JP2019137713A - Thermosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a composition having a uniform liquid phase in which a thermosetting compound is dissolved in a solvent and which is rapidly cured by heat treatment to form a cured product having super heat resistance. A thermosetting composition that can be provided is provided. SOLUTION: The thermosetting composition of the present invention is obtained by dissolving a thermosetting compound represented by the following formula (1) in a solvent. In formula (1), R1 and R2 represent thermosetting groups, and D1 and D2 represent single bonds or linking groups that are the same or different. Ar1, Ar2, and Ar3 are the same or different, and have a divalent aromatic hydrocarbon group or a single bond of two or more aromatic hydrocarbons, a divalent aliphatic hydrocarbon group, or a divalent alicyclic group. A divalent group bonded via a hydrocarbon group is shown, and E represents an ester bond. [Chemical 1] [Selection diagram] None

Description

  The present invention relates to a thermosetting composition and a cured product thereof.

  In recent years, with the development of technology in the field of semiconductors and circuit boards, it has super heat resistance, that is, it has a high thermal decomposition temperature and can form a cured product that maintains high hardness even in a high temperature environment of 250 ° C. or higher. There is a need for a composition.

  In Patent Documents 1 to 3, a composition containing a thermosetting compound having a phenylethynyl group, a phenylmaleimido-N-yl group, or a nadiimido-N-yl group as a thermosetting group at a terminal of a liquid crystal oligomer is disclosed. It is described that a cured product having excellent heat resistance can be formed and used as a coating agent.

  However, in order to cure the thermosetting composition, it is necessary to heat at a high temperature of 350 ° C. or higher for a long time. For example, when used as a coating agent (or varnish), the object to be coated is heated by high temperature during curing. It was a problem that deteriorated. Further, the cured product of the thermosetting composition itself may be decomposed by high-temperature heating during curing.

  On the other hand, in Patent Document 4, a liquid crystal polyester having a hydroxyl group and / or an acyloxy group at a molecular chain terminal and a compound having a functional group that reacts with a hydroxyl group and / or an acyloxy group and a thermosetting group are melt-mixed. It is described that the thermosetting polyester composition obtained in this way is thermoset at a temperature of 250 ° C. or lower to obtain a cured product having excellent heat resistance.

JP-T-2004-509190 US Pat. No. 6,993,940 US Pat. No. 7,507,784 International Publication No. 2014/050850

  However, the thermosetting polyester composition has poor solvent solubility, and even if a solvent is added, it is difficult to use as a coating agent (or varnish) because an insoluble matter or a precipitate is generated. Moreover, since the curability is poor and heat curing requires a long time (for example, about 6 hours), workability is poor, and when it is heated at a high temperature of 300 ° C. or more for the purpose of curing in a short time, it is easily decomposed.

Accordingly, an object of the present invention is a composition in which a thermosetting compound dissolves in a solvent and exhibits a uniform liquid phase, and is cured rapidly by heat treatment and has a super heat resistance. It is providing the thermosetting composition which can form.
Another object of the present invention is to provide a coating film that can be rapidly cured by heat treatment to form a cured film having super heat resistance.
Another object of the present invention is to provide a cured product having super heat resistance.
Another object of the present invention is to provide a method for producing the thermosetting composition.

  As a result of intensive studies to solve the above problems, the inventors of the present invention show that the compound represented by the following formula (1) exhibits good solvent solubility, cures rapidly by heat treatment, and is super heat resistant. It has been found that a cured product having properties is formed. The present invention has been completed based on these findings.

（式中、Ｒ¹、Ｒ²は熱硬化性基を示し、Ｄ¹、Ｄ²は、同一又は異なって、単結合又は連結基を示す。Ａｒ¹、Ａｒ²、Ａｒ³は、同一又は異なって、２価の芳香族炭化水素基、又は２個以上の芳香族炭化水素が単結合、２価の脂肪族炭化水素基、若しくは２価の脂環式炭化水素基を介して結合した２価の基を示し、Ｅはエステル結合［−（Ｃ＝Ｏ）Ｏ−又は−Ｏ（Ｃ＝Ｏ）−］を示す） That is, this invention provides the thermosetting composition formed by melt | dissolving the thermosetting compound represented by following formula (1) in a solvent.

(In the formula, R ¹ and R ² represent thermosetting groups, D ¹ and D ² are the same or different and represent a single bond or a linking group. Ar ¹ , Ar ² and Ar ³ are the same or different. A divalent aromatic hydrocarbon group or two or more aromatic hydrocarbons bonded via a single bond, a divalent aliphatic hydrocarbon group, or a divalent alicyclic hydrocarbon group E represents an ester bond [— (C═O) O— or —O (C═O) —])

  The present invention also provides the thermosetting composition, wherein the solvent is a solvent having a boiling point of 150 ° C. or higher under normal pressure.

  The present invention also provides the thermosetting composition, wherein the solvent is at least one solvent selected from N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, and N, N-dimethylformamide. .

