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 group to be formed (ester group, acid anhydride group, acid halide group, etc.), amino group, etc.) is not particularly limited. 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 And a method of reacting a compound having a conjugated diene structure and capable of reacting with the reactive functional group (for example, (1-methyl-2,4-cyclopentadien-1-yl) methanol). Is mentioned.

The average degree of polymerization of the aromatic polyester (A) is not particularly limited, but is preferably 3 to 30, more preferably 4 to 25, and still more preferably 5 to 20. When the average degree of polymerization is within the above range, the curing reactivity is unlikely to decrease, and the reaction temperature at the time of curing does not become too high. 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 300 to 20000, more preferably 400 to 15000, and still more preferably 500 to 15000. When the molecular weight is within the above range, the melting point of the aromatic polyester does not become too high, and the mixing can be performed in a temperature range where a crosslinking reaction hardly occurs when mixing with the thermosetting agent. In addition, the molecular weight of aromatic polyester (A) can be calculated | required by GPC measurement, for example.

The glass transition temperature (Tg) of the aromatic polyester (A) is not particularly limited, but is preferably 30 to 150 ° C, more preferably 40 to 120 ° C, and further preferably 50 to 100 ° C. 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) can be melt-mixed at a relatively low temperature (200 ° C. or lower). The polymerization reaction of the thermally polymerizable functional group of the crosslinkable compound (B) hardly occurs during melt mixing. 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) is not particularly limited, but is preferably 250 ° C. or lower (eg, 80 to 250 ° C.), more preferably 220 ° C. or lower, further preferably 200 ° C. or lower, and 180 ° C. or lower. Particularly preferred. When the melting point is 250 ° C. or lower, the aromatic polyester (A) and the crosslinkable compound (B) can be melt-mixed at a relatively low temperature (200 ° C. or lower), and the viscosity increases rapidly due to the thermal polymerization reaction. Hard to wake up. 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.

[Crosslinking Compound (B)]
The crosslinkable compound (B) functions as a thermosetting agent, and as described above, the reactive functional group (a) (hydroxyl group, hydroxyl group, aromatic molecule (A) at the molecular chain terminal in the molecule (in one molecule). A functional group (sometimes referred to as “reactive functional group (b)”) that reacts with an acyloxy group, an aromatic cyclic group, and at least one selected from the group consisting of conjugated diene structures; It is a compound having at least a 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. 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, 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); epoxy group; maleimide group; ester group; acid anhydride group (for example, maleic anhydride group); carboxyl group 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, maleimide groups and acid anhydride groups (particularly maleic anhydride groups) are reactive to react with an aromatic ring (for example, cycloaddition reaction). It is a reactive functional group that reacts with a functional group and / or a conjugated diene structure (for example, 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, Examples thereof include a nitrile group, a phthalonitrile group, a styryl group, an ethynyl group, a propargyl ether group, a benzocyclobutene group, a biphenylene group, and 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 thermally polymerizable functional groups 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 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, the crosslinkable compound (B) includes 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 group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group and 2-pentenyl group. 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 (particularly 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 divalent or higher valent group corresponding thereto. 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, And a group linked by a thioester bond, —NR— (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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, and a 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). The total of n1 and n2 is preferably, for example, an integer of 1 to 10 (more preferably an integer of 1 to 5). 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.

In addition, as the crosslinkable compound (B), a compound represented by the following formula (ii) (α, β-unsaturated carbonyl group (when the unsaturated group is a triple bond) and a compound having a thermopolymerizable 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). The total of n3 and n4 is preferably, for example, an integer of 1 to 10 (more preferably an integer of 1 to 5). 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. Examples of the alkoxy group include alkoxy groups having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group, and derivatives thereof. 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. As n6, for example, an integer of 1 to 10 (more preferably an integer of 1 to 5) is preferable. 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 to R ⁵ in the above formula (iv) are the same or different and each represents a hydrogen atom or an alkyl group which may have 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).

More specifically, examples of the crosslinkable compound (B) include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane. , Ethylene bismaleimide, o-phenylene bismaleimide, p-phenylene bismaleimide, m-toluylene bismaleimide, 4,4'-biphenylene bismaleimide, 4,4 '-[3,3'-dimethyl-biphenylene] bismaleimide 4,4 ′-[3,3′-dimethyldiphenylmethane] bismaleimide, 4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, 4,4′-diphenylpropane bismaleimide, 4,4′- Diphenyl ether bismaleimide, 3,3′-diphenylsulfone bismaleimide, 4,4′-diphe And bismaleimide compounds such as nylsulfone bismaleimide; 4-maleimidobenzoic acid; 4-maleimidobenzoic acid methyl; 4-maleimidobenzoic acid ethyl and the like.

The melting point (Tm) of the crosslinkable compound (B) is not particularly limited, but is preferably 250 ° C. or lower (60 to 250 ° C.), more preferably 230 ° C. or lower, and further preferably 210 ° C. or lower. Since the melting point is 250 ° C. or lower, the crosslinkable compound (B) can also be melted at a temperature at which the aromatic polyester (A) melts. In addition, the said melting | fusing point shows the endothermic peak of DSC.

The heat generation starting temperature of the crosslinkable compound (B) is not particularly limited, but is preferably 300 ° C. or lower (100 to 300 ° C.), more preferably 280 ° C. or lower, and further preferably 260 ° C. or lower. When the exothermic start temperature is 300 ° C. or lower, 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 is a temperature at which the curve starts to rise from the baseline in DSC.

The difference between the heat generation start temperature and the melting point (Tm) of the crosslinkable compound (B) is not particularly limited, but 50 ° C. or less is particularly useful (40 ° C. or less is more useful, and 30 ° C. or less is more useful). When the difference between the exothermic start temperature and the melting point (Tm) is 50 ° C. or less, the time during which melt mixing can be performed from the time when the crosslinkable compound (B) is melted until the curing reaction starts and the increase in viscosity starts is short, Viscosity is likely to increase. For this reason, the production method of the present invention has a great effect of suppressing an increase in viscosity. In general, the heat generation start temperature is higher than the melting point (Tm).

[Maleimide derivative (B ′)]
The maleimide derivative (B ′) has a melting point of 150 ° C. or less and / or a difference between the melting point and the exothermic starting temperature of the maleimide derivative is 30 ° C. or more, and the aromatic polyester (A) is a molecule in the molecule (in one molecule). A maleimide group that reacts with the reactive functional group (a) at the chain end (at least one selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic cyclic group, and a conjugated diene structure), and a thermopolymerizable functional group Having at least two maleimide groups. The maleimide derivative (B ′) may be included in the crosslinkable compound (B), and the maleimide derivative (B ′) may be used as the crosslinkable compound (B).

The number of maleimide groups in the maleimide derivative (B ′) is not particularly limited as long as it is 2 or more, but is preferably 2 to 10, more preferably 2 to 5.

The maleimide derivative (B ′) needs to have at least one maleimide group that reacts with the reactive functional group (a) and at least one thermopolymerizable functional group. For example, the maleimide group in which the maleimide derivative (B ′) functions as both a reactive functional group and a thermopolymerizable functional group needs 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 ring, or conjugated diene structure of the aromatic polyester (A), and can no longer function as a thermopolymerizable functional group. Because.

