Amino group-containing compound, curable resin composition, cured product, and laminate

Abstract

Provided are a compound which is a curable resin and can easily achieve reparability and reshaping properties in a cured product, a curable resin composition using the same, and a cured product thereof. The amino group-containing compound of the present invention is an amino group-containing compound represented by the following general formula (1) and having a molecular weight of less than 1000. [Chemical formula 1] TIFF0007687541000033.tif31170 (In the general formula (1), m is an integer of 1 to 10.) Z 1 each independently represents a hydrogen atom, an amino group, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and at least one of Z 1 is an amino group or a group having an amino group as a substituent. Z 3 is any of the structures represented by the text formula (2).

Description

Technical Field

[0001] The present invention relates to an amino group-containing compound having a specific structure, a curable resin composition containing the same, a cured product, and a laminate containing a layer made of the cured product. This application claims priority based on Japanese Patent Application No. 2023-131563 filed in Japan on August 10, 2023, and incorporates the content herein by reference.

Background Art

[0002] A cured product obtained from an epoxy resin is excellent in heat resistance, mechanical strength, electrical properties, adhesiveness, etc., and is an indispensable material in various fields such as electric and electronic, paints, and adhesives.

[0003] On the other hand, cured products using thermosetting resins such as epoxy resins have low long-term reliability. For example, when a cured product of an epoxy resin oxidatively deteriorates, cracks may occur.

[0004] In addition, a cured product obtained by once curing a thermosetting resin such as an epoxy resin cannot be dissolved in a solvent (insoluble) and does not melt even at high temperatures (infusible). For this reason, it has poor recyclability and reusability, and the cured product after use becomes waste. Therefore, it has become an issue to reduce waste and the environmental load.

[0005] Therefore, there is a demand for solving the problems of extending the life and reducing waste of cured products using epoxy resins and the like. For solving these problems, it is considered effective to impart easy disassembly, reparability, and reshaping ability to the cured products.

[0006] Under such a background, a method has been disclosed in which a compound having pyrolytic properties is previously blended with a reaction system adhesive component, and after use, the adhesive strength is reduced by heating to a certain degree to enable disassembly (see, for example, Patent Document 1).

[0007] In addition, even when cracks or peeling occur in a sealing material using an epoxy resin or the like, a technique for obtaining a self-healing sealing material by using a first thermosetting resin and microcapsule particles encapsulating a second thermosetting resin precursor has been disclosed (see, for example, Patent Document 2).

[0008] In addition to the above, in order to impart reparability and re-moldability, research using reversible bonds such as dynamic covalent bonds and supramolecular bonds in the cured product has also been actively conducted.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] In the technique provided in Patent Document 1, the adhesive after disassembly is to be discarded. Although the base material as the adherend is recyclable, there is a problem that the recyclability as a whole is insufficient. Further, in the technique of Patent Document 2, although it has a certain degree of self-healing property, it is not a solution from the viewpoint of reuse, and the problem of waste when it becomes unnecessary remains. Further, in the raw materials used for the reversible bond, since it is necessary to ensure the molecular mobility thereof, there is a problem that the use of raw materials is limited to gel-like substances having poor mechanical strength. At present, in any case, improvement is required. Therefore, an object of the present invention is to provide a compound that can easily realize reparability and re-moldability in a cured product while being a curable resin, a curable resin composition using the same, and a cured product thereof.

Means for Solving the Problems

[0011] As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by using an amino group-containing compound having a specific structure and using it as a curable resin composition, and have completed the invention.

[0012] That is, the present invention includes the following aspects. 〔1〕An amino group-containing compound represented by the following general formula and having a molecular weight of less than 1000. [Chemical formula] 〔In general formula (1), m is an integer of 1 to 10. Z 1 Each independently represents a hydrogen atom, an amino group, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amide group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and at least one of Z 1 is an amino group or a group having an amino group as a substituent. Z 3 is any of the structures represented by the following formula (2). [Chemical formula] (In formula (2), R’ is a divalent hydrocarbon group having 2 to 12 carbon atoms, and R 1 , R 2 , R’’ each independently represents a hydrogen atom, a methyl group or an ethyl group, n1 is an integer of 1 to 30, n2 is an average value of the number of repetitions and is 0.5 to 8, and * represents a bonding point.)〕

[0013] 〔2〕A curable resin composition comprising, as essential components, the amino group-containing compound described in the above [1] and a compound (I) reactive with the amino group-containing compound. 〔3〕The curable resin composition according to the above [2], wherein the concentration of reversible bonds in the amino group-containing compound is 0.10 mmol / g or more with respect to the total mass of the curable components in the curable resin composition. 〔4〕The curable resin composition according to the above 〔2〕 or 〔3〕, wherein the compound (I) reactive with the amino group-containing compound is an epoxy resin. 〔5〕The curable resin composition according to the above 〔4〕, further containing a curing agent for an epoxy resin other than the amino group-containing compound. 〔6〕The curable resin composition according to the above 〔4〕 or 〔5〕, wherein the epoxy resin is represented by the following formula (3) and has an epoxy equivalent of 500 to 10,000 g / eq.

[0014]

Chemical formula

[0015]

Chemical formula

[0016] [In formulas (3-1) and (3-2), Ar is the same as defined above. R 1 、R 2 are each independently a hydrogen atom, a methyl group or an ethyl group. R’ is a divalent hydrocarbon group having 2 to 12 carbon atoms. R 3 、R 4 、R 7 、R 8 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group. R 5 、R 6 、R 9 、R 10 are each independently a hydrogen atom or a methyl group. n1 is an integer of 4 to 16. n2 is an average value of repeating units and is 2 to 30. ] R 11 、R 12Each is independently a glycidyl ether group or a 2-methylglycidyl ether group, R 13 and R 14 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group, R 15 and R 16 are a hydrogen atom or a methyl group, m3, m4, p1, p2, q are average values of repetition, m3 and m4 are each independently 0 to 25, and m3 + m4 ≥ 1, p1 and p2 are each independently 0 to 5, q is 0.5 to 5. However, the bond between X' represented by the general formula (3-2) and Y' represented by the general formula (3-2) may be random or block, indicating that the total number of each structural unit X', Y' present in one molecule is m3, m4 respectively.〕

[0017] 〔7〕The epoxy resin is the curable resin composition according to 〔6〕 represented by the following formula (4).

[0018]

Chemical formula

Chemical formula

Advantages of the Invention

[0019] According to the present invention, it is possible to impart reparability and remoldability to a cured product composed of a curable resin composition, contributing to the extension of the lifespan of the cured product itself and the reduction of waste.

Modes for Carrying Out the Invention

[0020] Next, modes for carrying out the present invention will be described in detail. It should be understood that the present invention is not limited to the following embodiments, and that changes in design, improvements, etc. can be appropriately made based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention.

[0021] The amino group-containing compound as one form of the present invention is a compound represented by the following general formula and having a molecular weight of less than 1000.

[0022]

Chemical formula

Chemical formula

[0023] (In formula (2), R’ is a divalent hydrocarbon group having 2 to 12 carbon atoms, and R 1 , R 2 , R’’ are each independently a hydrogen atom, a methyl group or an ethyl group, n1 is an integer from 1 to 30, n2 is the average value of the number of repetitions and is from 0.5 to 8, and * represents a bonding point.)

[0024] The general formula (1) has a reversible bond formed by an anthracene structure and a maleimide structure at the molecular terminal. The terminal anthracene structure in the general formula (1) has one or more Z 1 , and this amino group contributes to the curing reaction in the curable resin composition described later. m is the number of Z 1 in the anthracene-derived structure, and is an integer from 1 to 10. From the viewpoints of easy availability of industrial raw materials, easy control of the curing reaction, etc., it is preferably in the range of 1 to 4, and more preferably 1 or 2.

[0025] Z 1 in the formula is preferably of the following structural formula.

[0026]

Chemical formula

[0027] In the above structural formula, * represents a bonding point.

[0028] In the general formula (1), the site connecting the maleimide-derived structure is Z3 and is any of the structures represented by the general formula (2).

[0029] In the general formula (2), n1 is an integer of 1 to 30, preferably in the range of 1 to 12. n2 is the average value of the number of repetitions, which is 0.5 to 8, preferably in the range of 2 to 3. n3 is the average value of the number of repetitions, which is 0.5 to 6, preferably in the range of 2 to 4.

