JP2014080494A - Curable imide compound, method for producing the same, curable resin composition, and cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new curable imide compound having excellent moldability and capable of providing a cured matter having a high glass transition temperature, a high thermal decomposition temperature and a high residual carbon ratio and having a low thermal expansion coefficient.SOLUTION: In one embodiment, a curable imide compound represented by the following formula (1) is provided: in the formula (1), Rand Reach independently denote a hydrogen, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent or an aralkyl group which may have a substituent; and m denotes an integer of 1 to 4.

Description

  The present invention relates to a curable imide compound, a production method thereof, a curable resin composition containing the curable imide compound, a cured product obtained by curing the curable imide compound or the curable resin composition, and the like.

  Conventionally, thermosetting compounds have been used as electrical insulating materials, structural materials, and adhesives. Currently, thermosetting compounds are required to have good moldability, and from the viewpoints of flame retardancy and reliability, the glass transition temperature, pyrolysis temperature and residual carbon ratio are high, and the thermal expansion coefficient is low. There is a demand for things to be obtained.

  A curable imide compound having a thermosetting reactive group is also known as a thermosetting compound. However, with a known curable imide compound, good moldability cannot be obtained, and a glass transition temperature and a thermal decomposition temperature are not obtained. In addition, there is a problem that a cured product having a high residual carbon ratio and a low thermal expansion coefficient cannot be obtained.

  Patent Document 1 discloses an oligoimide or polyimide end-capped with phenylethynyl trimellitic anhydride (PETA). However, Patent Document 1 pays attention not only to obtaining good moldability but also to obtain a cured product having a high glass transition temperature, thermal decomposition temperature and residual carbon ratio and a low thermal expansion coefficient. Absent. In addition, the oligoimide or polyimide of Patent Document 1 contains not only monomer residues such as phenylethynylcarbonyl group and 4,4'-oxydianiline but also monomer residues such as pyromellitic anhydride. Furthermore, the molecular weight of the end-capped polyimide is as large as 1000-20000.

European Patent Application No. 2380867

  The present invention has been made to solve the above problems. That is, a novel curable imide compound that is excellent in moldability and has a glass transition temperature, a thermal decomposition temperature, a residual carbon ratio, and a low thermal expansion coefficient when cured, a method for producing the same, It aims at providing the curable resin composition containing a curable imide compound, the hardened | cured material of a curable imide compound or a curable resin composition, etc.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable imide compound having a specific structure is excellent in moldability and has a glass transition temperature, a thermal decomposition temperature, and a residual carbon ratio when cured. It has been found that the cured product has a high thermal expansion coefficient and a low thermal expansion coefficient. The present invention has been completed based on such findings.

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、または置換基を有してもよいアラルキル基を表し、ｍは、１〜４の整数を表す。） According to one aspect of the present invention, a curable imide compound represented by the following formula (1) is provided.

(In Formula (1), R ¹ and R ² each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an aralkyl group which may have a substituent, m represents an integer of 1 to 4)

（式（３）中、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、または置換基を有してもよいアラルキル基を表し、ｎは、１〜４の整数を表す。） According to another aspect of the present invention, the method includes a step of reacting a phenylethynyl trimellitic anhydride represented by the following formula (2) with a diamine represented by the following formula (3) in an organic solvent. A method for producing a curable imide compound is provided.

(In Formula (3), R ³ and R ⁴ each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. An alkynyl group which may have a substituent, an alkynyl group which may have a substituent, or an aralkyl group which may have a substituent, and n represents an integer of 1 to 4.

  According to the other aspect of this invention, the curable resin composition characterized by including said curable imide compound and an epoxy compound is provided.

  According to the other aspect of this invention, the hardened | cured material obtained by hardening said curable imide compound or said curable resin composition is provided.

  According to another aspect of the present invention, there is provided a cast resin composition, a printed wiring board material, a structural member material, or an adhesive using the above curable imide compound or curable resin composition. .

  According to the curable imide compound of one aspect of the present invention, since the curable imide compound is represented by the above formula (1), the glass transition temperature is excellent when it is excellent in moldability and cured. A cured product having a high thermal decomposition temperature and a residual carbon ratio and a low thermal expansion coefficient can be obtained.