  The present invention also provides the thermosetting composition having a water content of less than 5000 ppm.

  The present invention also provides the thermosetting composition which is a coating agent.

  The present invention also provides a coating film comprising a solidified product of the thermosetting composition.

  The present invention also provides a cured product of the coating film.

（式中、Ｒ¹、Ｒ²は熱硬化性基を示し、Ｄ¹、Ｄ²は、同一又は異なって、単結合又は連結基を示す。Ａｒ¹、Ａｒ²、Ａｒ³は、同一又は異なって、２価の芳香族炭化水素基、又は２個以上の芳香族炭化水素が単結合、２価の脂肪族炭化水素基、若しくは２価の脂環式炭化水素基を介して結合した２価の基を示し、Ｅはエステル結合［−（Ｃ＝Ｏ）Ｏ−又は−Ｏ（Ｃ＝Ｏ）−］を示す） In the present invention, a thermosetting compound represented by the following formula (1) and a solvent are mixed, and the thermosetting compound represented by the following formula (1) is dissolved in the solvent. The manufacturing method of the thermosetting composition which obtains an adhesive composition is provided.

(In the formula, R ¹ and R ² represent thermosetting groups, D ¹ and D ² are the same or different and represent a single bond or a linking group. Ar ¹ , Ar ² and Ar ³ are the same or different. A divalent aromatic hydrocarbon group or two or more aromatic hydrocarbons bonded via a single bond, a divalent aliphatic hydrocarbon group, or a divalent alicyclic hydrocarbon group E represents an ester bond [— (C═O) O— or —O (C═O) —])

  In the thermosetting composition of the present invention, the thermosetting compound dissolves in a solvent to exhibit a uniform liquid phase, and has no insoluble matter or precipitate. Further, the thermosetting composition of the present invention does not decompose even when heated at a high temperature. For example, after the solvent is volatilized, it is rapidly cured by applying a heat treatment at a high temperature and has super heat resistance. A cured product can be formed. Therefore, the thermosetting composition of the present invention can be suitably used as a coating agent or the like.

[Thermosetting composition]
The thermosetting composition of the present invention is obtained by dissolving the thermosetting compound represented by the formula (1) in a solvent. The thermosetting composition of this invention may contain the thermosetting compound and the solvent individually by 1 type, respectively, and may contain it in combination of 2 or more types.

(Thermosetting compound)
The thermosetting compound in the present invention is represented by the following formula (1).

In formula (1), R < ¹ >, R < ² > shows a thermosetting group, D < ¹ >, D < ² > is the same or different and shows a single bond or a coupling group. Ar ¹ , Ar ² , Ar ³ may be the same or different and each is a divalent aromatic hydrocarbon group, or two or more aromatic hydrocarbons are a single bond, a divalent aliphatic hydrocarbon group, or a divalent A divalent group bonded through an alicyclic hydrocarbon group is represented, and E represents an ester bond [— (C═O) O— or —O (C═O) —].

The divalent aromatic hydrocarbon group in Ar ¹ , Ar ² , and Ar ³ is a structural formula of an aromatic hydrocarbon (for example, an aromatic hydrocarbon having 6 to 14 carbon atoms such as benzene, naphthalene, anthracene, phenanthrene). From which two hydrogen atoms are removed.

  Examples of the divalent aliphatic hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms, and a linear or branched alkenylene group having 2 to 18 carbon atoms. Can be mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the linear or branched alkenylene group having 2 to 18 carbon atoms include vinylene group, 1-methylvinylene group, propenylene group, 1-butenylene group, 2-butenylene group and the like.

  Examples of the divalent alicyclic hydrocarbon group include a divalent alicyclic hydrocarbon group having 3 to 18 carbon atoms, such as 1,2-cyclopentylene group, 1,3- Cycloalkylene groups (including cycloalkylidene groups) such as cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group Etc.

Ar ¹ , Ar ² and Ar ³ are preferably the same or different and selected from groups represented by the following formulas (a1) to (a4). In addition, the attachment position in the following formula is not particularly limited.

Examples of the thermosetting group in R ¹ and R ² include phenylethynyl group, styryl group, maleimide group, nadiimide group, biphenylene group, ethynyl group, isocyanate group, cyanate group, nitrile group, phthalonitrile group, cyclobenzo Examples include a butene group, a benzoxazine group, an oxetane group, and a vinyl group. R ¹ and R ² may each represent the same group or different groups.

As the thermosetting group in R ¹ and R ² , a phenylethynyl group, a styryl group, a maleimide group, a nadiimide group are particularly preferable in that a cured product having thermotropic liquid crystal properties and particularly excellent heat resistance can be obtained. And a group selected from the group consisting of a biphenylene group, a phthalonitrile group, a cyclobenzobutene group, and a benzoxazine group.

Examples of the linking group in D ¹ and D ² include a divalent hydrocarbon group, a divalent heterocyclic group, a carbonyl group, an ether bond, an ester bond, a carbonate bond, an amide bond, an imide bond, and the like. Examples include a group in which a plurality of groups are connected.