[0030] Examples of the amino group-containing compound of the present invention include, but are not limited to, those represented below.

[0031]

Chemical formula

[0032] The method for producing the amino group-containing compound according to an embodiment of the present invention is not particularly limited. Depending on the target structure, it may be produced step by step using known reactions, and commercially available materials can also be appropriately combined as raw materials. Hereinafter, typical synthesis methods will be described.

[0033] The general formula (1) has two Diels-Alder reaction units in the molecule. The Diels-Alder reaction unit is an addition reaction part formed by a Diels-Alder reaction consisting of an anthracene structure and a maleimide structure as a reversible bond. And in the general formula (1), Z 1 can be obtained by using an anthracene compound having the structure of.

[0034] The so-called Diels-Alder reaction in which a conjugated diene such as an anthracene structure and a dienophile such as a maleimide structure undergo an addition reaction to form a six-membered ring is an equilibrium reaction. At a temperature higher than the temperature at which the above addition reaction proceeds, a retro-Diels-Alder reaction, which is a reverse reaction in which the addition reaction part dissociates and returns to the original conjugated diene and dienophile, proceeds. These are widely known.

[0035] The above Z 1Examples of the anthracene compound having the structure include any of the compounds listed in the following formula. Among these, 1-aminoanthracene, 2-aminoanthracene, and 9-aminoanthracene are preferred because of their good curability. 1-Aminoanthracene and 2-aminoanthracene are particularly preferred in terms of the balance between reactivity, cured product physical properties, and reparability and remoldability.

[0036] [Chemical formula]

[0037] Note that the structures of the above maleimide compound and anthracene compound each independently include those having a hydrogen atom, halogen atom, alkoxy group, aralkyloxy group, aryloxy group, nitro group, amide group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, alkyl group, cycloalkyl group, aralkyl group, or aryl group as a substituent. In addition, in the structures of the compounds listed in the above formula, the alkoxy group, aralkyloxy group, aryloxy group, carboxy group, alkyloxycarbonyl group, aryloxycarbonyl group, alkyl group, cycloalkyl group, aralkyl group, and aryl group also include those in which various substituents are further bonded to the carbon atoms they have.

[0038] The Diels-Alder reaction may use a known method. For example, a conjugated diene compound and a dienophile compound are mixed in equimolar amounts, and in some cases, one component is mixed in excess. Then, it is heated and melted or dissolved in a solvent and stirred at a temperature of room temperature to 200 °C for 1 to 24 hours. Thereafter, it can be obtained by filtration or solvent distillation without purification as it is. Alternatively, it can also be obtained by commonly used isolation and purification methods such as recrystallization, reprecipitation, and chromatography.

[0039] For the synthesis of sites other than the reversible binding site, it can be synthesized by known methods. For example, a diglycidyl ether or divinyl compound of a dihydroxy compound can be reacted with hydroxyphenylmaleimide to obtain a compound having a maleimide group at the terminal. Then, according to the above, by performing a Diels-Alder reaction with an anthracene compound having an amino group, the compound represented by the general formula (1) can be obtained.

[0040] Alternatively, after obtaining a compound having a hydroxy group at the terminal, this is epoxidized to make the terminal a glycidyl ether group. Then, by reacting with hydroxyphenylmaleimide or the like, a maleimide structure is introduced at the terminal. Further, according to the above, by performing a Diels-Alder reaction with an anthracene compound having an amino group, the compound represented by the general formula (1) can be obtained.

[0041] Alternatively, a compound having a maleimide group at the terminal can be obtained by reacting hydroxyphenylmaleimide or the like with an alkylene dihalide compound or an aralkyl dihalide compound. Then, according to the above, by performing a Diels-Alder reaction with an anthracene compound having an amino group, the compound represented by the general formula (1) can be obtained.

[0042] The diglycidyl ether of the aliphatic dihydroxy compound is not particularly limited. For example, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, 1,14-tetradecanediol diglycidyl ether, 1,15-pentadecanediol diglycidyl ether, 1,16-hexadecanediol diglycidyl ether, 2-methyl-1,11-undecanediol diglycidyl ether, 3-methyl-1,11-undecanediol diglycidyl ether, 2,6,10-trimethyl-1,11-undecanediol, diglycidyl ether, etc. may be mentioned, and they may be used alone or in combination of two or more.On the one hand, as the diglycidyl ether of an aromatic dihydroxy compound, there are diglycidyl ethers of dihydroxybenzenes such as hydroquinone, resorcinol, and catechol, diglycidyl ethers of dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, diglycidyl ethers of bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone, diglycidyl ethers of biphenols such as 2,2’-biphenol, 4,4’-biphenol, (1,1’-biphenyl)-3,4-diol, 3,3’-dimethyl-(1,1’-biphenyl)-4,4’-diol, 3-methyl-(1,1’-biphenyl)-4,4’-diol, 3,3’,5,5’-tetramethylbiphenyl-2,2’-diol, 3,3’,5,5’-tetramethylbiphenyl-4,4’-diol, 5-methyl-(1,1’-biphenyl)-3,4’-diol, 3’-methyl-(1,1’-biphenyl)-3,4’-diol, 4’-methyl-(1,1’-biphenyl)-3,4’-diol, diglycidyl ethers of alicyclic structure-containing phenols such as the polyaddition product of phenol and dicyclopentadiene and the polyaddition product of phenol and terpene compounds, diglycidyl ethers of naphthols such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane, and diglycidyl ethers of the so-called Zylonite-type phenol resin which is a condensation reaction product of phenol and phenylenedimethyl chloride or biphenylenedimethyl chloride, etc. These can be used alone or in combination of two or more kinds.

[0043] Among these, from the viewpoint of excellent balance between the flexibility and heat resistance of the obtained cured product, a compound having a structure in which glycidyl groups are linked via ether groups at both ends of an alkylene chain having 4 to 12 carbon atoms is preferable, and it is most preferable to use 1,6 - hexanediol diglycidyl ether or 1,10 - decanediol diglycidyl ether. On the other hand, from the viewpoint of excellent balance between the rigidity and heat resistance of the obtained cured product, it is preferable to use diglycidyl ethers of dihydroxybenzenes such as hydroquinone, resorcinol, and catechol.

[0044] The divinyl compound is not particularly limited. For example, divinyl ethers of linear alkylene groups such as polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,3 - butylene glycol divinyl ether, 1,4 - butanediol divinyl ether, 1,6 - hexanediol divinyl ether, 1,9 - nonanediol divinyl ether, 1,10 - decanediol divinyl ether; divinyl ethers of branched alkylene groups such as neopentyl glycol divinyl ether; divinyl ethers containing cycloalkane structures such as 1,4 - cyclohexanediol divinyl ether, 1,4 - cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl ether, tricyclodecanedimethanol divinyl ether, pentacyclopentadecanedimethanol divinyl ether, pentacyclopentadecanediol divinyl ether; bisphenol A divinyl ether, bisphenol F divinyl ether, hydroquinone divinyl ether, divinylbenzene, etc. These can be used alone or in combination of two or more.

[0045] Among these, a polyether structure or a divinyl ether having a linear alkylene chain with 9 to 10 carbon atoms is preferred because of the excellent balance between the flexibility and toughness of the resulting cured product. It is most preferred to use polyethylene glycol divinyl ether, polypropylene glycol divinyl ether, polytetramethylene glycol divinyl ether, 1,12-dodecanediol diglycidyl ether, 1,13-tridecanediol, or 1,14-tetradecanediol diglycidyl ether. On the other hand, it is preferable to use hydroquinone divinyl ether, divinylbenzene, etc. because of the excellent balance between the rigidity and heat resistance of the resulting cured product.