  According to the method for producing a curable imide compound of another aspect of the present invention, since the curable imide compound represented by the above formula (1) can be produced, the moldability is excellent and the composition is cured. Can obtain a curable imide compound having a glass transition temperature, a thermal decomposition temperature, a residual carbon ratio, and a cured product having a low coefficient of thermal expansion.

  According to the curable resin composition of the other aspect of the present invention, since the curable imide compound is included, the moldability is excellent as compared with the case where the curable imide compound is not included, and the glass transition temperature, A cured product having a high thermal decomposition temperature and a residual carbon ratio and a low thermal expansion coefficient can be obtained.

  According to the hardened | cured material etc. of the other aspect of this invention, the hardened | cured material etc. with a high glass transition temperature, a thermal decomposition temperature, and a residual carbon ratio, and a low thermal expansion coefficient can be provided.

  Hereinafter, the curable imide compound of the present invention, the production method thereof, the curable resin composition, and the cured product will be described.

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、または置換基を有してもよいアラルキル基を表し、ｍは、１〜４の整数を表す。） <Curable imide compound>
The curable imide compound of the present invention is a compound represented by the following formula (1).

(In Formula (1), R ¹ and R ² each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an aralkyl group which may have a substituent, m represents an integer of 1 to 4)

R ¹ and R ² are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Is an alkynyl group that may have a substituent, or an aralkyl group that may have a substituent, but among these, the glass transition temperature, the thermal decomposition temperature and the residual carbon ratio are higher, and the thermal expansion coefficient is lower. From the viewpoint of obtaining a product, a hydrogen atom or an aryl group is preferable.

  As an alkyl group which may have the said substituent, C1-C6 alkyl groups, such as a methyl group and a cyclohexyl group, are mentioned, for example.

  Examples of the aryl group that may have a substituent include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Among these, a phenyl group and a naphthyl group are preferable.

  Examples of the alkenyl group which may have a substituent include 2 carbon atoms such as vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 2-pentenyl group and 2-hexenyl group. -6 alkenyl groups. Examples of the alkynyl group that may have a substituent include alkynyl groups having 2 to 6 carbon atoms such as ethynyl group, 1-propynyl group, 2-butynyl group, 2-pentynyl group, and 2-hexynyl group. Is mentioned. Furthermore, examples of the aralkyl group that may have a substituent include aralkyl groups having 7 to 15 carbon atoms such as a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

上記式（１ａ）および式（１ｂ）中のＲ^１およびＲ^２は、式（１）中のＲ^１およびＲ^２と同様である。 Although m is an integer of 1-4, it is preferable that it is an integer of 1 or 2 from a viewpoint of obtaining the outstanding moldability. Specifically, when m in the above formula (1) is 1, the curable imide compound is represented by the following formula (1a), and when m in the above formula (1) is 2, it is cured. The functional imide compound is represented by the following formula (1b).

^{R 1} and ^{R 2} in the formula (1a) and formula (1b) is the same as ^{R 1} and ^{R 2} in the formula (1).

  The curable imide compound represented by the above formula (1a) has a glass transition temperature, a thermal decomposition temperature and a residual carbon ratio higher than those of the curable imide compound represented by the above formula (1b), and has a coefficient of thermal expansion. Since a low cured product can be obtained, the curable imide compound represented by the above formula (1a) is more preferable than the curable imide compound represented by the above formula (1b).

  The curable imide compound has a phenylethynylcarbonyl group at both ends, as shown in the above formula (1). By having a phenylethynylcarbonyl group, the imide compounds can be cross-linked with each other, and thus show curability. Further, since the phenylethynylcarbonyl group has a carbonyl group adjacent to the phenylethynyl group, the phenylethynylcarbonyl group has a high degree of freedom and can lower the curing temperature than that of the phenylethynyl group alone.

Examples of the curable imide compound include those represented by the following formulas (1c) to (1f). Among these, the compound represented by the following formula (1c) and the following formula (1d) is preferable, and the compound represented by the following formula (1c) is most preferable.