  The divalent hydrocarbon group includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group, and examples thereof are the same as above. It is done.

The heterocyclic ring constituting the divalent heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. As such a heterocyclic ring, a 3- to 10-membered ring (preferably a 4- to 6-membered ring) having a carbon atom and at least one hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) as atoms constituting the ring. Ring), and condensed rings thereof. Specifically, a heterocycle containing an oxygen atom as a hetero atom (for example, a 3-membered ring such as an oxirane ring; a 4-membered ring such as an oxetane ring; a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, a γ-butyrolactone ring 5-membered rings such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring, etc .; benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, isochroman ring, etc. Condensed ring; 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring Bridged rings, etc.), heterocycles containing a sulfur atom as a hetero atom (for example, 5-membered rings such as thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring; 4-oxo-4H-thi A 6-membered ring such as a pyran ring; a condensed ring such as a benzothiophene ring), a heterocycle containing a nitrogen atom as a hetero atom (for example, a 5-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring; 6-membered ring such as isocyanuric ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring; condensed ring such as indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring, purine ring Etc.). Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from the above structural formula of the heterocyclic ring.

Examples of D ¹ and D ² include a single bond or a divalent hydrocarbon group (preferably a divalent aromatic hydrocarbon group, particularly preferably a C 6-14 divalent aromatic hydrocarbon group. Most preferably, groups selected from the groups represented by the above formulas (a1) to (a4) are particularly preferable in that a cured product having excellent heat resistance is obtained.

Accordingly, the R ¹ -D ¹ group and the R ² -D ² group in the formula (1) are the same or different and are nadiimide group, biphenylene group, ethynyl group, isocyanate group, cyanate group, nitrile group, phthalonitrile. Group, cyclobenzobutene group, benzoxazine group, oxetane group, vinyl group, methylmaleimide group, cinnamoyl group, propargyl ether group, and groups represented by the following formulas (r-1) to (r-12) The group selected from the groups represented by the following formulas (r-1) to (r-12) is particularly preferable.

  One or more substituents may be bonded to the aromatic hydrocarbon ring of the thermosetting compound represented by the formula (1), and examples of the substituent include 1 to 1 carbon atoms. 6 alkyl groups, C6-C10 aryl groups, C1-C6 alkoxy groups, C6-C10 aryloxy groups, and halogen atoms.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups. A chain or branched alkyl group is exemplified.

  Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.

  Examples of the alkoxy group having 1 to 6 carbon atoms include linear or branched alkoxy groups such as a methoxy group, an ethoxy group, a butoxy group, and a t-butyloxy group.

  Examples of the aryloxy group having 6 to 10 carbon atoms include a phenyloxy group and a 2-naphthyloxy group.

  The molecular weight of the thermosetting compound represented by the above formula (1) is 748 or more. Therefore, the hardened | cured material obtained by thermosetting has super heat resistance. On the other hand, when the molecular weight is below the above range, a cured product having super heat resistance tends to be difficult to obtain. In addition, the molecular weight of a thermosetting compound can be calculated | required by GPC measurement, HPLC measurement, NMR measurement, etc., for example.

  The upper limit of the molecular weight of the thermosetting compound represented by the above formula (1) is, for example, 1300, preferably 1200, particularly preferably 1000, most preferably 900. A molecular weight of 1300 or less is preferred in that it melts at a relatively low temperature, exhibits particularly excellent solubility in a solvent, and has fast curability.

  The melting point (Tm) of the thermosetting compound represented by the above formula (1) is, for example, 350 ° C. or less (for example, 100 to 350 ° C., preferably 100 to 300 ° C., particularly preferably 120 to 290 ° C., most preferably 150). ~ 280 ° C). Therefore, it can be melted at a relatively low temperature, and when the thermosetting composition of the present invention is used as a coating agent, while suppressing the deterioration of the coated body due to heat on the surface of the coated body. A coating film can be formed. In addition, melting | fusing point can be measured by thermal analysis and dynamic viscoelasticity measurements, such as DSC and TGA, for example.

Among the thermosetting compounds represented by the above formula (1), the compounds in which the R ¹ -D ¹ group and the R ² -D ² group are groups represented by the above formula (r-2) include, for example, It can be manufactured through steps [1] and [2]. Among the thermosetting compounds represented by the above formula (1), the R ¹ -D ¹ group and the R ² -D ² group are groups other than the group represented by the above formula (r-2). The compound can be produced by a method according to the following production method.
Step [1]: As a reaction substrate, aromatic diol, aromatic dicarboxylic acid and aromatic hydroxycarboxylic acid are reacted one molecule at a time (esterification reaction), or aromatic diol, aromatic dicarboxylic acid and aromatic hydroxycarboxylic acid. Carboxylic acid ester having hydroxyl group and / or carboxyl group at both ends by reacting (esterification reaction) with another type (2 molecules) selected from the above to one type (1 molecule) selected from Step [2] for obtaining (trimer): N- having a functional group that reacts with a hydroxyl group and / or a carboxyl group on a carboxylic acid ester (trimer) having a hydroxyl group and / or a carboxyl group at both ends By reacting phenylmaleimide (esterification reaction), a thermosetting compound represented by the formula (1) is obtained.