Examples of the maleimide derivative (B ′) include compounds having 100 or less (preferably 10 to 50) carbon atoms. Among them, the maleimide derivative (B ′) 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 (B ′) include 2,2-bis [4- (4-maleimidophenoxy) as an aromatic bismaleimide compound containing three or more aromatic rings (phenylene groups) in one molecule. Phenyl] propane, bis [4-maleimide (4-phenoxyphenyl)] sulfone, 1,1 ′-[1,4-phenylenebis (oxy-4,1-phenylene)] bismaleimide, 1,1 ′-[sulfonyl Bis (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, '-[(2,2', 3,3 ', 5,5', 6,6'-octafluoro [1,1'-biphenyl] -4,4'-diyl) bis (oxy-3,1- Phenylene)] bismaleimide and the like. 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.

As the maleimide derivative (B ′), specifically, as the aromatic bismaleimide compound containing two aromatic rings (phenylene groups) in one molecule, N, N ′-(4,4′-biphenylene) bis Maleimide, 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 ′-[1,4-butanediylbis (oxy- p-phenylene)] bismaleimide and the like. Of these, 4,4'-diphenyl sulfide bismaleimide and 4,4'-diphenyl ether bismaleimide are preferable.

As the maleimide derivative (B ′), specifically, as an aromatic bismaleimide compound containing one aromatic ring (phenylene group) in one molecule, 4-methyl-1,3-phenylenebismaleimide, 1, Examples include 3-phenylene 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 (B ′) include 1,6-bismaleimide- (2,2,4-trimethyl) hexane and 1,6-bismaleimide- (2,4) as aliphatic bismaleimide compounds. , 4-trimethyl) hexane, N, N′-decamethylene bismaleimide, N, N′-decamethylene bismaleimide, N, N′-octamethylene bismaleimide, N, N′-heptamethylene bismaleimide, N, N '-Hexamethylene bismaleimide, N, N'-pentamethylene bismaleimide, N, N'-tetramethylene bismaleimide, N, N'-trimethylene bismaleimide, N, N'-ethylene bismaleimide, N, N' -(Oxydimethylene) bismaleimide, 1,13-bismaleimide-4,7,10-trioxatridecane, 1,11 Bis (maleimide) -3,6,9-like 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 (i), may be mentioned. One of these maleimide derivatives (B ′) can be used alone, or two or more can be used in combination.

As the maleimide derivative (B ′), a commercially available product can be used. The trade name “BMI-1000”, the trade name “BMI-1100”, the trade name “BMI-2000”, the trade name “BMI-2300”, the trade name “BMI-TMH” (manufactured by Daiwa Kasei Co., Ltd.), product name “BMI-3000”, product name “BMI-689”, product name “BMI-1500” (above, Air Brown Co., Ltd.) Manufactured).

In particular, polyphenylmethanemaleimide, which is a compound represented by the following formula (i), is a compound represented by the following formula (ii) because it has a low melting point and is easily mixed with the aromatic polyester (A) at a low temperature. 1,6-Bismaleimide- (2,2,4-trimethyl) hexane is preferred.

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

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

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

The melting point (Tm) of the maleimide derivative (B ′) is preferably 150 ° C. or lower (60 to 150 ° C.), more preferably 130 ° C. or lower, still more preferably 110 ° C. or lower, and particularly preferably 90 ° C. or lower. When the melting point is 150 ° C. or lower, mixing can be performed 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 of DSC.

Specifically, the melting point (Tm) of the maleimide derivative (B ′) is polyphenylmethane maleimide (trade name “BMI-2300”, manufactured by Daiwa Kasei Co., Ltd.), which is a compound represented by the above formula (i). ) Is 63 ° C., a compound represented by the above formula (ii), 1,6-bismaleimide- (2,2,4-trimethyl) hexane (trade name “BMI-TMH”, manufactured by Daiwa Kasei Co., Ltd. ) Is 81 ° C., and m-phenylene bismaleimide (trade name “BMI-3000”, manufactured by Air Brown Co., Ltd.) is 62 ° C.

The heat generation starting temperature of the maleimide derivative (B ′) is not particularly limited, but is preferably 250 ° C. or lower (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 mixing with the aromatic polyester (A) is relatively low, and the curing temperature (curing temperature) becomes high. Not too much. The heat generation start temperature is a temperature at which the curve starts to rise from the baseline in DSC.

The exothermic start temperature of the maleimide derivative (B ′) is specifically polyphenylmethane maleimide (trade name “BMI-2300”, manufactured by Daiwa Kasei Co., Ltd.), which is a compound represented by the above formula (i). 1,6-bismaleimide- (2,2,4-trimethyl) hexane (trade name “BMI-TMH”, manufactured by Daiwa Kasei Co., Ltd.), which is a compound represented by the above formula (ii) at 120 ° C. Is 190 ° C., and m-phenylene bismaleimide (trade name “BMI-3000”, manufactured by Air Brown Co., Ltd.) is 230 ° C.

The difference between the heat generation starting temperature and the melting point (Tm) of the maleimide derivative (B ′) is particularly useful when it is 30 ° C. or higher (30 to 120 ° C.) (40 ° C. or higher is more useful, and 50 ° C. or higher is more useful). ). When the difference between the melting point and the heat generation start temperature is 30 ° C. or more, it is easy to maintain a long mixing time from the time when the maleimide derivative (B ′) is melted until the curing reaction starts and the viscosity starts to increase. In general, the heat generation start temperature is higher than the melting point (Tm). Among these, the maleimide derivative (B ′) preferably has a melting point of 150 ° C. or lower and a difference between the melting point and the heat generation start temperature of 30 ° C. or higher.

Specifically, the difference between the exothermic onset temperature and the melting point (Tm) of the maleimide derivative (B ′) is specifically the polyphenylmethane maleimide (trade name “BMI-2300”) which is a compound represented by the above formula (i). 1,6-bismaleimide- (2,2,4-trimethyl) hexane (trade name “BMI-TMH”), which is a compound represented by the above formula (ii) at 57 ° C., manufactured by Daiwa Kasei Co., Ltd. Yamato Kasei Co., Ltd.) is 109 ° C., and m-phenylene bismaleimide (trade name “BMI-3000”, Air Brown Co., Ltd.) is 168 ° C.

[Additive]
The thermosetting aromatic polyester composition in the present invention lowers 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, additives such as inorganic fillers are added. 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 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 , Montmorillona , 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 magnet, magnetic powder 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. 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 a thermosetting aromatic polyester composition for semiconductor sealing materials, it is preferable to use a silica (silica filler) etc., and adjust the heat conductivity and heat dissipation characteristic of hardened | cured material. In this case, it is preferable to use alumina (alumina fine particles) or the like.

Additives other than the above inorganic fillers are not particularly limited. For example, diamino compounds [eg diaminodiphenylmethane etc.], diallyl compounds [diallylbisphenol A etc.], triazines [eg 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.

[Curing accelerator]
In the method for producing the thermosetting aromatic polyester composition of the present invention, a curing accelerator may be used to accelerate the curing reaction and lower the thermosetting start temperature. The curing accelerator includes a radical generator described later.