  The molecular weight of the curable imide compound is preferably 700 or more and less than 1000, and more preferably 700 or more and 900 or less. When the molecular weight of the curable imide compound is within this range, it is possible to obtain a cured product having a high glass transition temperature, a thermal decomposition temperature and a residual carbon ratio and a low thermal expansion coefficient while maintaining excellent moldability.

  Since the curable imide compound of the present invention is represented by the above formula (1), it has excellent moldability and, when cured, has a high glass transition temperature, thermal decomposition temperature and residual carbon ratio, A cured product having a low expansion coefficient can be obtained. The reason for this is not clear, but the curable imide compound of the present invention has only a phenyl ether group inside the molecule as compared with the imide group as represented by the above formula (1). It has excellent heat resistance and oxidation resistance derived from it and has a flexible structure, and it is considered that the above-described effects can be obtained.

（式（３）中、Ｒ^３およびＲ^４は、それぞれ独立して、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、または置換基を有してもよいアラルキル基を表し、ｎは、１〜４の整数を表す。） <Method for producing curable imide compound>
Such a curable imide compound is obtained, for example, by reacting phenylethynyl trimellitic anhydride represented by the following formula (2) with a diamine represented by the following formula (3) in an organic solvent. be able to.

(In Formula (3), R ³ and R ⁴ each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. An alkynyl group which may have a substituent, an alkynyl group which may have a substituent, or an aralkyl group which may have a substituent, and n represents an integer of 1 to 4.

R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Is an alkynyl group that may have a substituent, or an aralkyl group that may have a substituent, but among these, the glass transition temperature, the thermal decomposition temperature and the residual carbon ratio are higher, and the thermal expansion coefficient is lower. From the viewpoint of obtaining a product, a hydrogen atom or an aryl group is preferable.

Examples of the alkyl group which may have the substituent in R ³ and R ^4, for example, an alkyl group having 1 to 6 carbon atoms such as a methyl group or a cyclohexyl group.

Examples of the aryl group that may have the above-described substituent in R ³ and R ⁴ include aryl groups having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Among these, a phenyl group and a naphthyl group are preferable.

Examples of the alkenyl group which may have the above substituent in R ³ and R ⁴ include, for example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 2-pentenyl group and 2-hexenyl. And C2-C6 alkenyl groups such as groups. Examples of the alkynyl group that may have a substituent include alkynyl groups having 2 to 6 carbon atoms such as ethynyl group, 1-propynyl group, 2-butynyl group, 2-pentynyl group, and 2-hexynyl group. Is mentioned. Furthermore, examples of the aralkyl group that may have a substituent include aralkyl groups having 7 to 15 carbon atoms such as a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

上記式（３ａ）および式（３ｂ）中のＲ^３およびＲ^４は、式（３）中のＲ^３およびＲ^４と同様である。 Although n is an integer of 1-4, it is preferable that it is an integer of 1 or 2 from a viewpoint of obtaining the outstanding moldability. Specifically, when n in the above formula (3) is 1, the curable imide compound is represented by the following formula (3a), and when n in the above formula (3) is 2, it is cured. The functional imide compound is represented by the following formula (3b).

^{R 3} and ^{R 4} in the formula (3a) and formula (3b) is the same as ^{R 3} and ^{R 4} in the formula (3).

  The phenylethynyl trimellitic anhydride is preferably blended in a proportion of 2 mol or more and 4 mol or less, more preferably 2 mol or more and 3 mol or less, per 1 mol of the diamine.

  Examples of the diamine represented by the formula (3) include 3,4′-oxydianiline, 4,4′-oxydianiline, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene and the like. Among these, 3,4'-oxydianiline and 1,3-bis (3-aminophenoxy) benzene are preferable from the viewpoint of moldability.

  Examples of the organic solvent include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, and N-methylcaprolactam. , Hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, m-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraglyme, dioxane, γ-butyrolactone , Dioxolane, cyclohexanone, cyclopentanone, and the like, but are not limited thereto. Two or more of these organic solvents may be used in combination. Among these, it is preferable to use NMP, N, N-dimethylacetamide, and γ-butyrolactone alone or in combination. In particular, NMP is preferably used because of its high solubility in phenylethynyl trimellitic anhydride and the diamine.