Among the above-mentioned formula (1) thermosetting compound represented by, 1 R ¹ -D ¹ group and R ² -D ² groups of the manufacturing method of the compound is a group represented by the above formula (r-2) An example is shown below. In the following formulae, Ar ¹ and Ar ² are the same as above. These may be the same or different.

  Examples of the aromatic diol include hydroquinone, 4,4′-dihydroxybiphenyl, 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, (1,1′-biphenyl) -2,5-diol, and derivatives thereof. . Examples of the derivative include a compound in which a substituent is bonded to the aromatic hydrocarbon group of the aromatic diol. Examples of the substituent include the same examples as the substituent that the aromatic hydrocarbon ring may have.

  Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4′-dibenzoic acid, and 4,4′-oxybis. Examples include benzoic acid, 4,4′-thiodibenzoic acid, 4- [2- (4-carboxyphenoxy) ethoxy] benzoic acid, and derivatives thereof. Examples of the derivative include a compound in which a substituent is bonded to the aromatic hydrocarbon group of the aromatic dicarboxylic acid. Examples of the substituent include the same examples as the substituent that the aromatic hydrocarbon ring may have.

  Examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 6-hydroxy-2-naphthoic acid, Examples include 5-hydroxy-1-naphthoic acid, 4′-hydroxy (1,1′-biphenyl) -4-carboxylic acid, and derivatives thereof. Examples of the derivative include a compound in which a substituent is bonded to the aromatic hydrocarbon group of the aromatic hydroxycarboxylic acid. Examples of the substituent include the same examples as the substituent that the aromatic hydrocarbon ring may have.

  In the N-phenylmaleimide having a functional group that reacts with the hydroxyl group and / or the carboxyl group, the functional group that reacts with the hydroxyl group is preferably a carboxyl group, and the functional group that reacts with the carboxyl group is preferably a hydroxyl group. Accordingly, N- (4-carboxyphenyl) maleimide is preferred as the N-phenylmaleimide having a functional group that reacts with a hydroxyl group, and N- (maleimide) having a functional group that reacts with a carboxyl group is preferred as N- ( 4-Hydroxyphenyl) maleimide is preferred.

  The esterification reaction in the above steps [1] and [2] is performed by, for example, (i) a method performed in the presence of a catalyst, (ii) a method performed in the presence of a condensing agent, or (iii) halogenation of a carboxyl group. It can carry out by the method of attaching | subjecting to esterification reaction.

As the catalyst in (i), either a protonic acid or a Lewis acid can be used. Examples of the protonic acid include super strong acids (SbF ₅ , SbF ₅ —HF, SbF ₅ —FSO ₃ H, SbF ₅ —CF ₃ SO ₃ H, etc.), sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, p- Examples include organic acids and inorganic acids such as toluenesulfonic acid, chloroacetic acid, picric acid, and heteropolyacid. Examples of the Lewis acid include B (OH) ₃ , BF ₃ , BF ₃ O (C ₂ H ₅ ) ₂ , AlCl ₃ , FeCl _{3 and the} like. These can be used alone or in combination of two or more.

  The usage-amount of the catalyst (when using 2 or more types, the total amount) is 1.0-50.0 mol% with respect to the total amount (mol) of a reaction substrate, for example.

  Examples of the condensing agent in (ii) include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1- [3- (dimethylamino) propyl] -3-ethylcarbodiimide, and N, N′-dicyclohexyl. Carbodiimide condensing agents such as carbodiimide, N, N′-diisopropylcarbodiimide, N-cyclohexyl-N ′-(2-morpholinoethyl) carbodiimide-p-toluenesulfonate; Imidazoles such as N, N′-carbonyldiimidazole Condensing agent; 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride n-hydrate, trifluoromethanesulfonic acid (4,6-dimethoxy- 1,3,5-triazin-2-yl). (2-octoxy-2-oxoethyl) dimethyl Ammonium and the like. These can be used alone or in combination of two or more.

  The amount of the condensing agent used (when two or more are used, the total amount) is, for example, 100 to 300 mol% with respect to the total amount (mol) of the reaction substrate.

  In (iii), examples of the halogenating agent used for halogenating the carboxyl group include thionyl chloride, oxalyl chloride, phosphorus pentachloride, phosphorus trichloride, thionyl bromide, phosphorus tribromide and the like. These can be used alone or in combination of two or more.

  The usage-amount of a halogenating agent is 1.0-3.0 mol with respect to 1 mol of carboxyl groups, for example.

  In (iii), hydrogen halide is produced as the esterification reaction proceeds, so that the reaction in the presence of a base that traps the produced hydrogen halide has the effect of promoting the progress of the esterification reaction. It is preferable at the point obtained. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and sodium hydrogen carbonate; and organic bases such as pyridine and triethylamine. These can be used alone or in combination of two or more.