[0046] The aromatic hydroxy compound is not particularly limited. For example, dihydroxybenzenes such as hydroquinone, resorcinol, and catechol; trihydroxybenzenes such as pyrogallol, 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene; triphenylmethane-type phenols such as 4,4’,4”-trihydroxytriphenylmethane; dihydroxynaphthalenes such as 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; tetrafunctional phenols such as 1,1’-methylenebis(2,7-naphthalenediol), 1,1’-binaphthalene-2,2’,7,7’-tetraol, and 1,1’-oxybis(2,7-naphthalenediol) obtained by subjecting dihydroxynaphthalenes to a coupling reaction; bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone; biphenols such as 2,2’-biphenol, 4,4’-biphenol, (1,1’-biphenyl)-3,4-diol, 3,3’-dimethyl-(1,1’-biphenyl)-4,4’-diol, 3-methyl-(1,1’-biphenyl)-4,4’-diol, 3,3’,5,5’-tetramethylbiphenyl-2,2’-diol, 3,3’,5,5’-tetramethylbiphenyl-4,4’-diol, 5-methyl-(1,1’-biphenyl)-3,4’-diol, 3’-methyl-(1,1’-biphenyl)-3,4’-diol, 4’-methyl-(1,1’-biphenyl)-3,Biphenols such as 4'-diol, adducts of phenol and dicyclopentadiene, and alicyclic structure-containing phenols such as adducts of phenol and terpene compounds, naphthols such as bis(2-hydroxy-1-naphthyl)methane and bis(2-hydroxy-1-naphthyl)propane, and so-called Zylok-type phenol resins which are condensation reaction products of phenol and phenylenedimethyl chloride or biphenylenedimethyl chloride can be mentioned, and they may be used alone or in combination of two or more. Further, bifunctional phenol compounds having a structure in which a methyl group, a t-butyl group, or a halogen atom is substituted as a substituent on the aromatic nucleus of each of the above compounds can also be mentioned. Incidentally, the alicyclic structure-containing phenols and the Zylok-type phenol resins may contain not only bifunctional components but also trifunctional or higher functional components, and they may be used as they are, or only bifunctional components may be taken out and used after a purification step such as a column.,

[0047] Among these, dihydroxybenzenes and bisphenols are preferable because of their excellent balance of flexibility and toughness when cured, and bis(4-hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane are particularly preferable because of their remarkable performance in imparting toughness. Also, when emphasis is placed on the moisture resistance of the cured product, it is preferable to use phenols containing an alicyclic structure.

[0048] The reaction ratio of the diglycidyl ether of the dihydroxy compound and the aromatic hydroxy compound is preferably such that the former / latter is in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio). Also, from the viewpoint of achieving a good balance between the flexibility and heat resistance of the resulting cured product, it is preferable that (a1) / (a2) is 1.0 / 1.1 to 1.0 / 3.0 (molar ratio).

[0049] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the hydroxyphenylmaleimide is preferably carried out in the presence of a catalyst. As the catalyst, various ones can be used. For example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate; phosphorus compounds such as triphenylphosphine; quaternary ammonium salts such as chlorides, bromides, iodides of DMP-30, DMAP, tetramethylammonium, tetraethylammonium, tetrabutylammonium, benzyltributylammonium, and chlorides, bromides, iodides of tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, benzyltributylphosphonium; tertiary amines such as triethylamine, N,N-dimethylbenzylamine, 1,8-diazabicyclo[5.4.0]undecene, 1,4-diazabicyclo[2.2.2]octane; imidazoles such as 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc. These may be used in combination of two or more kinds of catalysts. Among them, sodium hydroxide, potassium hydroxide, triphenylphosphine, and DMP-30 are preferred from the viewpoints that the reaction proceeds rapidly and the effect of reducing the amount of impurities is high. The amount of these catalysts used is not particularly limited, but it is preferably 0.0001 to 0.01 mol per 1 mol of the phenolic hydroxyl group of the hydroxyphenylmaleimide. The form of these catalysts is not particularly limited either, and they may be used in the form of an aqueous solution or in a solid form.

[0050] In addition, the reaction between the diglycidyl ether of the dihydroxy compound and the hydroxyphenyl maleimide can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone, dimethyl sulfoxide, propyl alcohol, butyl alcohol, and the like. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the charged raw materials. These organic solvents can be used alone or in combination of several kinds. In order to carry out the reaction promptly, no solvent is preferred. On the other hand, from the viewpoint of reducing impurities in the final product, the use of dimethyl sulfoxide is preferred.

[0051] The reaction temperature when carrying out the above reaction is usually 50 to 180°C, and the reaction time is usually 1 to 10 hours. From the viewpoint of reducing impurities in the final product, the reaction temperature is preferably 100 to 160°C. Further, when the obtained compound has a large coloration, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol-based compounds such as 2,6-dialkylphenol derivatives, divalent sulfur-based compounds, and phosphite-based compounds containing trivalent phosphorus atoms. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, or salts thereof.

[0052] After the completion of the reaction, neutralization or washing with water can also be carried out until the pH value of the reaction mixture becomes 3 to 7, preferably 5 to 7. The neutralization treatment and the washing with water can be carried out according to conventional methods. For example, when a basic catalyst is used, acidic substances such as hydrochloric acid, sodium monohydrogen phosphate, p-toluenesulfonic acid, and oxalic acid can be used as neutralizing agents. After the neutralization or washing with water, if necessary, the solvent is distilled off under reduced pressure and heating to concentrate the product, and the compound can be obtained.

[0053] The reaction ratio of the aliphatic divinyl ether and the hydroxyphenyl maleimide is preferably such that the former / latter is in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio). From the viewpoint of achieving a good balance between the flexibility and heat resistance of the resulting cured product, it is preferable that (a1) / (a2) is 1.0 / 1.02 to 1.0 / 3.0 (molar ratio).

[0054] The reaction between the diglycidyl ether of the aliphatic dihydroxy compound and the aromatic hydroxy compound proceeds sufficiently even without using a catalyst, but it can be used as appropriate from the viewpoints of raw material selection and increasing the reaction rate. Examples of the catalyst that can be used here include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; organic acids such as toluenesulfonic acid, methanesulfonic acid, xylenesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, and trifluoroacetic acid; and Lewis acids such as aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide, boron trifluoride ether complex, and boron trifluoride phenol complex. The amount of the catalyst used is usually in the range of 10 ppm to 1% by weight based on the mass of the divinyl ether compound. At this time, it is preferable to select the type and amount used so as not to cause a nucleophilic addition reaction of the vinyl group to the aromatic ring.

[0055] Also, the reaction between the divinyl compound and the hydroxyphenyl maleimide can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent include aromatic organic solvents such as benzene, toluene, and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohol-based organic solvents such as methanol, ethanol, isopropyl alcohol, and normal butanol. The amount of the organic solvent used is usually 50 to 300% by weight, preferably 100 to 250% by weight, based on the total mass of the charged raw materials. These organic solvents can be used alone or in combination of several types.

[0056] When carrying out the reaction, the reaction temperature is usually 50 to 150 °C, and the reaction time is usually 0.5 to 10 hours. At this time, in order to prevent the self-polymerization of vinyl, the reaction in an oxygen atmosphere is preferred.

[0057] After the completion of the reaction, when an organic solvent is used, it is removed under reduced pressure and heating. When a catalyst is used, it is deactivated with a deactivator or the like if necessary, and removed by washing with water or a filtration operation to obtain a compound.

[0058] The alkylene dihalide compound is not particularly limited. For example, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, 1,9-dichlorononane, 1,10-dichlorodecane, 1,11-dichloroundecane, 1,12-dichlorododecane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 1,8-dibromooctane, 1,9-dibromononane, 1,10-dibromodecane, 1,11-dibromoundecane, 1,12-dibromododecane, etc. may be mentioned. It may be used alone or in combination of two or more.

[0059] The aralkyl dihalide compound is not particularly limited. For example, dichloroxylene, dichloromethylbiphenyl, dibromoxylene, dibromomethylbiphenyl, etc. may be mentioned. It may be used alone or in combination of two or more.

[0060] The reaction ratio of the hydroxyphenylmaleimide to the alkylene dihalide compound or the aralkyl dihalide compound is preferably such that the former / latter is in the range of 1.0 / 1.01 to 1.0 / 5.0 (molar ratio). From the viewpoint of well-balancing the flexibility and heat resistance of the obtained cured product, it is preferable that (a1) / (a2) is 1.0 / 1.02 to 1.0 / 3.0 (molar ratio).