  The method for producing a curable imide compound may include a step of reacting phenylethynyl trimellitic anhydride and the diamine in an organic solvent, specifically, phenylethynyl trimellitic anhydride and the above. A method of dehydrating and condensing diamine with an organic solvent to produce an amic acid, which is imidized by heating or using a catalyst.

  Examples of the catalyst include acids, tertiary amine compounds, and acid anhydrides. Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N- Examples include at least one compound selected from ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, and isoquinoline. The amount of the catalyst used is preferably from 0.1 to 100 mol%, more preferably from 1 to 10 mol%, based on the amount of phenylethynyl trimellitic anhydride.

<Curable resin composition>
The curable resin composition of the present invention contains a curable imide compound and an epoxy compound as a curing agent. The curable resin composition may contain at least one of a curing agent other than the curable imide compound, a curing accelerator, a filler, and a solvent as other components.

(Curable imide compound)
The curable imide compound is the curable imide compound described above. From the viewpoint of moldability, the content of the curable imide compound contained in the curable resin composition is preferably 1% by mass or more and 50% by mass or less with respect to the total amount of the curable resin composition.

(Epoxy compound)
The epoxy compound has two or more epoxy groups in one molecule. Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolak. Type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, alicyclic epoxy Compound in which double bond such as resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, butadiene is epoxidized A compound obtained by a reaction of a hydroxyl-group-containing silicon resin with epichlorohydrin. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, naphthalene type epoxy resin, Biphenyl type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, etc. are preferable, bisphenol A Type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, phenol aralkyl type epoxy resin, Phenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resins, alicyclic epoxy resins are more preferable. These epoxy resins can be used alone or in combination.

  From the viewpoint of moldability, the content of the epoxy compound contained in the curable resin composition is preferably 9% by mass or more and 90% by mass or less with respect to the total amount of the curable resin composition.

(Curing agent)
Although it does not specifically limit as a hardening | curing agent, From a reactive viewpoint with an epoxy compound, the 1 or more thing selected from the group which consists of a phenol novolak resin, an amine, an acid anhydride, cyanate ester, and dicyandiamide is preferable. Examples of the acid anhydride include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and the like. Examples of the cyanate ester include novolak type cyanate ester and bisphenol type cyanate ester. Examples of the amine include diaminodiphenylmethane and diaminodiphenylsulfone.

  The content of the curing agent other than the curable imide compound contained in the curable resin composition is 5% by mass or more and 50% by mass with respect to the total amount of the curable resin composition from the viewpoint of reactivity with the epoxy group and moldability. It is preferable that it is below mass%.

(Curing accelerator)
Although the said curable resin composition is hardened | cured by heating even if it does not contain the hardening accelerator, in order to shorten hardening time, you may use a hardening accelerator together. Although it does not specifically limit as a hardening accelerator, From a viewpoint that it does not raise | generate a single reaction with an epoxy compound, the 1 or more thing selected from the group which consists of an organophosphorus compound, imidazole, and an organometallic complex is preferable. Examples of the organic phosphorus compound include triphenylphosphine and triphenyl phosphite. Examples of the imidazole include 1-cyanoethyl-2-ethyl-4-methylimidazole and 2-ethyl-4-methylimidazole. 1-benzyl-2-methylimidazole and the like. Examples of the organometallic complex include an aluminum acetylacetone complex.

  The content of the curing accelerator contained in the curable resin composition is 0.1% by mass or more and 5% by mass or less with respect to the total amount of the curable resin composition from the viewpoint of fluid moldability and curability. Is preferred.

(Filler)
Examples of the filler include an inorganic filler, an organic filler, and a mixture thereof. Examples of inorganic fillers include silicas such as natural silica, fused silica, amorphous silica, fumed silica, hollow silica, aluminum hydroxide, aluminum hydroxide heat-treated products (heat treatment of aluminum hydroxide, part of crystal water ), Metal hydroxides such as boehmite and magnesium hydroxide, molybdenum compounds such as molybdenum oxide and zinc molybdate, titanium oxide, barium titanate, barium sulfate, zinc borate, zinc stannate, alumina, clay , Kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, short glass fibers (glass fine powders such as E glass and D glass), hollow glass, whisker, carbon black and the like. Examples of the organic filler include one or more selected from the group consisting of rubber powder, polyimide resins other than the polyimide resin of the present invention, and polybutadiene. Examples of the rubber powder include butadiene nitrile rubber (CTBN) powder having a carboxyl group at the terminal. Two or more of these fillers may be used in appropriate combination.