The curing accelerator is not particularly limited as long as it is a compound having a function of promoting a curing reaction, and examples thereof include a radical generator, an imidazole derivative, an organic base and a salt thereof. These curing accelerators can be used singly or in combination of two or more. As the radical generator, the following can be used as light or thermal radical generators.

Examples of the photo radical generator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, 2-hydroxy-2- Methyl propiophenone, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd. Sakai Kayacure EPA, etc.), 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd. Kayacure DETX etc.), 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropano 2-amino-2-benzoyl-1-phenylalkane compounds such as 2-methyl-1- (4-morpholino) benzoyl-1-phenylpropane, tetra-1, Aminobenzene derivatives such as (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminobenzophenone, 2,2′-bis ( Imidazole compounds such as 2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (eg, Bodo-CIM manufactured by Hodogaya Chemical Co., Ltd.), 2,6-bis ( Halomethylated triazine compounds such as trichloromethyl) -4- (4-methoxynaphthalen-1-yl) -1,3,5-triazine And halomethyloxadiazole compounds such as 2-trichloromethyl-5- (2-benzofuran-2-yl-ethenyl) -1,3,4-oxadiazole. These radical photopolymerization initiators can be used alone or in combination of two or more. Moreover, a photosensitizer can be added to the resin composition of this invention as needed. As the photo radical polymerization initiator, for example, those activated by light having a wavelength of around 400 nm, such as diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, are preferable.

Examples of the thermal radical generator include organic peroxides. Examples of the organic peroxides that can be used include dialkyl peroxides, acyl peroxides, hydroperoxides, ketone peroxides, and peroxyesters. Specific examples of the organic peroxide include benzoyl peroxide, t-butylperoxy-2-ethylhexanate, 2,5-dimethyl-2,5-di (2-ethylhexanoyl) peroxyhexane, t- Butyl peroxybenzoate, t-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-dibutylperoxyhexane, 2,4-dichlorobenzoyl peroxide Oxide, di-t-butylperoxy-diisopropylbenzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, methyl ethyl ketone peroxide, 1,1,3,3-tetramethylbutyl Peroxy-2-ethylhexanoate and the like. Other radical generators include 2,3-dimethyl-2,3-diphenylbutane. Of these, dicumyl peroxide and 2,3-dimethyl-2,3-diphenylbutane are preferable. One of these radical generators can be used alone, or two or more thereof can be used in combination.

Furthermore, together with the above thermal radical generator, a metal salt such as naphthenic acid such as cobalt naphthenate, manganese naphthenate, zinc naphthenate, cobalt octenoate, cobalt octenoate, manganese, lead, zinc, vanadium, etc. it can. Similarly, tertiary amines such as dimethylaniline can be used.

Examples of the imidazole derivatives include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1 -Cyanoethyl-2-ethyl-4-methylimidazole and the like. These imidazole derivatives can be used alone or in combination of two or more.

Examples of the organic base and salts thereof include 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and salts thereof (for example, phenol salts, octylates, p-toluenesulfonates, Formate, tetraphenylborate salt); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and salts thereof (eg, phosphonium salts, sulfonium salts, quaternary ammonium salts, iodonium salts); benzyl Tertiary amines such as dimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine; 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methyl Imidazoles such as imidazole; Phosphates such as phosphate esters and triphenylphosphine; Tetra E sulfonyl phosphonium tetra (p- tolyl) phosphonium compounds such as borate and the like. These organic bases and salts thereof can be used singly or in combination of two or more.

Examples of the organic base and salts thereof include U-CAT SA 506, U-CAT SA 102, U-CAT 5003, U-CAT 18X (above, manufactured by San Apro Co., Ltd.), TPP-K, TPP-MK ( As described above, commercially available products such as Hokuko Chemical Co., Ltd. and PX-4ET (Nihon Chemical Industry Co., Ltd.) can also be used.

The amount of the curing accelerator is not particularly limited, but is preferably 0.01 to 10 parts by weight and more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the aromatic polyester (A).

[First manufacturing method]
As described above, in the first production method, the aromatic polyester (A) and the additive are melt-mixed in Step I, and the mixture obtained in Step I is added with the crosslinkable compound (B) and melt-mixed. There is no particular limitation as long as it includes step II. Examples of the additive include the above additives (particularly inorganic fillers). By adding the crosslinkable compound (B) to the mixture obtained in the step I and the aromatic polyester (A) and melt-mixing, the reactive functional group (a) of the aromatic polyester (A) (hydroxyl group, Reaction (for example, addition reaction) mainly with the reactive functional group (b) of the crosslinkable compound (B) and at least one selected from the group consisting of an acyloxy group, an aromatic ring, and a conjugated diene structure) It progresses and the aromatic polyester composition which has thermosetting property is obtained. In producing a thermosetting aromatic polyester composition, the aromatic polyester (A) can be used alone or in combination of two or more. Similarly, the crosslinkable compound (B) can be used alone or in combination of two or more.

The blending amount (blending ratio) of the aromatic polyester (A) and the additive (particularly inorganic filler) varies depending on the type of the additive and the like and is not particularly limited. The amount of the additive (particularly inorganic filler) is preferably 10 to 4000 parts by weight, more preferably 30 to 3000 parts by weight, and further 50 to 2000 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). 100 to 1500 parts by weight is preferable. When the blending amount of the additive is within the above range, the aromatic polyester (A) can be sufficiently diluted, the progress of the curing reaction can be suppressed, and the increase in the viscosity of the thermosetting aromatic polyester composition can be suppressed. Further, a large amount of the crosslinking agent does not remain in the thermosetting aromatic polyester composition, and the physical properties of the cured product are hardly adversely affected.

It is preferable to add at least 50% by weight (more preferably 80% by weight or more, still more preferably 90% by weight, particularly preferably 100% by weight) of the additive (particularly inorganic filler) to be blended in Step I.

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 400 parts by weight, more preferably 20 to 300 parts by weight, and even more preferably 30 to 250 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.

The crosslinkable compound (B) to be blended is preferably added in the whole amount in Step II, but a part (for example, 10% by weight or less of the total blended amount, preferably 5% by weight within the range not impairing the effects of the present invention) % Or less) may be added in step I.

In the thermosetting aromatic polyester composition of the present invention, the additive (especially inorganic filler) and the crosslinkable compound (B) are each added in an amount of 100 parts by weight of the aromatic polyester (A). 10 to 4000 parts by weight, the crosslinkable compound (B) is preferably 10 to 400 parts by weight, the additive is preferably 30 to 3000 parts by weight, and the crosslinkable compound (B) is more preferably 20 to 300 parts by weight.

In Step I, the mixing temperature when the aromatic polyester (A) and the additive (particularly inorganic filler) are melt-mixed may be any temperature that can melt the aromatic polyester (A). Although not limited, it is preferably 300 ° C. or lower (for example, 80 to 300 ° C.), more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower. The temperature of melt mixing can be controlled to be constant during melt mixing, or can be controlled to vary stepwise or continuously.

In Step I, the time for melting and mixing the aromatic polyester (A) and the additive (particularly inorganic filler) is not particularly limited, but is preferably 4 to 120 minutes, more preferably 6 to 60 minutes, and more preferably 8 to 30 minutes is more preferable. When the melt mixing time is within the above range, the productivity of the cured product does not decrease, and the additive can be more uniformly dispersed.