[0061] The reaction between the hydroxyphenylmaleimide and the dihalogenated alkylene compound or the dihalogenated aralkyl compound is preferably carried out in the presence of a catalyst. Various catalysts can be used, for example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and alkali metal carbonates such as sodium carbonate, potassium carbonate, etc. These may be used in combination of two or more catalysts. Among them, sodium hydroxide, potassium hydroxide, and potassium carbonate are preferred in terms of the rapid progress of the reaction and the high effect of reducing the amount of impurities. The amount of these catalysts used is not particularly limited, but it is preferably 0.0001 to 10 moles per mole of the phenolic hydroxyl group of the hydroxyphenylmaleimide. The form of these catalysts is not particularly limited either, and they may be used in the form of an aqueous solution or in a solid form.

[0062] In addition, the reaction between the hydroxyphenylmaleimide and the dihalogenated alkylene compound or the dihalogenated aralkyl compound can be carried out without a solvent or in the presence of an organic solvent. Examples of the organic solvent that can be used include toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, acetonitrile, dimethylformamide, etc. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 1000% by mass, based on the total mass of the charged raw materials. These organic solvents can be used alone or in a mixture of several types.

[0063] The reaction temperature when carrying out the reaction is usually room temperature to 150 °C, and the reaction time is usually 1 to 24 hours. From the point of reducing the impurities in the final product, the reaction temperature is preferably room temperature to 100 °C.

[0064] In this way, a compound having a maleimide group at the target terminal can be obtained. The Diels-Alder reaction for this compound is as described above.

[0065] The parent diene intermediate before performing the Diels-Alder reaction can be represented by the following general formula (1)'.

[0066] [Chemical formula]

[0067] The amino group-containing compound of the present invention can be made into a curable resin composition by using in combination a compound (I) having reactivity with the amino group-containing compound. The curable resin composition can be suitably used for various electrical and electronic member applications such as adhesives, paints, photoresists, printed wiring boards, and semiconductor encapsulation materials. The curable resin composition of the present invention is a curable resin composition comprising the amino group-containing compound of the present invention and a compound (I) having reactivity with the amino group-containing compound as essential components.

[0068] Examples of the compound (I) having reactivity with the amino group-containing compound include melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, resol resins, epoxy resins, isocyanate compounds, azide compounds, compounds containing a double bond such as an alkenyl ether group, acid anhydrides, hexamethylenetetramine and its modified products, oxazoline compounds, etc., which are substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group.

[0069] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated, etc.

[0070] The guanamine compound includes, for example, tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethyl benzoguanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxy guanamine, a compound in which 1 to 4 methylol groups of tetramethylol guanamine are acyloxymethylated, and the like.

[0071] The glycoluril compound includes, for example, 1,3,4,6-tetrakis(methoxymethyl) glycoluril, 1,3,4,6-tetrakis(butoxymethyl) glycoluril, 1,3,4,6-tetrakis(hydroxymethyl) glycoluril, and the like.

[0072] The urea compound includes, for example, 1,3-bis(hydroxymethyl) urea, 1,1,3,3-tetrakis(butoxymethyl) urea, 1,1,3,3-tetrakis(methoxymethyl) urea, and the like.

[0073] The resol resin includes, for example, polymers obtained by reacting phenolic hydroxyl group-containing compounds such as phenol, alkylphenols such as cresol and xylenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, dihydroxynaphthalene with aldehyde compounds under alkaline catalyst conditions.

[0074] The epoxy resin is, for example, a liquid epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, etc., a brominated epoxy resin such as brominated phenol novolak type epoxy resin, a solid bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolak type epoxy resin, etc. It may be used alone or in combination of two or more, and it is preferably selected and used according to the intended use, physical properties of the cured product, etc.

[0075] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, etc.

[0076] Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylenebisazide, 4,4'-oxybisazide, etc.

[0077] The compounds containing a double bond such as the alkenyl ether group include, for example, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

[0078] The acid anhydrides include, for example, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, 4,4'-(isopropylidene) diphthalic anhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride; alicyclic carboxylic acid anhydrides such as tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, trialkyltetrahydrophthalic anhydride, and the like.

[0079] The concentration of the reversible bond in the curable resin composition of the present invention is preferably 0.10 mmol / g or more with respect to the total mass of the curable components in the curable resin composition. According to such a configuration, both the reparability and the reshaping property of the cured product obtained from the curable resin composition become further better. The concentration of the aforementioned reversible bond is more preferably 0.10 to 3.00 mmol / g, and even more preferably 0.15 to 2.00 mmol / g. The concentration of the reversible bond of the present invention can be appropriately selected according to the glass transition temperature and the like defined at the tanδ peak top of the dynamic viscoelasticity measuring instrument (DMA) of the target cured product. For example, when using the glass transition temperature as a reference, if the glass transition temperature of the cured product is around room temperature, even in the low concentration side of the preferable range, sufficient reparability and reshaping property functions are likely to be exhibited. On the other hand, if the glass transition temperature of the target cured product exceeds 100°C as a reference, the functions are likely to be exhibited on the high concentration side of the preferable range. However, in the temperature region exceeding the glass transition temperature measured by DMA, generally the molecular mobility is high, and sufficient reparability and reshaping property functions are likely to be exhibited even when the concentration of the amino group-containing compound is low. From this, for example, by appropriately adjusting the aging temperature for repair and the heating temperature for reshaping in a timely manner, the expression effect of the reparability and reshaping property functions can also be adjusted. Thus, the relationship between the glass transition temperature of the cured product and the concentration of the reversible bond is not limited to these.

[0080] As the compound (I) having reactivity with the amino group-containing compound, it is particularly preferable to use an epoxy resin because it can form a curable resin composition excellent in curability, mechanical strength, heat resistance, etc. in the cured product.

[0081] As the epoxy resin, an epoxy resin represented by the following formula (3) and having an epoxy equivalent of 500 to 10,000 g / eq may be used.

[0082]

Chemical formula

[0083]

Chemical formula

[0084] [In formulas (3-1) and (3-2), Ar is the same as defined above, R 1 and R 2 are each independently a hydrogen atom, a methyl group or an ethyl group, R’ is a divalent hydrocarbon group having 2 to 12 carbon atoms, R 3 , R 4 , R 7 , R 8 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group, R 5 , R 6 , R 9 , R 10 are each independently a hydrogen atom or a methyl group, n1 is an integer from 2 to 16, n2 is an average value of repeating units and is from 2 to 30.] R 11 , R 12 are each independently a glycidyl ether group or a 2-methylglycidyl ether group, R 13 , R 14 are each independently a hydroxyl group, a glycidyl ether group or a 2-methylglycidyl ether group, R 15 , R 16 are a hydrogen atom or a methyl group, m3, m4, p1, p2, q are average values of repetition, and m3 and m4 are each independently from 0 to 25 and m3 + m4 ≧ 1, p1 and p2 are each independently from 0 to 5, q is from 0.5 to 5. However, the bond between X' represented by the general formula (3-1) and Y' represented by the general formula (3-2) may be random or block, and the total number of each structural unit X' and Y' present in one molecule is m3 and m4, respectively.

[0085] As the epoxy resin, an epoxy resin represented by the following formula (4) may be used. By using such an epoxy resin, the repairability and re-moldability effects of the cured epoxy resin are improved, and the balance between flexibility and toughness becomes good.

[0086]

Chemical formula

[0087] The epoxy resin represented by the general formula (3) or (4) may be used alone in combination with the amino group-containing compound of the present invention as a curable resin. Further, from the viewpoint of imparting flexibility to the cured product and easily expressing the repairability and re-moldability, it is also preferable to use in combination an epoxy resin having an epoxy equivalent of 100 to 300 g / eq.

[0088] As for the epoxy resin that can be used in combination, the epoxy equivalent may be in the range of 100 to 300 g / eq, and its structure is not limited. For example, liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, brominated epoxy resins such as brominated phenol novolak type epoxy resin, solid bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolak type epoxy resin, etc. can be mentioned. It may be used alone or in combination of two or more, and it is preferably selected and used according to the intended use, physical properties of the cured product, etc.

[0089] Among these, it is preferable to use an epoxy resin having an epoxy equivalent of 100 to 300 g / eq among liquid epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, polyhydroxybenzene type epoxy resin, polyhydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin. Particularly preferably, an epoxy resin having an epoxy equivalent of 100 to 300 g / eq is used among bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin.