  From the viewpoint of moldability, the content of the filler contained in the curable resin composition is preferably 5% by mass or more and 85% by mass or less with respect to the total amount of the curable resin composition.

(Organic solvent)
The organic solvent is used for decreasing the viscosity of the curable resin composition and improving the handling property. Any organic solvent can be used without particular limitation as long as the mixture of the curable imide compound and the epoxy compound of the present invention is compatible. Examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, and xylene, and amides such as dimethylformamide and dimethylacetamide, but are not limited thereto. is not. These organic solvents may be used alone or in combination of two or more.

  The curable resin composition contains a curable imide compound, an epoxy compound, and, if necessary, a curing agent other than the curable imide compound, a curing accelerator, and a filler in a known mixer such as a high-speed mixer, a current mixer. It can be obtained by mixing using a mixer, ribbon blender, kneader, intensive mixer, universal mixer, dissolver, static mixer or the like. The method of adding a curable imide compound or the like at the time of mixing is not particularly limited.

  According to the method for producing a curable imide compound of the present invention, the phenylethynyl trimellitic anhydride represented by the above formula (2) and the diamine represented by the above formula (3) are reacted in an organic solvent. Since the process is provided, the curable imide compound represented by the above formula (1) can be produced. Thereby, when it is excellent in moldability and cured, a curable imide compound can be obtained from which a cured product having a high glass transition temperature, a thermal decomposition temperature and a residual carbon ratio and a low thermal expansion coefficient can be obtained.

<Hardened product>
The cured product can be obtained by curing (crosslinking) the curable imide compound or the curable resin composition with heat or light. Specifically, it can be obtained by pouring a curable imide compound or a curable resin composition into a mold and curing it under predetermined conditions. In the case of thermosetting, if the curing temperature is too low, curing does not proceed, and if it is too high, the cured product is deteriorated.

  Since the cured product of the curable imide compound is obtained by curing the compound represented by the above formula (1), the glass transition temperature, the thermal decomposition temperature and the residual carbon ratio are high, and the thermal expansion coefficient is low. It has the characteristic. Specifically, the cured product of the curable imide compound preferably has the following glass transition temperature or the like.

  The glass transition temperature (Tg) of the cured product of the curable imide compound is preferably 150 ° C. or higher, and more preferably 170 ° C. or higher. The “glass transition temperature” is determined as follows. Using a dynamic viscoelasticity measuring device, solid dynamic viscoelasticity measurement is performed under the conditions of a frequency of 1 Hz and a heating rate of 2 ° C./min, the peak temperature of the obtained tan δ curve is obtained, and this peak temperature is determined as the glass transition temperature. And

  The 5% thermal decomposition temperature of the cured product of the curable imide compound is preferably 380 ° C. or higher, and more preferably 400 ° C. or higher. The “5% pyrolysis temperature” is determined by performing a thermogravimetric analysis using a thermogravimetric apparatus under a nitrogen atmosphere under a temperature increase rate of 10 ° C./min.

  The residual carbon ratio at 600 ° C. of the cured product of the curable imide compound is preferably 60% or more, and more preferably 65% or more. The “remaining carbon ratio” is obtained by performing thermogravimetric analysis using a thermogravimetric apparatus under a nitrogen atmosphere under a temperature increase rate of 10 ° C./min.

  The coefficient of thermal expansion of the cured product of the curable imide compound is preferably 60 ppm or less, and more preferably 50 ppm or less. “Thermal expansion coefficient” is obtained as follows. Using a thermomechanical analyzer, thermomechanical analysis is performed under a nitrogen atmosphere in a compression mode and at a rate of temperature increase of 2 ° C / min, and a coefficient of thermal expansion of 40 ° C to 60 ° C is determined from the slope of the obtained TMA curve.