In step II, the mixing temperature at the time of melt mixing with the crosslinkable compound (B) is a temperature at which the aromatic polyester (A) and the crosslinkable compound (B) can be melted (in particular, the aromatic polyester (A)). The melting point is not lower than 200 ° C. (for example, 80 to 200 ° C.), more preferably 190 ° C. or less, and even more preferably 180 ° C. or less. 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.

In Step II, the time for melt mixing with the crosslinkable compound (B) is not particularly limited, but is preferably 30 to 600 minutes, more preferably 40 to 400 minutes, and further preferably 50 to 200 minutes. 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.

In particular, in the first production method, in Step I, the mixing temperature when the aromatic polyester (A) and the additive (especially inorganic filler) are melt-mixed is 80 to 300 ° C., and in Step II, the crosslinkable compound ( It is preferable that the mixing temperature at the time of adding and mixing B) is 80 to 200 ° C. and the mixing time is 30 to 600 minutes.

In the first production method, in Step II, the melt viscosity of the thermosetting aromatic polyester composition when a uniform thermosetting aromatic polyester composition is obtained after the crosslinkable compound (B) is added and melt mixed. The (initial complex viscosity) is preferably at most 1000 Pa · s, more preferably at most 500 Pa · s, further preferably at most 200 Pa · s, particularly preferably at most 100 Pa · s at 200 ° C. or less (for example, 180 ° C.). 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 additives other than the inorganic filler can be blended together when the aromatic polyester (A) in Step I and the inorganic filler are melt-mixed, and when melt-mixed with the crosslinkable compound (B) in Step II. Can also be blended.

In Step I and Step II, the melt mixing can be performed under normal pressure, or can be performed under reduced pressure or under pressure. Moreover, the said melt mixing can also be performed in one step, and can also be performed by dividing into two or more steps.

In Step I and Step II, the melt mixing can be performed using a known or conventional device (melt mixing device). 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 fluidized mixer, a ribbon mixer, a Banbury mixer, a Haake mixer, a static mixer; Kneader etc. Is mentioned.

The thermosetting aromatic polyester composition in the present invention can be obtained by melt-mixing the aromatic polyester (A) and the crosslinkable compound (B). In the thermosetting aromatic polyester composition of the present invention, the reactive functional group (a) at the molecular chain end of the aromatic polyester (A) and the reactive functional group (b) of the crosslinkable compound (B) are melted. It is a composition which contains the reaction material formed by reacting at the time of mixing as an essential component. In the reaction product, one or more of the aromatic polyester (A) and one or more of the crosslinkable compound (B) are bonded by the above-described reaction (for example, addition reaction).

Specifically, the reaction product of the above-described aromatic polyester (A), additive, and crosslinkable compound (B) is, for example, when the aromatic polyester (A) has a hydroxyl group as the reactive functional group (a). And when the compound represented by the said Formula (i) is used as a crosslinkable compound (B), it represents with following formula (1).

L ¹ in the above formula (1) represents an aromatic polyester skeleton. Examples of the aromatic polyester skeleton include a skeleton obtained by removing one hydroxyl group (hydroxyl group at the end of the molecular chain) from the aromatic polyester (A), and two or more aromatic polyesters (A) having one or more crosslinkable compounds (B ) (A compound represented by the formula (i)) and a skeleton obtained by removing one hydroxyl group (hydroxyl group at the end of the molecular chain) from those formed by reacting and linking (reaction product).

X ¹ , X ² , R ¹ , R ² , Y ¹ , Y ² , n1, and n2 in the above formula (1) are the same as those in the above formula (i).

The reactant is, for example, a case where the aromatic polyester (A) has an aromatic cyclic group as the reactive functional group (a), and is represented by the formula (i) as the crosslinkable compound (B). When the compound is used, the aromatic ring of the aromatic polyester (A) and the carbon-carbon double bond of the crosslinkable compound (B) are formed by a cyclization reaction (for example, a cycloaddition reaction). May be a reaction product.

The reactant is, for example, a case where the aromatic polyester (A) has a conjugated diene structure as the reactive functional group (a), and is represented by the above formula (i) as the crosslinkable compound (B). When the compound is used, the conjugated diene structure of the aromatic polyester (A) and the carbon-carbon double bond of the crosslinkable compound (B) are formed by a cyclization reaction (for example, a cycloaddition reaction). It may be a reactant.

The reaction product of the aromatic polyester (A) and the crosslinkable compound (B) is, for example, a case where the aromatic polyester (A) has a hydroxyl group as the reactive functional group (a), and the crosslinkable compound When the compound represented by the above formula (ii) is used as (B), it is represented by the following formula (2).

L ² in the above formula (2) represents an aromatic polyester skeleton. Examples of the aromatic polyester skeleton include a skeleton obtained by removing one hydroxyl group (hydroxyl group at the end of the molecular chain) from the aromatic polyester (A), and two or more aromatic polyesters (A) having one or more crosslinkable compounds (B ) (A compound represented by the formula (ii)) and a skeleton obtained by removing one hydroxyl group (hydroxyl group at the end of the molecular chain) from those formed by reacting and linking (reaction product). X ³ , X ⁴ , Y ³ , Y ⁴ , n3, and n4 in the above formula (2) are the same as those in the above formula (ii).

The reaction product of the aromatic polyester (A) and the crosslinkable compound (B) is, for example, a case where the aromatic polyester (A) has a hydroxyl group or an acyloxy group as the reactive functional group (a). When the compound represented by the above formula (iii) is used as the crosslinkable compound (B), it is represented by the following formula (3).

L ³ in the above formula (3) represents an aromatic polyester skeleton. Examples of the aromatic polyester skeleton include a skeleton obtained by removing one hydroxyl group (hydroxyl group at the molecular chain terminal) or acyloxy group (acyloxy group at the molecular chain terminal) from the aromatic polyester (A), two or more aromatic polyesters ( One hydroxyl group (hydroxyl group at the end of the molecular chain) from one formed by reacting and linking A) with one or more crosslinkable compounds (B) (compound represented by formula (iii)) Alternatively, a skeleton excluding an acyloxy group (acyloxy group at the end of the molecular chain) may be used. X ⁵ , Y ⁵ , and n5 in the above formula (3) are the same as those in the above formula (iii).

The reaction product of the aromatic polyester (A) and the crosslinkable compound (B) is, for example, a case where the aromatic polyester (A) has a hydroxyl group as a reactive functional group, and the crosslinkable compound (B). When the compound represented by the above formula (iv) is used, it is represented by the following formula (4) or the following formula (5).

L ⁴ in the above formulas (4) and (5) represents an aromatic polyester skeleton. Examples of the aromatic polyester skeleton include a skeleton obtained by removing one hydroxyl group (hydroxyl group at the end of the molecular chain) from the aromatic polyester (A), and two or more aromatic polyesters (A) having one or more crosslinkable compounds (B ) (Compound represented by formula (iv)) and a skeleton obtained by removing one hydroxyl group (hydroxyl group at the end of the molecular chain) from those formed by reacting and linking (reaction product). In the above formulas (4) and (5), X ⁶ , Y ⁶ , R ³ to R ⁵ and n6 are the same as those in the above formula (iv).