[0090] The usage ratio of the epoxy resin represented by the general formula (3) or (4) and the epoxy resin having an epoxy equivalent of 100 to 300 g / eq is not particularly limited. However, from the viewpoint of easy phase separation in the cured product, the mass ratio of the former to the latter is 97:3 to 3:97, preferably 90:10 to 10:90, and particularly preferably 80:20 to 20:80. By phase separation in the cured product, a sea-island structure is formed, and both the adhesiveness and stress relaxation ability of the cured product are achieved. In particular, a high adhesive force is exhibited in a wide temperature range, and there is an effect of reducing the molding shrinkage rate before and after heat curing of the resin composition.

[0091] Furthermore, when the amino group-containing compound of the present invention is combined with an epoxy resin to form a curable resin composition, a curing agent for an epoxy resin other than the amino group-containing compound of the present invention may be blended.

[0092] Examples of the curing agent that can be used here include various known curing agents for epoxy resins such as amine compounds, acid anhydrides, amide compounds, phenolic hydroxyl group-containing compounds, carboxylic acid-based compounds, and thiol compounds.

[0093] Examples of the amine compound include aliphatic amine compounds such as trimethylenediamine, ethylenediamine, N,N,N’,N’-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N’,N’-tetramethylpropylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N’,N’-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, α-methylbenzylmethylamine;

[0094] alicyclic and heterocyclic amine compounds such as piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N,N’,N”-tris(dimethylaminopropyl)hexahydro-s-triazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N’-dimethylpiperazine, 1,8-diazabicyclo-[5.4.0]-undecene (DBU);

[0095] aromatic amine compounds such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, pyridine, picoline;

[0096] Examples of the modified amine compounds include epoxy compound-added polyamines, Michael addition polyamines, Mannich addition polyamines, thiourea addition polyamines, ketone-blocked polyamines, dicyandiamide, guanidine, organic acid hydrazides, diaminomaleonitrile, amine imides, boron trifluoride-piperidine complexes, boron trifluoride-monoethylamine complexes, and the like.

[0097] Examples of the acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride polypropylene glycol, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.

[0098] Examples of the phenolic hydroxyl group-containing compounds include bisphenols such as bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)sulfone; phenol novolak resins; cresol novolak resins; aromatic hydrocarbon formaldehyde resin-modified phenol resins; dicyclopentadiene phenol addition type resins; phenol aralkyl resins (zylok resins); naphthol aralkyl resins; trimethylolmethane resins; tetraphenylol ethane resins; naphthol novolak resins; naphthol-phenol co-condensed novolak resins; naphthol-cresol co-condensed novolak resins; biphenyl-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by bis(methylene) groups); biphenyl-modified naphthol resins (polyhydric naphthol compounds in which phenol nuclei are linked by bis(methylene) groups); aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, etc.); and alkoxy group-containing aromatic ring-modified novolak resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde), and the like.

[0099] Examples of the amide compound include dicyandiamide and polyamideamine. The polyamideamine can be obtained, for example, by reacting an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, a carboxylic acid compound such as a fatty acid or dimer acid, with an aliphatic polyamine or a polyamine having a polyoxyalkylene chain.

[0100] Examples of the carboxylic acid compound include carboxylic acid polymers such as carboxylic acid-terminated polyester, polyacrylic acid, and maleic acid-modified polypropylene glycol.

[0101] The thiol compound preferably contains two or more thiol groups in one molecule. Examples thereof include 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptopropionate), 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril, 4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, and the like.

[0102] When using these curing agents, only one type of curing agent may be used, or two or more types may be mixed. In addition, in applications such as underfill materials and general paint applications, it is preferable to use the amine-based compound, carboxylic acid-based compound, and / or acid anhydride-based compound. Further, in applications such as adhesives and flexible printed circuit boards, an amine-based compound, particularly dicyandiamide, is preferable from the viewpoints of workability, curability, and long-term stability. In addition, in applications for semiconductor encapsulation materials, a solid-type phenolic compound is preferable from the viewpoint of the heat resistance of the cured product. In addition, in battery applications, aliphatic amines and thiol compounds are preferable from the viewpoint of low-temperature curing.

[0103] Although the usage amounts of the epoxy resin and the curing agent are not particularly limited, from the viewpoint that the mechanical properties and the like of the obtained cured product are good, with respect to a total of 1 equivalent of epoxy groups in the resin composition, an amount such that the active groups capable of reacting with the epoxy groups, including the amino group-containing compound of the present invention, is 0.4 to 1.5 equivalents is preferable.

[0104] In addition, when using an epoxy resin, it may contain a curing accelerator. Various curing accelerators can be used, and examples thereof include urea compounds, phosphorus compounds, tertiary amines, imidazoles, imidazolines, organic acid metal salts, Lewis acids, amine complex salts, and the like. When used for adhesive applications, a urea compound, particularly 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU), is preferable from the viewpoints of excellent workability and low-temperature curability. When used for semiconductor encapsulation material applications, triphenylphosphine is preferable among phosphorus-based compounds, and 1,8-diazabicyclo-[5.4.0]-undecene is preferable among tertiary amines, from the viewpoints of excellent curability, heat resistance, electrical properties, moisture resistance reliability, and the like.

[0105] Examples of the phosphorus compound include alkylphosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine; dialkylphosphines such as dimethylphosphine and dipropylphosphine; secondary phosphines such as diphenylphosphine and methylethylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, and triphenylphosphine.

[0106] Examples of the imidazole include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole isocyanurate adduct, 2-methylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, and the like.

[0107] Examples of the imidazoline compound include 2-methylimidazoline, 2-phenylimidazoline, and the like.

[0108] Examples of the urea compound include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, N-(3-chloro-4-methylphenyl)-N',N'-dimethylurea, and the like.

[0109] In addition, the curable resin composition of the present invention may be used in combination with other thermosetting resins or thermoplastic resins as long as the effects of the present invention are not impaired.

[0110] Examples of other thermosetting resins include cyanate ester resins, resins having a benzoxazine structure, active ester resins, vinylbenzyl compounds, acrylic compounds, copolymers of styrene and maleic anhydride, and the like. When using the above-mentioned other thermosetting resins in combination, the amount used is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably in the range of 1 to 50 parts by mass in 100 parts by mass of the curable resin composition.

[0111] Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolak type cyanate ester resin, naphthol-cresol co-condensed novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resin, biphenyl-modified novolak type cyanate ester resin, anthracene type cyanate ester resin, and the like. These may be used alone or in combination of two or more.

[0112] Among these cyanate ester resins, in terms of obtaining a cured product with particularly excellent heat resistance, it is preferable to use bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthylene ether type cyanate ester resin, and novolak type cyanate ester resin. In terms of obtaining a cured product with excellent dielectric properties, dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable.

[0113] The resin having a benzoxazine structure is not particularly limited. For example, reaction products of bisphenol F with formalin and aniline (F-a type benzoxazine resin), reaction products of diaminodiphenylmethane with formalin and phenol (P-d type benzoxazine resin), reaction products of bisphenol A with formalin and aniline, reaction products of dihydroxydiphenyl ether with formalin and aniline, reaction products of diaminodiphenyl ether with formalin and phenol, reaction products of dicyclopentadiene-phenol adduct type resin with formalin and aniline, reaction products of phenolphthalein with formalin and aniline, reaction products of diphenyl sulfide with formalin and aniline, and the like can be mentioned. These may be used alone or in combination of two or more kinds.

[0114] The active ester resin is not particularly limited, but generally, compounds having two or more highly reactive ester groups such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. in one molecule are preferably used. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or its halide and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or its halide and a phenol compound and / or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc., or their halides. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-phenol addition type resin, etc.

[0115] Specific examples of the active ester resin include active ester resins containing a dicyclopentadiene-phenol addition structure, active ester resins containing a naphthalene structure, active ester resins that are acetylated products of phenol novolac, active ester resins that are benzoylated products of phenol novolac, etc. Among them, in terms of being excellent in improving peel strength, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferred.

[0116] Furthermore, various novolak resins, alicyclic diene compounds such as dicyclopentadiene, addition polymerization resins of alicyclic diene compounds and phenol compounds, modified novolak resins of phenolic hydroxyl group-containing compounds and alkoxy group-containing aromatic compounds, phenol aralkyl resins (Zylok resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylol ethane resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and various vinyl polymers may be used in combination.