  The amount of the base used is, for example, about 1.0 to 3.0 mol with respect to 1 mol of the acyl halide group in the halide of carboxylic acid.

  The esterification reaction in the above steps [1] and [2] can be performed in the presence of a solvent. Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonyl acetone, cyclohexanone, isophorone, 2-heptanone, and 3-heptanone; aromatic hydrocarbons such as benzene, toluene, and xylene; dichloromethane, Halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, dichlorobenzene and benzotrifluoride; and nitriles such as acetonitrile and benzonitrile. These can be used individually by 1 type or in combination of 2 or more types.

  The amount of the solvent used is, for example, about 5 to 20 times by weight with respect to the total (weight) of the reaction substrate. When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.

  The reaction atmosphere of the esterification reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.

  The reaction temperature of the esterification reaction in the steps [1] and [2] is, for example, about 0.0 to 200.0 ° C. The reaction time is, for example, about 0.5 to 3 hours. The esterification reaction can be performed by any method such as a batch method, a semibatch method, and a continuous method.

  After completion of the esterification reaction in the above steps [1] and [2], the obtained reaction product may be separated by means of separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc. , And can be separated and purified by separation means combining these.

(solvent)
As the solvent, the use of a solvent having a boiling point under normal pressure of, for example, 150 ° C. or higher (preferably 165 ° C. or higher, particularly preferably 180 ° C. or higher, most preferably 200 ° C. or higher) facilitates dissolution work. Is preferable.

  Examples of the solvent include N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, dimethylacetamide, N, N-dimethylformamide, and mixtures thereof.

  In the present invention, among them, it is preferable to use a solvent containing at least N-methyl-2-pyrrolidone from the viewpoint that the solubility of the thermosetting compound represented by the formula (1) is particularly excellent. The content of 2-pyrrolidone is preferably 60% by weight or more of the total amount of the solvent, more preferably 70% by weight or more, particularly preferably 80% by weight or more, most preferably 90% by weight or more, and particularly preferably 95% by weight or more. It is.

(Method for producing thermosetting composition)
The manufacturing method of the thermosetting composition of this invention mixes the 1 type (s) or 2 or more types of the thermosetting compound represented by the said Formula (1), and the 1 type (s) or 2 or more types of the solvent, A thermosetting composition obtained by dissolving the thermosetting compound represented by the formula (1) in a solvent is obtained.

  The thermosetting compound and the solvent are mixed by adding the solvent continuously or intermittently to the melted thermosetting compound, or mixing the thermosetting compound melted in the solvent continuously. Or it can carry out by adding intermittently and mixing.

  The temperature at the time of mixing the thermosetting compound and the solvent is, for example, 120 ° C. or higher, preferably 130 ° C. or higher, particularly preferably 140 ° C. or higher. The upper limit of the mixing temperature is, for example, 180 ° C., preferably 150 ° C. The mixing time is, for example, 5 minutes or more, preferably 10 minutes or more, particularly preferably 30 minutes or more, and most preferably 40 minutes or more. The upper limit of the mixing time is, for example, 120 minutes, preferably 60 minutes.

  In addition, when the thermosetting compound and the solvent are mixed, for example, a conventional dispersion such as a turbine stator type high-speed rotary stirring disperser (for example, a homogenizer), a colloid mill, an ultrasonic emulsifier, a high-pressure homogenizer, or the like. It is preferable to stir using a machine.

  The proportion of the content of the thermosetting compound represented by formula (1) in the total content of the thermosetting compound represented by formula (1) and the solvent is, for example, 1 to 10% by weight, preferably 3 -7% by weight.

  The total content of the thermosetting compound represented by the formula (1) and the solvent in the total amount of the thermosetting composition of the present invention is, for example, 30% by weight or more, preferably 50% by weight or more, and particularly preferably 70% by weight. % Or more, most preferably 90% by weight or more. The upper limit is 100% by weight.

  In addition to the above components, the thermosetting composition of the present invention may contain other components as necessary. As other components, known or commonly used additives can be used. For example, curable compounds other than the compound represented by the above formula (1), catalyst, filler, organic resin (silicone resin, epoxy resin, fluorine Resins), solvents, stabilizers (antioxidants, polymerization inhibitors, UV absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants) Flame retardant aids, reinforcing materials, nucleating agents, coupling agents, lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, fluidity improvers, colorants (dyes, pigments) Etc.), dispersants, antifoaming agents, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, thickeners and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Although the thermosetting composition of this invention may contain curable compounds other than the thermosetting compound represented by the said Formula (1) as a sclerosing | hardenable compound, all contained in a thermosetting composition. The proportion of the thermosetting compound represented by the above formula (1) in the curable compound is, for example, 70% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more.

  The thermosetting composition of the present invention preferably has a low water content (or water content) from the viewpoint of excellent solubility of the thermosetting compound represented by formula (1). It is preferably less than 5000 ppm, more preferably 4000 ppm or less, particularly preferably 3000 ppm or less, and most preferably 1000 ppm or less.