In the first production method, the heat generation starting temperature of the thermosetting aromatic polyester composition is not particularly limited, but is preferably 250 ° C. or lower (eg, 100 to 250 ° C.), more preferably 230 ° C. or lower, and 210 ° C. or lower. Is more preferable. When the heat generation start temperature is 250 ° C. or lower, the curing temperature (curing temperature) does not become too high. The heat generation start temperature is a temperature at which the curve starts to rise from the baseline in DSC.

As described above, in the first production method, the aromatic polyester (A) and the additive are melt-mixed, and the crosslinkable compound (B) is added to the mixture obtained in the step I and melt-mixed. By including Step II to be performed, the relative proportion of the aromatic polyester (A) in the thermosetting aromatic polyester composition at the time of melt mixing of the aromatic polyester (A) and the crosslinkable compound (B) is lowered. By diluting, the reaction rate of the crosslinking reaction (thermal polymerization reaction) decreases, and the heating time that the crosslinking compound (B) receives decreases, thereby suppressing the increase in viscosity of the thermosetting aromatic polyester composition. Can do.

[Second manufacturing method]
As described above, the second production method is not particularly limited as long as it includes a step of adding and mixing the maleimide derivative (B ′) to the aromatic polyester (A). The mixing may be performed in a state where at least a part of the aromatic polyester (A) and the maleimide derivative (B ′) is melted, or at least one of the aromatic polyester (A) and the maleimide derivative (B ′). You may carry out in the state which dissolved the part in the solvent. By the above mixing, the reactive functional group (a) of the aromatic polyester (A) (at least one selected from the group consisting of a hydroxyl group, an acyloxy group, an aromatic ring, and a conjugated diene structure) and a maleimide derivative (B ′ ) Reaction with a maleimide group (for example, an addition reaction) may proceed mainly to form a reaction product (for example, an adduct). In the production method of the present invention, in producing a thermosetting aromatic polyester composition, the aromatic polyester (A) can be used alone or in combination of two or more. You can also. Similarly, the maleimide derivative (B ′) can be used alone or in combination of two or more.

In the second production method, the blending ratio (blending amount) of the aromatic polyester (A) and the maleimide derivative (B ′) varies depending on the types of the aromatic polyester (A) and the maleimide derivative (B ′) and is particularly limited. Not. The blending amount of the maleimide derivative (B ′) is preferably 10 to 400 parts by weight, more preferably 20 to 300 parts by weight, and still more preferably 30 to 250 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). When the blending amount of the maleimide derivative (B ′) is within the above range, the curability of the thermosetting aromatic polyester composition does not decrease, and a large amount of the maleimide derivative (B ′) remains in the composition. It is difficult to adversely affect the physical properties of the cured product.

The mixing temperature when mixing the maleimide derivative (B ′) with the aromatic polyester (A) is a temperature at which the aromatic polyester (A) and the maleimide derivative (B ′) can be melted or dissolved in a solvent. Although not particularly limited, it is preferably 200 ° C. or lower (80 to 200 ° C.), more preferably 160 ° C. or lower. When the mixing temperature is 200 ° C. or lower, the crosslinking reaction does not proceed, and an increase in the viscosity of the composition can be suppressed. In addition, the temperature at the time of mixing can be controlled so that it may become constant during mixing, and can also be controlled so that it may fluctuate | vary stepwise or continuously.

The time for mixing the maleimide derivative (B ′) with the aromatic polyester (A) is not particularly limited, but is preferably 30 to 600 minutes, more preferably 50 to 480 minutes. When the mixing time is in the above range, the productivity of the cured product does not decrease, and the reaction progress of the aromatic polyester (A) and the maleimide derivative (B ′) can be sufficiently advanced.

In the second production method, the thermosetting aromatic polyester composition is obtained when the maleimide derivative (B ′) is added to the aromatic polyester (A), and after mixing, a uniform thermosetting aromatic polyester composition is obtained. The melt viscosity (initial complex viscosity) is preferably not more than 80 Pa · s, more preferably not more than 50 Pa · s, still more preferably not more than 20 Pa · s, particularly preferably not more than 10 Pa · s at 200 ° C. or less (for example, 180 ° C.). preferable. When the initial complex viscosity is 80 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).

In the second production method, the heat generation starting temperature of the thermosetting aromatic polyester composition is not particularly limited, but is preferably 250 ° C. or lower (100 to 250 ° C.), more preferably 230 ° C. or lower, and further 210 ° C. or lower. preferable. When the heat generation start temperature is 250 ° C. or lower, the curing temperature (curing temperature) does not become too high. The heat generation start temperature is a temperature at which the curve starts to rise from the baseline in DSC.

Specifically, the heat generation starting temperature of the thermosetting aromatic polyester composition is, as the maleimide derivative (B ′), polyphenylmethane maleimide (trade name “BMI-”), which is a compound represented by the above formula (i). 2300 ”(manufactured by Daiwa Kasei Co., Ltd.) is 1,6-bismaleimide- (2,2,4-trimethyl) hexane, which is a compound represented by the above formula (ii) at 180 ° C. When using (trade name “BMI-TMH”, manufactured by Daiwa Kasei Co., Ltd.), the temperature is 200 ° C. The composition in which the aromatic polyester (A) and the maleimide derivative (B ′) are mixed is higher in heat generation than the maleimide derivative (B ′) alone, and the composition is more thermally stabilized. It has become.

The above mixing can be performed under normal pressure, or can be performed under reduced pressure or under pressure. Moreover, the said mixing can also be performed in one step, and can also be divided and performed in two or more steps.

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

The above mixing can also be performed in the presence of a solvent. Specific examples of the solvent include, but are not limited to, pentafluorophenol (PFP), N, N-dimethylformamide (DMF), dimethylacetamide (DMA), o-dichlorobenzene, and the like.

The amount of the solvent used is not particularly limited, but is preferably 5 to 1000 parts by weight with respect to the total amount (100 parts by weight) of the aromatic polyester (A) and the maleimide derivative (B ′), and 10 to 800 parts by weight. Is more preferable.

In the thermosetting aromatic polyester composition of the present invention, the reactive functional group (a) at the molecular chain end of the aromatic polyester (A) and the maleimide group of the maleimide derivative (B ′) are mixed with each other (for example, , An adduct) may be formed, or the aromatic polyester (A) and the maleimide derivative (B ′) may be dispersed. The reaction product is obtained by bonding one or more aromatic polyesters (A) and one or more maleimide derivatives (B ′) by a reaction (for example, an addition reaction).

In the second production method, the additive such as an inorganic filler can be included in order to adjust the performance of the cured product according to the purpose (use). Among these, an inorganic filler is preferably used as the additive. In the second production method, the curing accelerator may be used to accelerate the curing reaction and lower the thermosetting start temperature.