[0117] More specifically, the various novolak resins include polymers obtained by reacting phenolic hydroxyl group-containing compounds such as phenol, phenylphenol, resorcinol, biphenyl, bisphenols such as bisphenol A and bisphenol F, naphthol, and dihydroxynaphthalene with aldehyde compounds under acid catalyst conditions.

[0118] The various vinyl polymers include homopolymers of vinyl compounds such as polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly(meth)acrylate, or copolymers thereof.

[0119] A thermoplastic resin refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, cyclic polyolefin resin, and the like. These thermoplastic resins can be used alone or in combination of two or more.

[0120] When using these other resins, the blending ratio of the amino group-containing compound of the present invention and the other resin can be arbitrarily set according to the application. Further, from the viewpoint of not inhibiting the reparability and remoldability exhibited by the present invention, it is preferable that the other resin is in a ratio of 0.5 to 100 parts by mass with respect to 100 parts by mass of the amino group-containing compound of the present invention.

[0121] Furthermore, a curing accelerator may be used in combination with the curable resin composition of the present invention. Examples of the curing accelerator include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride and boron trifluoride monoethylamine complex; organic acid compounds such as thiodipropionic acid; benzoxazine compounds such as thiodiphenol benzoxazine and sulfonylbenzoxazine; and sulfonyl compounds. These may be used alone or in combination of two or more. The addition amount of these catalysts is preferably in the range of 0.001 to 15 parts by mass per 100 parts by mass of the curable resin composition.

[0122] In addition, when the curable resin composition of the present invention is used for applications where high flame retardancy is required, a non-halogen-based flame retardant substantially free of halogen atoms may be blended.

[0123] Examples of the non-halogen-based flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic-based flame retardants, and organic metal salt-based flame retardants. There are no particular restrictions on their use, and they may be used alone, a plurality of the same type of flame retardant may be used, or different types of flame retardants may be combined and used.

[0124] Both inorganic and organic phosphorus-based flame retardants can be used. Examples of the inorganic compounds include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide.

[0125] Furthermore, it is preferable that the red phosphorus is surface-treated for the purpose of preventing hydrolysis or the like. Examples of the surface treatment method include the following methods (i) to (iii). (i) A method of coating with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof. (ii) A method of coating with a mixture of inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc., and thermosetting resins such as phenolic resins. (iii) A method of double coating with a thermosetting resin such as a phenolic resin on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc.

[0126] Examples of the organic phosphorus compounds include general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as cyclic organic phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting the same with compounds such as epoxy resins and phenolic resins.

[0127] The compounding amount of these phosphorus-based flame retardants is appropriately selected depending on the type of phosphorus-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, when using red phosphorus as a non-halogen-based flame retardant in 100 parts by mass of a resin composition containing all non-halogen-based flame retardants and other fillers and additives, etc., it is preferably compounded in the range of 0.1 part by mass to 2.0 parts by mass. When using an organic phosphorus compound, it is similarly preferably compounded in the range of 0.1 part by mass to 10.0 parts by mass, and more preferably in the range of 0.5 part by mass to 6.0 parts by mass.

[0128] When using the phosphorus-based flame retardant, it may be used in combination with hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, black dyes, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc.

[0129] The nitrogen-based flame retardant includes, for example, triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, etc., and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred.

[0130] The triazine compounds include, for example, melamine, acetoguanamine, benzoguanamine, melem, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, etc. In addition, for example, (1) aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, and melam sulfate; (2) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol, etc. with melamines such as melamine, benzoguanamine, acetoguanamine, formoguanamine, etc. and formaldehyde; (3) mixtures of the co-condensates of (2) with phenolic resins such as phenol-formaldehyde condensates; (4) those obtained by further modifying (2) and (3) with tung oil, isomerized linseed oil, etc.

[0131] Examples of the cyanuric acid compounds include cyanuric acid, melamine cyanurate, etc.

[0132] The blending amount of the nitrogen-based flame retardant is appropriately selected according to the type of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. For example, in 100 parts by mass of the resin composition containing all of the non-halogen-based flame retardant and other fillers and additives, etc., it is preferably blended in the range of 0.05 to 10 parts by mass, and more preferably blended in the range of 0.1 part by mass to 5 parts by mass.

[0133] When using the nitrogen-based flame retardant, metal hydroxides, molybdenum compounds, etc. may be used in combination.

[0134] The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom. Examples thereof include silicone oil, silicone rubber, and silicone resin. The blending amount of the silicone-based flame retardant is appropriately selected according to the type of the silicone-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. Further, for example, it is preferably blended in the range of 0.05 to 20 parts by mass in 100 parts by mass of the resin composition containing all of a non-halogen-based flame retardant and other fillers and additives. When using the silicone-based flame retardant, a molybdenum compound, alumina, etc. may be used in combination.

[0135] Examples of the inorganic-based flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low melting point glasses, etc.

[0136] Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, etc.

[0137] Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide, etc.

[0138] Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate, etc.

[0139] Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc.

[0140] Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, borax, and the like.

[0141] Examples of the low melting point glass include Seepley (manufactured by Boxy Brown), hydrated glass SiO 2 -MgO-H 2 O, PbO-B 2 O 3 system, ZnO-P 2 O 5 -MgO system, P 2 O 5 -B 2 O 3 -PbO-MgO system, P-Sn-O-F system, PbO-V 2 O 5 -TeO 2 system, Al 2 O 3 -H 2 O system, lead borosilicate system, and other glassy compounds can be mentioned.

[0142] The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. Further, for example, in 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers and additives, it is preferably blended in the range of 0.05 part by mass to 20 parts by mass, and more preferably blended in the range of 0.5 part by mass to 15 parts by mass.

[0143] Examples of the organometallic salt-based flame retardant include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, and a compound in which a metal atom and an aromatic compound or a heterocyclic compound are ionically bonded or coordinately bonded.

[0144] The blending amount of the organometallic salt-based flame retardant is appropriately selected according to the type of the organometallic salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. Further, for example, in 100 parts by mass of the resin composition containing all of the non-halogen flame retardant and other fillers and additives, it is preferably blended in the range of 0.005 part by mass to 10 parts by mass.

[0145] The curable resin composition of the present invention may contain a filler. Examples of the filler include inorganic fillers and organic fillers. Examples of the inorganic filler include inorganic fine particles.

[0146] Examples of the inorganic fine particles include, for those having excellent heat resistance, alumina, magnesia, titania, zirconia, silica (quartz, fumed silica, precipitated silica, anhydrous silicic acid, fused silica, crystalline silica, ultrafine amorphous silica, etc.); for those having excellent thermal conductivity, boron nitride, aluminum nitride, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, diamond, etc.; for those having excellent conductivity, metal fillers and / or metal-coated fillers using a simple metal or an alloy (for example, iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.), tin oxide, indium oxide, etc.; for those having excellent barrier properties, minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, smectite, etc. and potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; for those having a high refractive index, barium titanate, zirconia oxide, titanium oxide, etc.; for those exhibiting photocatalytic properties, photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., composites of the above metals, their oxides, etc.; for those having excellent wear resistance, metals such as silica, alumina, zirconia, magnesium oxide, etc., and their composites and oxides, etc.; for those having excellent insulation properties, silica, etc.; for those having excellent ultraviolet shielding properties, titanium oxide, zinc oxide, etc. These inorganic fine particles may be appropriately selected according to the use, and may be used alone or in combination of a plurality of types. Further, since the above inorganic fine particles have various properties other than the properties listed in the examples, they may be appropriately selected according to the use at the appropriate time.

[0147] For example, when using silica as the inorganic fine particles, there is no particular limitation, and known silica fine particles such as powdery silica and colloidal silica can be used. Examples of commercially available powdery silica fine particles include Aerosil 50, 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, H122 manufactured by Asahi Glass Co., Ltd., E220A, E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Chemical Ltd., SG Flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

[0148] Examples of commercially available colloidal silica include methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. manufactured by Nissan Chemical Industries, Ltd.