<Uses of curable imide compound and curable resin composition>
The above-described curable imide compound or curable resin composition can be used as a casting resin composition, a printed wiring board material, a structural member material, and an adhesive, but this is an example. Other uses of the compound and the curable resin composition may be used.

  The casting resin composition is a resin composition used for casting methods such as monomer casting and potting. The casting resin composition can be used, for example, for electrical insulation and sealing of parts.

  The printed wiring board material is used for, for example, a package substrate or a mother board on which a semiconductor element is mounted. Specifically, for example, it is used for a prepreg of a printed wiring board. The manufacturing method of a prepreg is not specifically limited, A well-known method is applicable. For example, a method in which an inorganic and / or organic fiber base material is impregnated with a varnish of a curable resin composition, dried, and B-staged into a prepreg can be applied.

  The structural member material is used as a matrix resin for structural members in automobiles, railways, ships, aircrafts, and the like.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited to these descriptions.

<Synthesis of curable imide compound>
(Synthesis Example 1)
A 3-neck 100 mL separable flask equipped with a calcium chloride tube and a mechanical stirrer was charged with 5.84 g (0.02 mol) of 1,3-bis (3-aminophenoxy) benzene and 40 ml of N-methylpyrrolidone as a solvent at room temperature. And stirred to dissolve. To this solution, 11.06 g (0.04 mol) of phenylethynyl trimellitic anhydride (NEXIMID 300, PETA manufactured by NEXAM CHEMICAL) was added at room temperature and dissolved by stirring. Then, it was made to react at room temperature for 24 hours, and the amic acid was synthesize | combined. To this reaction solution, 8.16 g (0.08 mol) of acetic anhydride and 6.32 g (0.08 mol) of pyridine were added and reacted at room temperature for 15 minutes, and phenyl ethynylcarbonyl group as a thermosetting reactive group at both ends. A curable imide compound 1 was obtained. The curable imide compound 1 was represented by the following formula (1e).

(Synthesis Example 2)
To a three-necked 100 mL separable flask equipped with a calcium chloride tube and a mechanical stirrer, 4.04 g (0.02 mol) of 3,4'-oxydianiline and 40 ml of N-methylpyrrolidone as a solvent were added at room temperature and stirred. And dissolved. To this solution, 11.06 g (0.04 mol) of phenylethynyl trimellitic anhydride (NEXIMID 300, PETA manufactured by NEXAM CHEMICAL) was added at room temperature and dissolved by stirring. Then, it was made to react at room temperature for 24 hours, and the amic acid was synthesize | combined. To this reaction solution, 8.16 g (0.08 mol) of acetic anhydride and 6.32 g (0.08 mol) of pyridine were added and reacted at room temperature for 15 minutes, and phenyl ethynylcarbonyl group as a thermosetting reactive group at both ends. The curable imide compound 2 having The curable imide compound 2 was represented by the following formula (1c).

(Synthesis Example 3)
A three-necked 100 mL separable flask equipped with a calcium chloride tube and a mechanical stirrer was charged with 8.21 g (0.02 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and N- 40 ml of methylpyrrolidone was added at room temperature and stirred to dissolve. To this solution, 11.06 g (0.04 mol) of phenylethynyl trimellitic anhydride (NEXIMID 300, PETA manufactured by NEXAM CHEMICAL) was added at room temperature and dissolved by stirring. Then, it was made to react at room temperature for 24 hours, and the amic acid was synthesize | combined. To this reaction solution, 8.16 g (0.08 mol) of acetic anhydride and 6.32 g (0.08 mol) of pyridine were added and reacted at room temperature for 30 minutes, and phenyl ethynylcarbonyl group as a thermosetting reactive group at both ends. A curable imide compound 3 was obtained. The curable imide compound 3 was represented by the following formula (4).