[Thermosetting aromatic polyester composition]
The thermosetting aromatic polyester composition of the present invention (sometimes referred to as “the composition of the present invention”) includes the aromatic polyester (A) and the crosslinkable compound (B), and includes an aromatic polyester (A ) Is lower by 30 ° C. or more than the curing temperature of the crosslinkable compound (B). The composition of the present invention is not limited to the thermosetting aromatic polyester composition obtained by the production method (the first production method or the second production method) of the present invention. The softening temperature of the aromatic polyester (A) in the composition of the present invention means a temperature at which the composition can be prepared by kneading the aromatic polyester (A) and the crosslinkable compound (B). It can measure by the method of an Example description using the polarization microscope which attached the stage. The curing temperature of the crosslinkable compound (B) is the exothermic peak temperature by DSC measurement.

The average degree of polymerization of the aromatic polyester (A) in the composition of the present invention is not particularly limited, but is preferably 3 to 30, more preferably 3 to 25, and still more preferably 3 to 20. 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) in the composition of the present invention 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.

The softening temperature of the aromatic polyester (A) in the composition of the present invention is not particularly limited, but is preferably 40 to 200 ° C, more preferably 50 to 180 ° C, and further preferably 80 to 160 ° C. 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) in the composition of the present invention 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 the pentamer is 90 to 100 ° C., and the softening temperature in the case of the 10-mer. Is 140 to 150 ° C., and the softening temperature in the case of a 20-mer is 170 to 180 ° C.

The crosslinkable compound (B) in the composition of the present invention is not particularly limited, but a maleimide derivative is preferable. Among these, as the maleimide derivative, the compounds mentioned as the maleimide derivative (B ′) are particularly preferable.

The molecular weight of the crosslinkable compound (B) (particularly the maleimide derivative) in the composition of the present invention is not particularly limited, but is preferably 200 to 10,000, more preferably 200 to 8000, and further 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 crosslinkable compound (B) (particularly the maleimide derivative) in the composition of the present invention is preferably 200 ° C. or less (eg, 60 to 200 ° C.), more preferably 180 ° C. or less, and 160 ° C. or less. Is more preferable. 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 heat generation starting temperature of the crosslinkable compound (B) (particularly the maleimide derivative) in the composition of the present invention is not particularly limited, but is preferably 250 ° C. or lower (for example, 90 to 250 ° C.), more preferably 230 ° C. or lower. 210 ° C. or lower is more preferable. 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 crosslinkable compound (B) (especially the maleimide derivative) in the composition of the present invention is not particularly limited, but is preferably 70 to 250 ° C, more preferably 80 to 240 ° C, and further preferably 90 to 230 ° C. preferable. When the curing temperature 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 crosslinkable compound (B) (particularly the maleimide derivative) in the composition of the present invention is 2,2-bis [4- as an aromatic bismaleimide compound containing 3 or more aromatic rings in one molecule. In the case of (4-maleimidophenoxy) phenyl] propane, the temperature is 240 ° C., and as an aromatic bismaleimide compound containing two aromatic rings, in the case of 4,4′-diphenylmethane bismaleimide, the temperature is 202 ° C., and the aromatic ring is 1 In the case of 4-methyl-1,3-phenylene bismaleimide, the aromatic bismaleimide compound to be contained is 210 ° C., and in the case of polyphenylmethane maleimide, which is a compound represented by the above formula (2), 226 In the case of 1,6-bismaleimide- (2,2,4-trimethyl) hexane which is a compound represented by the above formula (3) at 285 ° C. A.

In the composition of the present invention, the curing temperature of the crosslinkable compound (B) including the maleimide derivative tends to increase as the ratio of the aromatic cyclic group in the molecule increases, and in particular, polycyclic compounds such as naphthalene and anthracene. As the proportion of aromatic rings 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) when the crosslinkable compound (B) in the composition of the present invention is the maleimide derivative is not particularly limited, but is 10 to 300 weights per 100 weight parts of the aromatic polyester (A). Part by weight, preferably 10 to 250 parts by weight, more preferably 20 to 200 parts by weight. 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) in the composition of the present invention 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.

Particularly, the composition of the present invention is characterized in that the softening temperature of the aromatic polyester (A) is lower by 30 ° C. or more 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, but arises because 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) in the composition of the present invention 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.

The composition of the present invention is inorganic in order to reduce the concentration of the aromatic polyester (A) to suppress the curing reaction at the time of adjusting the composition, and to adjust the performance of the cured product according to the purpose (use). The additive such as a filler is preferably contained. Among these, an inorganic filler is preferably used as the additive.

The additive (including the inorganic filler) in the composition of the present invention is prepared by melt-mixing the aromatic polyester (A) and the crosslinkable compound (B) when preparing the thermosetting aromatic polyester composition of the present invention. In this case, the thermosetting aromatic polyester composition of the present invention can be blended once and then blended.

The composition of the present invention is not particularly limited as long as it contains an aromatic polyester (A) and a crosslinkable compound (B), but is melted by adding the aromatic polyester (A), the crosslinkable compound (B), and other additives. It is preferable to mix.

The mixing temperature at the time of melt-mixing the aromatic polyester (A) and the crosslinkable compound (B) in the composition of the present invention is a temperature at which the aromatic polyester (A) and the crosslinkable compound (B) can be melted ( The melting point of the aromatic polyester (A) is not particularly limited and 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.

The time for melt mixing the aromatic polyester (A) and the crosslinkable compound (B) in the composition of the present invention is not particularly limited, but is preferably 3 to 600 minutes, more preferably 4 to 400 minutes, and still more preferably. Is 5 to 200 minutes. 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) in the composition of the present invention is preferably 1000 Pa · s or less, more preferably 500 Pa · s or less, even more preferably 200 Pa · s or less, at 200 ° C. or less (eg, 180 ° C.), 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 fluidized mixer, a ribbon mixer, a Banbury mixer, a Haake mixer, a static mixer; Kneader etc. Is mentioned.

The composition of the present invention has a crosslinkable reactive functional group (a) 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 cured. It is preferable that an adduct formed by reacting with the reactive functional group (b) of the functional compound (B) during 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, in the composition of the present invention, the softening temperature of the aromatic polyester (A) is 30 ° C. or more lower than the curing temperature of the crosslinkable compound (B), so that the crosslinking reaction of the crosslinkable compound (B) proceeds. The aromatic polyester (A) and the crosslinkable compound (B) can be melt-mixed at a temperature that does not. Therefore, the thermosetting aromatic polyester composition can suppress an increase in viscosity and is excellent in moldability such as transfer molding.

[Cured product]
Curing by curing the thermosetting aromatic polyester composition obtained by the production method (first or second production method) of the present invention or the composition of the present invention by heating (advancing the curing reaction). Product (sometimes referred to as “cured product of the present invention”). By heating, a reaction (polymerization reaction) between the thermally polymerizable functional groups mainly caused by the crosslinkable compound (B) (or maleimide derivative (B ′)) proceeds to form a cured product. 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 is not particularly limited, but is preferably 170 to 250 ° C, more preferably 210 to 250 ° C, and further preferably 220 to 250 ° C. 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 is not particularly limited, but is preferably 30 to 600 minutes, more preferably 50 to 480 minutes, and further preferably 60 to 360 minutes. 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.