[0149] Silica fine particles with surface modification may also be used. For example, those obtained by surface-treating the silica fine particles with a reactive silane coupling agent having a hydrophobic group, or those modified with a compound having a (meth)acryloyl group can be mentioned. Examples of commercially available powdery silica modified with a compound having a (meth)acryloyl group include Aerosil RM50, R711, etc. manufactured by Nippon Aerosil Co., Ltd., and examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, etc. manufactured by Nissan Chemical Industries, Ltd.

[0150] The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-shaped, plate-shaped, fibrous, or irregularly shaped ones can be used. Also, the primary particle diameter is preferably in the range of 5 to 200 nm.

[0151] As the titanium oxide fine particles, not only extender pigments but also ultraviolet light-responsive photocatalysts can be used. For example, anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, etc. can be used. Furthermore, particles designed to respond to visible light by doping a heterogeneous element into the crystal structure of titanium oxide can also be used. As the element to be doped into titanium oxide, anionic elements such as nitrogen, sulfur, carbon, fluorine, phosphorus, etc. and cationic elements such as chromium, iron, cobalt, manganese, etc. are preferably used. Also, as the form, powders, sols or slurries dispersed in an organic solvent or water can be used. Examples of commercially available powdered titanium oxide fine particles include Aerosil P-25 manufactured by Nippon Aerosil Co., Ltd., ATM-100 manufactured by Tayca Corporation, etc. Examples of commercially available slurry-type titanium oxide fine particles include TKD-701 manufactured by Tayca Corporation, etc.

[0152] The curable resin composition of the present invention may further contain a fibrous substrate. The fibrous substrate is not particularly limited, but those used in fiber-reinforced resins are preferable, and examples include inorganic fibers and organic fibers.

[0153] Examples of the inorganic fibers include carbon fibers, glass fibers, boron fibers, alumina fibers, silicon carbide fibers, etc., and also include carbon fibers, activated carbon fibers, graphite fibers, tungsten carbide fibers, silicon carbide fibers (carbonized silicon fibers), ceramic fibers, natural fibers, mineral fibers such as basalt, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the above metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0154] Examples of the organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, polyarylate, etc., natural fibers such as cellulose, pulp, cotton, wool, silk, and regenerated fibers such as protein, polypeptide, and alginic acid.

[0155] Among these, carbon fiber and glass fiber are preferable because they have a wide range of industrial applications. Only one of these may be used, or a plurality of types may be used simultaneously.

[0156] The fibrous substrate may be an aggregate of fibers, and the fibers may be continuous, discontinuous, woven, or non-woven. Further, it may be a fiber bundle in which the fibers are aligned in one direction, or a sheet-like structure in which the fiber bundles are arranged. Further, it may have a three-dimensional shape in which the aggregate of fibers has a thickness.

[0157] For the purpose of adjusting the solid content and viscosity of the resin composition, the curable resin composition of the present invention may use a dispersion medium. The dispersion medium may be any liquid medium that does not impair the effects of the present invention, and examples include various organic solvents and liquid organic polymers.

[0158] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); cyclic ethers such as tetrahydrofuran (THF) and dioxolane; esters such as methyl acetate, ethyl acetate, and butyl acetate; aromatics such as toluene and xylene; and alcohols such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These can be used alone or in combination, and among them, methyl ethyl ketone is preferable in terms of volatility during coating and solvent recovery.

[0159] The liquid organic polymer is a liquid organic polymer that does not directly contribute to the curing reaction, and examples include acrylic polymers (Flowlen WK-20: Kyoeisha), amine salts of special modified phosphoric esters (HIPLAAD ED-251: Kusumoto Chemicals), and modified acrylic block copolymers (DISPERBYK 2000; BYK-Chemie).

[0160] The resin composition of the present invention may have other formulations. For example, catalysts, polymerization initiators, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, flame retardants, plasticizers, reactive diluents, etc. can be mentioned. The resin composition of the present invention may be a curable resin composition that is a self-healing composition or a composition for a remolding material.

[0161] By curing the resin composition of the present invention, a cured product can be obtained. When curing, curing may be performed at room temperature or by heating. When performing thermal curing, it may be cured by a single heating, or it may be cured through a multi-step heating process.

[0162] Also, the curable resin composition of the present invention can also be cured with active energy rays. In that case, a photo cationic polymerization initiator may be used as the polymerization initiator. As the active energy rays, visible light, ultraviolet rays, X-rays, electron beams, etc. can be used.

[0163] Examples of the photo cationic polymerization initiator include aryl-sulfonium salts, aryl-iodonium salts, etc. Specifically, arylsulfonium hexafluorophosphate, arylsulfonium hexafluoroantimonate, arylsulfonium tetrakis(pentafluoro)borate, tri(alkylphenyl)sulfonium hexafluorophosphate, etc. can be used. The photo cationic polymerization initiator may be used alone or in combination of two or more.

[0164] The curable resin composition of the present invention may be prepared by uniformly mixing the above-mentioned respective components, and the method is not particularly limited. For example, it can be prepared by uniformly mixing using a pot mill, ball mill, bead mill, roll mill, homogenizer, super mill, homodisper, universal mixer, Banbury mixer, kneader, etc.

[0165] The curable resin composition of the present invention dissolves the aforementioned amino group-containing compound of the present invention, the compound (I) reactive with the amino group-containing compound, and further, if necessary, the aforementioned curative agent, filler, fibrous substrate, dispersion medium, and resin other than the aforementioned various compounds in a dispersion medium such as the aforementioned organic solvent. After dissolution, the solvent is distilled off, and the curable resin composition can be obtained by drying under reduced pressure using a vacuum oven or the like. Further, the curable resin composition of the present invention may be in a state where the aforementioned constituent materials are uniformly mixed. At this time, it is preferably uniformly mixed with a mixer or the like. The blending ratio of each constituent material can be appropriately adjusted according to the properties of the cured product to be desired, such as mechanical strength, heat resistance, reparability, and remoldability. Further, in the production of the curable resin composition, the mixing order of the specific constituent materials is not particularly limited.

[0166] The cured product of the present invention is obtained by curing the compound (I) reactive with the amino group-containing compound with the amino group-containing compound of the present invention. As the curing method, a known method can be appropriately selected and employed depending on the properties of the compound (I) reactive with the amino group-containing compound used.

[0167] Since the cured product of the present invention is cured by the amino group-containing compound of the present invention as described above, by exhibiting an appropriate crosslink density, good mechanical strength can be maintained. Further, when mechanical energy such as a scratch or external force is applied to the cured product of the present invention, the reversible bond is broken, but since the equilibrium moves in the bonding direction, an adduct is formed again, and it is considered that the scratch can be repaired and remolding is possible.

[0168] The structure of the obtained cured product can be confirmed by infrared absorption (IR) spectrometry using Fourier transform infrared spectroscopy (FT-IR) or the like, elemental analysis, X-ray scattering method, or the like.

[0169] As described above, the cured product according to one embodiment of the present invention can be obtained by using the amino group-containing compound of the present invention as one component of the curable resin composition. Further, by using the above-mentioned parent diene intermediate, which is an intermediate of the amino group-containing compound, and using in combination a compound capable of undergoing an addition reaction by the Diels-Alder reaction, a cured product can be obtained while forming the amino group-containing compound (while synthesizing in situ) during the curing process.

[0170] For example, when a curing reaction is carried out using the formula (1)’, anthracene having an amino group, and a compound (I) reactive with the amino group-containing compound as essential raw materials, an amino group-containing compound represented by the formula (1) can be obtained during the curing reaction process, and further, a cured product can be obtained as the curing reaction progresses. The anthracene having an amino group that can be used at this time is the same as described above.

[0171] The curable resin composition of the present invention and the cured product produced by the curable resin composition are excellent in both heat resistance and reparability, and have reshaping properties, and are useful for the following applications.

[0172] The cured product of the curable resin of the present invention can be made into a laminate by laminating it with a substrate. As the substrate of the laminate, inorganic materials such as metals and glass, organic materials such as plastics and wood, etc. can be used as appropriate according to the application, and the shape of the laminate may also be used, such as a flat plate, a sheet shape, or may have a three-dimensional structure, or may be three-dimensional. It may have any shape according to the purpose, such as having curvature on the whole or in part. Also, there are no restrictions on the hardness, thickness, etc. of the substrate. Further, it may be a multilayer laminate laminated in the order of a first substrate, a layer made of the cured product of the curable resin composition of the present invention, and a second substrate. Since the curable resin composition of the present embodiment is excellent in adhesiveness, it can be suitably used as an adhesive for adhering the first substrate and the second substrate. Also, the cured product of the curable resin of the present invention may be used as a substrate, and further, the cured product of the present invention may be laminated.