(Synthesis Example 4)
To a three-necked 100 mL separable flask equipped with a calcium chloride tube and a mechanical stirrer, 2.16 g (0.02 mol) of m-phenylenediamine and 40 ml of N-methylpyrrolidone as a solvent were added at room temperature and dissolved by stirring. . To this solution, 11.06 g (0.04 mol) of phenylethynyl trimellitic anhydride (NEXIMID 300, PETA manufactured by NEXAM CHEMICAL) was added at room temperature and dissolved by stirring. Then, it was made to react at room temperature for 24 hours, and the amic acid was synthesize | combined. To this reaction solution, 8.16 g (0.08 mol) of acetic anhydride and 6.32 g (0.08 mol) of pyridine were added and reacted at room temperature for 15 minutes, and phenyl ethynylcarbonyl group as a thermosetting reactive group at both ends. A curable imide compound 4 was obtained. The curable imide compound 4 was represented by the following formula (5).

(Synthesis Example 5)
In a three-necked 100 mL separable flask equipped with a calcium chloride tube and a mechanical stirrer, 2.72 g (0.02 mol) of metaxylylenediamine and 40 ml of N-methylpyrrolidone as a solvent were added at room temperature and stirred to dissolve. . To this solution, 11.06 g (0.04 mol) of phenylethynyl trimellitic anhydride (NEXIMID 300, PETA manufactured by NEXAM CHEMICAL) was added at room temperature and dissolved by stirring. Then, it was made to react at room temperature for 24 hours, and the amic acid was synthesize | combined. To this reaction solution, 8.16 g (0.08 mol) of acetic anhydride and 6.32 g (0.08 mol) of pyridine were added and reacted at room temperature for 60 minutes, and phenyl ethynylcarbonyl group as a thermosetting reactive group at both ends. A curable imide compound 5 having the following was obtained. The curable imide compound 5 was represented by the following formula (6).

(Synthesis Example 6)
To a three-necked 100 mL separable flask equipped with a calcium chloride tube and a mechanical stirrer was added 3.96 g (0.02 mol) of 4,4′-diaminodiphenylmethane and 40 ml of N-methylpyrrolidone as a solvent at room temperature and stirred. Dissolved. To this solution, 11.06 g (0.04 mol) of phenylethynyl trimellitic anhydride (NEXIMID 300, PETA manufactured by NEXAM CHEMICAL) was added at room temperature and dissolved by stirring. Then, it was made to react at room temperature for 24 hours, and the amic acid was synthesize | combined. To this reaction solution, 8.16 g (0.08 mol) of acetic anhydride and 6.32 g (0.08 mol) of pyridine were added and reacted at room temperature for 60 minutes, and phenyl ethynylcarbonyl group as a thermosetting reactive group at both ends. The curable imide compound 6 having The curable imide compound 6 was represented by the following formula (7).

When the obtained curable imide compounds 1 to 6 were analyzed by Fourier transform infrared spectroscopy (FT-IR), an imide bond C = O asymmetric stretching vibration in the vicinity of 1780 cm ⁻¹ , and an imide bond in the vicinity of 1725 cm ^−1. the C = O symmetric stretch appears stretching vibration of phenylethynyl group near 2213cm ^-1, 1600cm aromatic around ^-1 C = C, absorption by C-N stretching vibration of an imide bond near 1370 cm ^-1, respectively, an amide The characteristic absorption derived from the imide bond formed by the ring closure of the acid and the absorption due to the phenylethynylcarbonyl group appeared, confirming the structure.

Moreover, as a result of performing differential scanning calorimetry (DSC) of the obtained curable imide compounds 1 to 6, an exothermic peak due to the curing reaction of the phenylethynylcarbonyl group was observed. The peak temperature of each compound is as shown in Table 1. Then, from the obtained DSC peak temperature, the curing conditions of each compound were determined as shown in Table 1.

<Example 1>
The resulting curable imide compound 1 was cast into a silicone rubber mold and cured under the curing conditions shown in Table 1 to produce a cured product.

<Example 2 and Comparative Examples 1-4>
In the same manner as in Example 1, the obtained curable imide compounds 2 to 6 were each cast into a silicone rubber mold and cured under the curing conditions shown in Table 1 to prepare a cured product.

<Moldability of cured product>
In the hardened | cured material which concerns on Examples 1, 2 and Comparative Examples 1-4, the moldability of hardened | cured material was evaluated visually. The evaluation criteria were as follows.
○: Formability was good.
X: Could not be molded, or could be molded but was very brittle.