  Moreover, it is preferable that the thermosetting composition of the present invention has a small content of the antioxidant in terms of excellent solubility of the thermosetting compound represented by the formula (1), and the content of the antioxidant is It is preferable that it is 5 weight% or less of a thermosetting compound, for example, More preferably, it is 3 weight% or less, Especially preferably, it is 1 weight% or less, Most preferably, it is 0.5 weight% or less.

  Furthermore, it is preferable that the thermosetting composition of the present invention has a small content of the polymerization inhibitor in terms of excellent solubility of the thermosetting compound represented by the formula (1), and the content of the polymerization inhibitor is It is preferable that it is 5 weight% or less of a thermosetting compound, for example, More preferably, it is 3 weight% or less, Especially preferably, it is 1 weight% or less, Most preferably, it is 0.5 weight% or less.

Furthermore, the thermosetting composition of the present invention does not contain a crosslinking agent or a curing accelerator (for example, the total content of the crosslinking agent and the curing accelerator in the total amount of the thermosetting composition of the present invention is, for example, 3 A cured product can be rapidly formed (even if it is less than 1% by weight, preferably less than 1% by weight). Therefore, the obtained cured product has a high 5% weight loss temperature (T _d5 ) and has super heat resistance. Moreover, since content of an unreacted hardening accelerator and the decomposition product of a hardening accelerator can be suppressed very low in hardened | cured material, generation | occurrence | production of the outgas derived from these can also be suppressed.

  Since the thermosetting composition of this invention contains the said thermosetting compound, it hardens | cures rapidly by giving heat processing and can form the hardened | cured material which has super heat resistance.

The thermosetting composition of the present invention has a 5% weight loss temperature (T _d5 ) measured at a rate of temperature increase of 10 ° C./min (in nitrogen), for example, 400 ° C. or higher. The 5% weight loss temperature in this specification can be measured by, for example, TG / DTA (simultaneous measurement of differential heat and thermogravimetry).

  Moreover, the exothermic peak temperature of the thermosetting compound represented by Formula (1) is 200-350 degreeC (preferably 250-340 degreeC, Most preferably, it is 280-330 degreeC), for example. The exothermic peak temperature can be measured by DSC thermal analysis, for example.

  Therefore, the thermosetting composition of this invention containing the thermosetting compound represented by Formula (1) is 200-350 degreeC (preferably 250-340 degreeC, Especially preferably, it is 280-330 degreeC), for example. For example, by heating for 10 to 120 minutes (preferably for 10 to 60 minutes, particularly preferably for 10 to 30 minutes), it is possible to quickly cure and form a cured product having super heat resistance. In addition, heating may be performed in a state where the temperature is kept constant within the above temperature range, or may be performed in a stepwise manner. The heating temperature is preferably adjusted as appropriate within the above range according to the heating time. For example, when it is desired to shorten the heating time, it is preferable to set the heating temperature higher. The thermosetting composition of the present invention can form a cured product without being decomposed even when heated at a high temperature, and can be formed with excellent workability by heating at a high temperature for a short time. . The heating means is not particularly limited, and a known or conventional means can be used.

  Curing of the thermosetting composition of the present invention can be carried out under normal pressure, or under reduced pressure or under pressure.

The cured product of the thermosetting composition of the present invention has super heat resistance, and the 5% weight loss temperature (T _d5 ) is, for example, 400 ° C. or higher.

  In addition, the cured product of the thermosetting composition of the present invention has super heat resistance, and the glass transition temperature (Tg) is, for example, 300 ° C. or higher, preferably 350 ° C. or higher, particularly preferably 400 ° C. or higher.

  Furthermore, the cured product of the thermosetting composition of the present invention has high hardness even under a high temperature environment, and the storage elastic modulus (E ′) at 250 ° C. is, for example, 1 GPa or more (for example, 1-2 GPa), preferably 1. 1 GPa or more, particularly preferably 1.15 GPa or more.

  The thermosetting composition of the present invention can be quickly cured by heat treatment to form a cured product having super heat resistance. Therefore, for example, sealing agents, coating agents, adhesives, inks, sealants, resists, forming materials [for example, base materials, electrical insulating materials (insulating films, etc.), laminates, composite materials (fiber reinforced plastics, prepregs, etc.) , Optical elements (lenses, etc.), stereolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, holographic memory, etc.], etc. it can.

(Coating)
The coating film of this invention consists of the solidified material of the said thermosetting composition. Since the thermosetting composition dissolves the thermosetting compound in a solvent and exhibits a uniform liquid phase, the coating film of the present invention has a smooth coating surface and a uniform film thickness.

  In the coating film of the present invention, for example, the above-mentioned thermosetting composition is applied to the surface of a member that requires formation of a coating film such as a substrate, and the applied thermosetting composition is dried (= the solvent is evaporated). ) To solidify the thermosetting composition.

  The thickness of the coating film can be appropriately adjusted according to the application.