The curing of the thermosetting aromatic polyester 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 elevation rate of 10 ° C./min (in air) is not particularly limited, but is 350 ° C. or higher (eg, 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 obtained by the production method of the present invention, it has excellent heat resistance and excellent processing. Properties, dimensional stability, low linear expansion, high thermal conductivity, low hygroscopicity, and dielectric properties. Furthermore, since the cured product of the present invention is obtained by heating the thermosetting aromatic polyester composition at a relatively low temperature of 250 ° C. or lower, 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, semiconductor encapsulants. That is, the thermosetting aromatic polyester composition obtained by the production method of the present invention is, in particular, a film thermosetting composition, a prepreg thermosetting composition, a printed wiring board thermosetting composition, and a semiconductor. It can be preferably used as a thermosetting composition for sealing materials.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Glass transition temperature (Tg), melting point (Tm), exothermic start temperature]
The melting point (Tm) and exothermic start temperature of the maleimide derivatives used in the above examples and comparative examples were increased by 20 ° C./min with a differential scanning calorimeter (“DSC6200”, manufactured by Seiko Instruments Inc.). The measurement was performed under conditions (under a nitrogen stream).

[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 Co., Ltd.), the sample was melted while being heated at a temperature rising 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 Example 1 and Comparative Example 1 was 10 ° C. at TG / DTA (“TG / DTA6300”, manufactured by Seiko Instruments Inc.). It was measured under the temperature rising condition (in air) per minute.

Production Example 1
[Production of Aromatic Polyester E (Decamer)]
In a 500 mL flask equipped with a condenser and a stirrer, as shown in Table 1, 94.3 g (0.682 mol) of 4-hydroxybenzoic acid, 102.7 g (0.546 mol) of 6-hydroxy-2-naphthoic acid, 4 , 4′-dihydroxybiphenyl, 26.3 g (0.136 mol), acetic anhydride 156.3 g (1.53 mol), and potassium acetate 10.0 mg (0.10 mol) were added and gradually heated to 140 ° C. under a nitrogen atmosphere. After raising the temperature, the reaction was continued for 3 hours while maintaining the temperature to complete the acetylation reaction. 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. The thermal analysis result [glass transition temperature (Tg), melting point (Tm)] of the obtained aromatic polyester E was as shown in Table 1. The obtained aromatic polyester E was calculated by calculating the number of terminals of the aromatic polyester E (by the amine decomposition HPLC method described in JP-A No. 5-271394), and as a result of GPC measurement, It was estimated to be a body.

Production Example 2
[Production of aromatic polyester F (pentamer)]
As shown in Table 1, 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), 4,4 ′ -The amount of dihydroxybiphenyl used was 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). Operation similar to manufacture example 1 was performed, and the aromatic polyester F 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 result of the obtained aromatic polyester F was as shown in Table 1. The obtained aromatic polyester F was obtained by calculating the number of terminals of the aromatic polyester F (by the amine decomposition HPLC method described in JP-A No. 5-271394) and by GPC measurement, It was estimated to be a body.

Production 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.

Production 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

Example 1
4.61 g of aromatic polyester E obtained in Production Example 1 and 4.61 g of silica filler (trade name “FB-5SDC”, manufactured by Denki Kagaku Kogyo Co., Ltd.) as an additive were melt-mixed at 190 ° C. for 15 minutes, A melt was obtained (Step I). Thereafter, 9.22 g of the obtained melt and 2.50 g of 4,4′-diphenylmethane bismaleimide are melt-mixed at 170 ° C. for 60 minutes to obtain a uniform melt (thermosetting aromatic polyester composition). (Step II). Thereafter, the obtained melt was sandwiched between glass plates and heated to 240 ° C. with a hot plate, and the curing reaction was allowed to proceed for 6 hours to obtain a uniform cured product. Table 2 shows the initial complex viscosity at 180 ° C. of the obtained melt and the 5% weight loss temperature (T _d5 ) of the cured product.

Example 2
Melting and mixing 4.61 g of aromatic polyester F obtained in Production Example 2 and 4.61 g of silica filler (trade name “FB-5SDC”, manufactured by Denki Kagaku Kogyo Co., Ltd.) as an additive at 190 ° C. for 15 minutes, A melt was obtained (Step I). Thereafter, 9.22 g of the obtained melt and 2.50 g of 4,4′-diphenylmethane bismaleimide are melt-mixed at 170 ° C. for 60 minutes to obtain a uniform melt (thermosetting aromatic polyester composition). (Step II). Thereafter, the obtained melt was sandwiched between glass plates and heated to 240 ° C. with a hot plate, and the curing reaction was allowed to proceed for 6 hours to obtain a uniform cured product. Table 2 shows the initial complex viscosity at 180 ° C. of the obtained melt and the 5% weight loss temperature (T _d5 ) of the cured product.

Comparative Example 1
3.94 g of aromatic polyester E obtained in Production Example 1 and 2.13 g of 4,4′-diphenylmethane bismaleimide were melted and mixed at 170 ° C. for 60 minutes to obtain a melt (Step II). Thereafter, 6.07 g of the obtained melt and 3.93 g of silica filler (trade name “FB-5SDC”, manufactured by Denki Kagaku Kogyo Co., Ltd.) as an additive were melt-mixed at 190 ° C. for 10 minutes to obtain a uniform melt. A product (thermosetting aromatic polyester composition) was obtained (Step I). Thereafter, the obtained melt was sandwiched between glass plates and heated to 240 ° C. with a hot plate, and the curing reaction was allowed to proceed for 6 hours to obtain a uniform cured product. Table 2 shows the initial complex viscosity at 180 ° C. of the obtained melt and the 5% weight loss temperature (T _d5 ) of the cured product.

Example 3
29.12 g of the aromatic polyester E obtained in Production Example 1 and 43.78 g of polyphenylmethane maleimide (trade name “BMI-2300”, manufactured by Daiwa Kasei Co., Ltd.) were melt-mixed at 150 ° C. for 1 hour, A uniform melt (thermosetting aromatic polyester composition) was obtained. Thereafter, the obtained melt was sandwiched between glass plates and heated to 240 ° C. with a hot plate, and the curing reaction was allowed to proceed for 6 hours to obtain a uniform cured product. The initial complex viscosity at 180 ° C. of the obtained melt and the 5% weight reduction temperature (T _d5 ) of the cured product were as shown in Table 2. The melting point (Tm) and exothermic start temperature of the polyphenylmethane maleimide used as the maleimide derivative (B) were as shown in Table 2.

Examples 4-6, Comparative Examples 2-3
The thermosetting aromatic polyester composition was prepared in the same manner as in Example 1 except that the type and amount of the aromatic polyester (A), the type and amount of the maleimide derivative, and the mixing conditions were changed as shown in Table 3. Obtained. The initial complex viscosity at 180 ° C. of these melts (thermosetting aromatic polyester composition) and the 5% weight loss temperature (T _d5 ) of the cured product were as shown in Table 3. The polyphenylmethane maleimide and 4,4′-diphenylmethane bismaleimide used had a melting point (Tm) and an exothermic onset temperature as shown in Table 3. In Comparative Example 2, since the aromatic polyester and the maleimide derivative could not be uniformly dispersed and phase-separated, the initial complex viscosity could not be measured.

Example 7
29.1 g of the aromatic polyester E obtained in Production 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 8
30.1 g of the aromatic polyester F obtained in Production Example 2 was melted at 100 ° C. and melted as a maleimide derivative with 48.0 g of polyphenylmethane maleimide (trade name “BMI-2300” manufactured by Daiwa Kasei Co., Ltd.) for 1 hour. Mixing was performed to obtain a melt (thermosetting aromatic polyester composition).