<Evaluation of physical properties of cured product>
(Glass-transition temperature)
In the cured products according to Examples 1 and 2, the glass transition temperature was determined. Specifically, using a dynamic viscoelasticity measuring device (product name “DMS110”, manufactured by SII Nano Technology Co., Ltd.), solid dynamic viscoelasticity under the conditions of a frequency of 1 Hz and a heating rate of 2 ° C./min. Measurement was performed to determine the peak temperature of the obtained tan δ curve, and this peak temperature was taken as the glass transition temperature. In Comparative Examples 1 to 4, the cured product was very brittle, and a cured product having a shape capable of performing solid dynamic viscoelasticity measurement could not be obtained.

(Coefficient of thermal expansion)
In the cured products according to Examples 1 and 2, the coefficient of thermal expansion was measured. Specifically, using a thermomechanical analyzer (product name “TMA / SS600”, manufactured by SII NanoTechnology Co., Ltd.), a thermomechanical machine under a nitrogen atmosphere, in a compression mode, at a heating rate of 2 ° C./min. The thermal expansion coefficient of 40 to 60 degreeC was calculated | required from the gradient of the TMA curve obtained by analyzing. In Comparative Examples 1 to 4, the cured product was very brittle, and a cured product having a shape capable of performing thermomechanical analysis could not be obtained.

(5% thermal decomposition temperature)
In the cured products according to Examples 1 and 2 and Comparative Examples 1 to 4, a 5% thermal decomposition temperature was measured. The 5% pyrolysis temperature is thermogravimetrically analyzed using a thermogravimetric measuring device (product name “TGA5200”, manufactured by SII NanoTechnology Co., Ltd.) under a nitrogen atmosphere at a heating rate of 10 ° C./min. Was sought by.

(Remaining charcoal rate)
In the hardened | cured material which concerns on Examples 1, 2 and Comparative Examples 1-4, the residual carbon rate in 600 degreeC was measured. The residual charcoal rate is obtained by performing thermogravimetric analysis using a thermogravimetric measuring device (product name “TGA5200”, manufactured by SII Nanotechnology Co., Ltd.) under a nitrogen atmosphere under a temperature rising rate of 10 ° C./min. I was asked.

The results will be described below.

  As shown in Table 2, in Comparative Examples 1 to 4, cured products having poor moldability, high glass transition temperature, thermal decomposition temperature and residual carbon ratio, and low thermal expansion coefficient were not obtained. On the other hand, as shown in Table 2, in Examples 1 and 2, cured products having excellent moldability, high glass transition temperature, thermal decomposition temperature and residual carbon ratio, and low thermal expansion coefficient were obtained. I understand that.

Claims (10)

A curable imide compound represented by the following formula (1).

(In Formula (1), R ¹ and R ² each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, or an aralkyl group which may have a substituent, m represents an integer of 1 to 4)   The curable imide compound according to claim 1, wherein m in the formula (1) is 1 or 2.   The curable imide compound according to claim 1, wherein m in the formula (1) is 1. A curable imide compound comprising a step of reacting a phenylethynyl trimellitic anhydride represented by the following formula (2) and a diamine represented by the following formula (3) in an organic solvent: Production method.

(In Formula (3), R ³ and R ⁴ each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. An alkynyl group which may have a substituent, an alkynyl group which may have a substituent, or an aralkyl group which may have a substituent, and n represents an integer of 1 to 4.   A curable resin composition comprising the curable imide compound according to any one of claims 1 to 3 and an epoxy compound.   Hardened | cured material obtained by hardening the curable imide compound as described in any one of Claims 1 thru | or 3, or the curable resin composition of Claim 5.   A cast resin composition using the curable imide compound according to any one of claims 1 to 3 or the curable resin composition according to claim 5.   A printed wiring board material using the curable imide compound according to any one of claims 1 to 3 or the curable resin composition according to claim 5.   A structural member material using the curable imide compound according to any one of claims 1 to 3 or the curable resin composition according to claim 5.   An adhesive using the curable imide compound according to any one of claims 1 to 3 or the curable resin composition according to claim 5.