  The coating film of the present invention can be cured by the same method as the above-mentioned thermosetting composition, and a cured product of the coating film (that is, a cured film) is obtained.

  The cured product of the coating film of the present invention has super heat resistance and high hardness in the same manner as the cured product of the thermosetting composition described above. Therefore, the coating film (or cured product thereof) of the present invention is suitably used for a semiconductor sealant, a printed wiring board material, and the like.

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

NMR measurement was performed under the following conditions.
An NMR (nuclear magnetic resonance) measuring apparatus (trade name “JNM-ECA500”, manufactured by JEOL RESONANCE Co., Ltd.) was used. DMSO-d ₆ was used as the measurement solvent, and the chemical shift was based on TMS.

Preparation Example 1
In a 100 mL three-necked flask equipped with a stirrer, condenser and Dean-Stark apparatus, 22.0 mL (178.2 mol) of xylene, 4.0 g (21.7 mmol) of 4,4′-biphenol, 3.0 g of hydroxybenzoic acid (21.7 mmol), 0.044 g (0.72 mmol) of boric acid and 0.95 g (9.7 mmol) of sulfuric acid were added and stirred for 1 hour under reflux in a nitrogen atmosphere to complete the esterification reaction. Thereafter, the temperature of the reaction solution was lowered to room temperature, and the precipitate was collected, washed with methanol, and dried to obtain 1.7 g (4.0 mmol) of Compound (I-1) as white crystals. When the chemical structure of the obtained compound (I-1) was identified by NMR measurement, the compound represented by the following formula (I-1) (1,1′-biphenyl-4,4′-diylbis (4- Hydroxybenzoate), molecular weight: 426.42).

¹H-NMR(DMSO-d₆)
δ：6.95(4H,d,J=9.5Hz),7.35(4H,d,J=9.5Hz),7.76(4H,d,J=9.5Hz),8.02(4H,d,J=9.5Hz),10.55(2H,s).

¹ H-NMR (DMSO-d ₆ )
δ: 6.95 (4H, d, J = 9.5Hz), 7.35 (4H, d, J = 9.5Hz), 7.76 (4H, d, J = 9.5Hz), 8.02 (4H, d, J = 9.5Hz), 10.55 (2H, s).

In a 500 mL three-necked flask equipped with a stirrer and a condenser, 31.0 mL (291.7 mmol) of toluene, 6.7 g (31.0 mmol) of 4-maleimidobenzoic acid, 3.0 mL (41.2 mmol) of thionyl chloride, N , N-dimethylformamide (0.48 mL, 6.2 mmol) was added and stirred at 80 ° C. for 1 hour under a nitrogen atmosphere to complete the chlorination reaction. Thereafter, the volatile component was distilled off under reduced pressure to obtain 4-maleimidobenzoic acid chloride as yellowish white crystals.
Subsequently, 7.3 g (31.0 mmol) of the obtained 4-maleimidobenzoic acid chloride, 135.0 mL (1.2 mol) of o-dichlorobenzene, 6.0 g (14.1 mmol) of compound (I-1), triethylamine 4 .3 mL (31.0 mmol) was stirred for 1 hour while heating to 80 ° C. under a nitrogen atmosphere to complete the esterification reaction. Thereafter, the temperature of the reaction solution was lowered to room temperature, and the precipitate was collected, washed with methanol, and dried to obtain 8.7 g (10.6 mmol) of Compound (1) as yellowish white crystals.
When the chemical structure of the obtained compound (1) was identified by NMR measurement, it was confirmed to be a compound represented by the following formula (I) (molecular weight: 824.8).
In addition, it was confirmed that the compound (1) exhibits a thermotropic liquid crystallinity by observation with a polarizing microscope.
Furthermore, using a DSC (Differential Scanning Calorimetry) apparatus (trade name “DSC6200”, manufactured by SII Nano Technology Co., Ltd.) under a nitrogen stream (50 mL / min) at a temperature rising temperature of 10 ° C./min, the compound (1) When 5 mg was heated and the melting point (Tm) and the exothermic peak temperature were measured, the melting point (Tm) was 340 ° C. or lower and the exothermic peak temperature was 299.9 ° C.

¹H-NMR(DMSO-d₆)
δ:7.27(4H,s),7.45(4H,d,J=8.0Hz),7.60(4H,d,J=8.5Hz),7.66(4H,d,J=8.5Hz),7.83(4H,d,J=8.0Hz),8.30(8H,d,J=8.5Hz).

¹ H-NMR (DMSO-d ₆ )
δ: 7.27 (4H, s), 7.45 (4H, d, J = 8.0Hz), 7.60 (4H, d, J = 8.5Hz), 7.66 (4H, d, J = 8.5Hz), 7.83 (4H, d , J = 8.0Hz), 8.30 (8H, d, J = 8.5Hz).