Example 9
44.0 g of the aromatic polyester G synthesized in Production 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 4
44.0 g of the aromatic polyester H synthesized in Production Example 4 was melted at 265 ° C., and melt-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. As a result, a melt (thermosetting aromatic polyester composition) was obtained. The obtained melt was non-uniform and the maleimide derivative alone cured significantly.

Table 4 shows the initial complex viscosity at 180 ° C. and the 5% weight loss temperature (T _d5 ) of the cured product of the thermosetting aromatic polyester compositions obtained in Examples 7 to 9 and Comparative Example 4. there were.

As shown in Table 2, the thermosetting aromatic polyester composition obtained by the method of the example (first production method) was thermoset as compared with the thermosetting aromatic polyester composition of the comparative example. The initial complex viscosity of the curable aromatic polyester composition was low, and an increase in the viscosity of the thermosetting aromatic polyester composition when the crosslinkable compound (B) was melt-mixed and uniformly dispersed could be suppressed. Further, the obtained cured product had a high 5% weight loss temperature and had very excellent heat resistance.

As shown in Table 3, when the maleimide derivative (B) having a low melting point and / or a large difference between the melting point and the exothermic start temperature is used (in the case of the second production method), the aromatic is in a temperature range where the crosslinking reaction does not proceed. Mixing with the polyester (A) was possible, and an increase in the viscosity of the aromatic polyester composition could be suppressed. Therefore, the thermosetting aromatic polyester composition obtained by the second production method can be easily molded by transfer molding or the like by suppressing an increase in the viscosity of the aromatic polyester composition. Further, the obtained cured product had a high 5% weight loss temperature and had very excellent heat resistance.

As shown in Table 4, the thermosetting aromatic polyester compositions (compositions of the present invention) obtained in the examples can be melt-mixed at a relatively low temperature, have a low initial complex viscosity, and are thermally cured. Increase in viscosity of the water-soluble aromatic polyester composition could be suppressed. Moreover, the obtained cured product had a high 5% weight loss temperature and had very excellent heat resistance.

The thermosetting aromatic polyester composition obtained by the production method (the first production method or the second production method) of the present invention and the cured product obtained by curing the composition of the present invention include various members and various structural materials. It can be used for various applications such as. In particular, it is excellent in various properties such as processability, dimensional stability, low linear expansion, high thermal conductivity, low hygroscopicity, dielectric properties, etc., so it can be preferably used for applications such as films, prepregs, printed wiring boards, and semiconductor encapsulants . That is, the thermosetting aromatic polyester composition in the present invention is, in particular, a thermosetting composition for a film, a thermosetting composition for a prepreg, a thermosetting composition for a printed wiring board, and a thermosetting for a semiconductor sealing material. It can be preferably used as an adhesive composition.

Claims

A method for producing a thermosetting polyester composition containing an aromatic polyester and a crosslinkable compound, which is obtained in Step I of melt-mixing the following aromatic polyester (A) and an additive, and in Step I above. The manufacturing method of the thermosetting aromatic polyester composition including the process II which melt-mixes the following crosslinkable compound (B) to a mixture.
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 amount of the additive is 10 to 4000 parts by weight and the amount of the crosslinkable compound (B) is 10 to 400 parts by weight with respect to 100 parts by weight of the aromatic polyester (A). The manufacturing method of the thermosetting aromatic polyester composition as described in any one of.
The production of the thermosetting aromatic polyester composition according to claim 1 or 2, wherein the mixing temperature when the aromatic polyester (A) and the additive are melt-mixed in the step I is 80 to 300 ° C. Method.
The mixing temperature according to any one of claims 1 to 3, wherein in the step II, the mixing temperature when the crosslinkable compound (B) is added and melt mixed is 80 to 200 ° C, and the mixing time is 30 to 600 minutes. A method for producing a thermosetting aromatic polyester composition.
The method for producing a thermosetting aromatic polyester composition according to any one of claims 1 to 4, wherein the additive is an inorganic filler.
The method for producing a thermosetting aromatic polyester composition according to claim 5, wherein the inorganic filler is a silica filler.
The manufacturing method of the thermosetting aromatic polyester composition characterized by including the process of adding the following maleimide derivative (B ') to the following aromatic polyester (A), and mixing.
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 end Maleimide derivative (B ′ ): Melting point of 150 ° C. or less and / or difference in heat generation start temperature between the melting point and the maleimide derivative is 30 ° C. or more, and a maleimide group that reacts with the aromatic polyester (A) in the molecule and a thermopolymerizable functional group Maleimide derivative having a maleimide group as a group
The method for producing a thermosetting aromatic polyester composition according to claim 7, wherein the amount of the maleimide derivative (B ') is 10 to 400 parts by weight with respect to 100 parts by weight of the aromatic polyester (A).
9. The thermosetting according to claim 7 or 8, wherein the maleimide derivative (B ′) is added to the aromatic polyester (A) and the mixing temperature is 80 to 200 ° C. and the mixing time is 30 to 600 minutes. A method for producing an aromatic polyester composition.
10. The maleimide derivative (B ′) is at least one compound selected from a compound represented by the following formula (i) and a compound represented by the formula (ii): The manufacturing method of the thermosetting polyester composition as described in any one of.

[N in the above formula (i) represents an integer of 0 to 10]
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 (A) (the ratio of the total amount when the structural unit is two or more) is 60 to 100% by weight. 11. The method for producing a thermosetting aromatic polyester composition according to any one of 1 to 10.
The method for producing a thermosetting aromatic polyester composition according to any one of claims 1 to 11, wherein the aromatic polyester (A) has a melting point of 250 ° C or lower.
The method for producing a thermosetting aromatic polyester composition according to any one of claims 1 to 12, wherein the aromatic polyester (A) has a molecular weight of 300 to 20000.
The ratio of the hydroxyl group is 5 to 100% and the ratio of the acyloxy group is 0 to 90% with respect to the entire terminal group at the molecular chain end of the aromatic polyester (A). The method for producing a thermosetting aromatic polyester composition according to any one of claims 1 to 13, wherein the ratio of groups other than is from 0 to 90%.
A thermosetting aromatic polyester composition obtained by the method for producing a thermosetting aromatic polyester composition according to any one of claims 1 to 14.
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 16, wherein the softening temperature of the aromatic polyester (A) is 40 to 200 ° C.
The thermosetting aromatic polyester composition according to claim 16 or 17, 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 16 to 18, wherein the average degree of polymerization of the aromatic polyester (A) is 3 to 30.
The thermosetting aromatic polyester composition according to any one of claims 16 to 19, wherein the crosslinkable compound (B) is a maleimide derivative.
The thermosetting fragrance according to any one of claims 16 to 20, wherein a blending 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.
A cured product obtained by curing the thermosetting aromatic polyester composition according to any one of claims 15 to 21.
23. The 5% weight reduction rate measured at a temperature elevation rate of 10 ° C./min (in air) is 350 ° C. or higher, and the activation energy of the thermal decomposition reaction in air is 150 kJ / mol or higher. Cured product.