Example 1
In a 100 mL three-necked flask, 10 mL of NMP (N-methyl-2-pyrrolidone, boiling point 202 ° C.) as a solvent and 0.5 g of the compound (1) obtained in Preparation Example 1 were placed. The compound (1) was dissolved in NMP by heating and stirring in a bath at 140 ° C. for 60 minutes. Then, it was rapidly cooled to room temperature (20 ° C.) (cooled over 5 minutes) to obtain a thermosetting composition (1).

The solubility of the obtained thermosetting composition (1) was evaluated by the following method.
<Solubility evaluation method>
The thermosetting composition was visually observed and the solubility was evaluated according to the following criteria.
◎: Completely dissolved at 8 hours after preparation, no precipitate ○: Completely dissolved at 4 hours after preparation, but no precipitate, but deposited at 8 hours after preparation Yes Δ: Completely dissolved immediately after preparation and no precipitate was present, but there was a precipitate 4 hours after preparation ×: Precipitate immediately after preparation

A cured product obtained by heating the thermosetting composition (1) at 350 ° C. for 15 minutes was used as a test piece, and the glass transition temperature (Tg; ° C.) was determined under the following conditions. The temperature was not confirmed. Therefore, it was confirmed that the glass transition temperature was higher than 400 ° C.
Test piece: length 10 mm x width 5 mm x thickness 5 mm
Measuring device: thermomechanical measuring device (TMA), trade name “TMA / SS6000”, manufactured by Seiko Instruments Inc. Measurement mode: compression (penetration), constant load measurement Measuring temperature: 25 ° C. to 400 ° C. Speed: 5 ° C / min

Moreover, when the 5% weight reduction | decrease temperature ( _Td5 ; degreeC) of the hardened | cured material (about 5 mg) obtained by the method similar to the above was calculated | required on the following conditions, it was 400 degreeC or more. Note that alumina was used as the reference material.
Measuring device: TG / DTA (thermogravimetric measurement / differential thermal analysis) device, trade name “EXSTAR6300”, manufactured by SII Nanotechnology Inc. Measuring atmosphere: under nitrogen stream (300 mL / min)
Measurement temperature: Temperature rising temperature 10 ° C / min

Examples 2-14
The thermosetting composition in the same manner as in Example 1 except that the presence or absence of additives, heating and dissolution conditions [heating temperature (° C.) × heating time (minutes)], and cooling method were changed as described in the following table. The product was obtained and the solubility of the obtained thermosetting composition was evaluated.
In Examples 10 to 14, the temperature was raised from 20 ° C. to 140 ° C. at a rate of 5 ° C./min to dissolve the compound (1) by heating, and after reaching 140 ° C., cooling was started immediately.
Moreover, slow cooling is cooling over 1 hour to room temperature (20 degreeC).

The abbreviations in the above table are described below.
BHT: dibutylhydroxytoluene, antioxidant HQ: hydroquinone, polymerization inhibitor Q1301: N-nitrosophenylhydroxylamine aluminum salt, polymerization inhibitor

Example 15
The thermosetting composition (1) obtained in Example 1 was applied onto a polyimide substrate and dried by heating at 140 ° C. for 5 minutes to obtain a coating film (thickness: 50 μm). Moreover, when the obtained coating film was heated at 350 ° C. for 15 minutes, it rapidly cured. Thereby, a cured film was obtained.

Claims (8)

A thermosetting composition obtained by dissolving a thermosetting compound represented by the following formula (1) in a solvent.

(In the formula, R ¹ and R ² represent thermosetting groups, D ¹ and D ² are the same or different and represent a single bond or a linking group. Ar ¹ , Ar ² and Ar ³ are the same or different. A divalent aromatic hydrocarbon group or two or more aromatic hydrocarbons bonded via a single bond, a divalent aliphatic hydrocarbon group, or a divalent alicyclic hydrocarbon group E represents an ester bond [— (C═O) O— or —O (C═O) —])   The thermosetting composition according to claim 1, wherein the solvent is a solvent having a boiling point of 150 ° C or higher under normal pressure.   The thermosetting composition according to claim 1, wherein the solvent is at least one solvent selected from N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, and N, N-dimethylformamide.   The thermosetting composition according to any one of claims 1 to 3, wherein the water content is less than 5000 ppm.   The thermosetting composition according to any one of claims 1 to 4, which is a coating agent.   The coating film which consists of a solidified material of the thermosetting composition of any one of Claims 1-5.   Hardened | cured material of the coating film of Claim 6. A thermosetting compound represented by the following formula (1) is mixed with a solvent to obtain a thermosetting composition in which the thermosetting compound represented by the following formula (1) is dissolved in the solvent. A method for producing a thermosetting composition.

(In the formula, R ¹ and R ² represent thermosetting groups, D ¹ and D ² are the same or different and represent a single bond or a linking group. Ar ¹ , Ar ² and Ar ³ are the same or different. A divalent aromatic hydrocarbon group or two or more aromatic hydrocarbons bonded via a single bond, a divalent aliphatic hydrocarbon group, or a divalent alicyclic hydrocarbon group E represents an ester bond [— (C═O) O— or —O (C═O) —])