[0173] In addition, since the cured product of the curable resin of the present invention can relieve stress, it can be particularly suitably used for bonding dissimilar materials. For example, even if the base material is metal and / or metal oxide and the second base material is a laminate of dissimilar materials such as a plastic layer, the adhesive strength is maintained due to the stress relaxation ability of the cured product of the present invention.

[0174] In a laminate formed by laminating the cured product of the present invention and a base material, the layer containing the cured product may be formed directly on the base material by coating or molding, or a pre-formed one may be laminated. When directly coating, the coating method is not particularly limited, and examples include spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, screen printing method, inkjet method, etc. When directly molding, examples include in-mold molding, insert molding, vacuum molding, extrusion lamination molding, press molding, etc. When laminating the molded composition, an uncured or semi-cured composition layer may be laminated and then cured, or a layer containing a cured product obtained by completely curing the composition may be laminated on the base material. Further, a precursor that can serve as a base material may be coated on the cured product of the present invention and cured to effect lamination, or the precursor that can serve as a base material or the composition of the present invention may be cured after being adhered in an uncured or semi-cured state. The precursor that can serve as a base material is not particularly limited, and examples include various curable resin compositions.

[0175] The cured product obtained by using the curable resin composition of the present invention has particularly high adhesiveness to metal and / or metal oxide, and thus can be particularly preferably used as a primer for metal. Examples of the metal include copper, aluminum, gold, silver, iron, platinum, chromium, nickel, tin, titanium, zinc, various alloys, and materials obtained by combining these. Examples of the metal oxide include single oxides and / or composite oxides of these metals. Since it has excellent adhesiveness particularly to iron, copper, and aluminum, it can be preferably used as an adhesive for iron, copper, and aluminum.

[0176] The curable resin composition of the present invention can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering, electronics, aircraft, and space industries. When used as an adhesive for bonding different materials such as between metal and non-metal, this adhesive can maintain high adhesiveness without being affected by changes in temperature environment, and peeling and the like are less likely to occur. In addition to being used for structural members, this adhesive can also be used as an adhesive for general office use, medical use, carbon fiber, cells, modules, and cases of storage batteries. It can be used as an adhesive for bonding optical components, an adhesive for laminating optical discs, an adhesive for mounting printed wiring boards, a die bonding adhesive, a semiconductor adhesive such as underfill, an underfill for reinforcing BGA, an anisotropic conductive film, and an anisotropic conductive paste for mounting.

[0177] When the curable resin composition of the present invention has a fibrous substrate and the fibrous substrate is a reinforcing fiber, the curable resin composition containing the fibrous substrate can be used as a fiber-reinforced resin. The method of incorporating the fibrous substrate into the composition is not particularly limited as long as the effects of the present invention are not impaired. Examples of methods for combining the fibrous substrate and the composition include methods of compounding them by kneading, coating, impregnating, injecting, pressure bonding, and the like. These methods can be appropriately selected according to the form of the fiber and the use of the fiber-reinforced resin.

[0178] The method for molding the fiber-reinforced resin is not particularly limited. If a plate-shaped product is to be manufactured, the extrusion molding method is common, but it is also possible by a flat press. In addition, it is possible to use an extrusion molding method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, etc. Also, if a film-shaped product is to be manufactured, in addition to the melt extrusion method, the solution casting method can be used. When using a melt molding method, inflation film molding, cast molding, extrusion lamination molding, calender molding, sheet molding, fiber molding, blow molding, injection molding, rotational molding, coating molding, etc. can be mentioned. Further, in the case of a resin cured by active energy rays, a cured product can be manufactured using various curing methods using active energy rays. In particular, when a thermosetting resin is the main component of the matrix resin, a molding method in which the molding material is prepreged and pressure-heated by a press or an autoclave can be mentioned. In addition, RTM (Resin Transfer Molding) molding, VaRTM (Vacuum assist Resin Transfer Molding) molding, lamination molding, hand lay-up molding, etc. can be mentioned.

[0179] Since the cured product obtained by using the curable resin composition of the present invention has both good heat resistance and reparability and has remoldability, it can be used as a molding material for large cases, motor housings, in-mold injection materials inside cases, gears, pulleys, etc. These may be cured products of resin alone or fiber-reinforced cured products such as glass chips.

[0180] The fiber-reinforced resin can form a state called uncured or semi-cured prepreg. After distributing the product in the prepreg state, final curing may be performed to form a cured product. When forming a laminate, after forming the prepreg, laminating other layers and then performing final curing can form a laminate in which each layer is adhered, which is preferable. The mass ratio of the composition and the fibrous substrate used at this time is not particularly limited, but usually, it is preferably prepared so that the resin content in the prepreg is 20 to 60% by mass.

[0181] The cured product of the present invention has good heat resistance and reparability, and has reshaping properties, and can be used as a heat-resistant material and an electronic material. In particular, it can be suitably used for semiconductor encapsulants, circuit boards, build-up films, build-up substrates, etc., as well as adhesives and resist materials. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance. The heat-resistant members and electronic members thus obtained can be suitably used for various applications. For example, industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc. can be mentioned. Moreover, it is not limited to these.

[0182] Among them, taking advantage of the excellent flexibility of the cured product, it can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering, electronics, aircraft, and space industries. The adhesive of the present invention can maintain high adhesiveness without being affected by changes in the temperature environment even when used for bonding different materials such as between metal and non-metal, and peeling and the like are less likely to occur. In addition, the adhesive of the present invention can be used not only for structural member applications but also as an adhesive for general office use, medical use, carbon fiber, cells, modules, and cases of storage batteries. Examples of the adhesive of the present invention include adhesives for optical component bonding, adhesives for optical disk bonding, adhesives for printed wiring board mounting, die bonding adhesives, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, anisotropic conductive films, and adhesives for mounting such as anisotropic conductive pastes.

[0183] Hereinafter, examples will be given and described for representative products.

[0184] 1. Semiconductor Encapsulation Material As a method for obtaining a semiconductor encapsulant from the resin composition of the present invention, a method of uniformly melt-mixing the resin composition, a curing accelerator, and compounding agents such as an inorganic filler using an extruder, kneader, roll, etc. as necessary until uniform is mentioned. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, high filling of crystalline silica, alumina, silicon nitride, etc. with a higher thermal conductivity than fused silica, or the use of fused silica, crystalline silica, alumina, silicon nitride, etc. is preferable. The filling rate is preferably in the range of 30 to 95% by mass of the inorganic filler per 100 parts by mass of the curable resin composition. Among them, in order to improve flame retardancy, moisture resistance, solder crack resistance, and reduce the linear expansion coefficient, 70 parts by mass or more is more preferable, and 80 parts by mass or more is even more preferable.

[0185] 2. Semiconductor device As semiconductor package molding for obtaining a semiconductor device from the curable resin composition of the present invention, a method of molding the above semiconductor encapsulant using a casting mold, a transfer molding machine, an injection molding machine, etc., and further heating at 50 to 250 °C for 2 to 10 hours is mentioned.

[0186] 3. Printed circuit board As a method for obtaining a printed circuit board from the composition of the present invention, a method of laminating the above prepreg by a conventional method, appropriately stacking a copper foil, and heat-pressure bonding at 170 to 300 °C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa is mentioned.

[0187] 4. Flexible substrate As a method for manufacturing a flexible substrate from the crosslinkable resin composition of the present invention, a method consisting of the following three steps can be mentioned. The first step is a step of applying a crosslinkable resin composition containing a resin component, an organic solvent, etc. to an electrically insulating film using a coater such as a reverse roll coater or a comma coater. The second step is a step of heating the electrical insulating film coated with the crosslinkable resin composition at 60 to 170 °C for 1 to 15 minutes using a heating machine, volatilizing the solvent from the electrical insulating film, and B-staging the crosslinkable resin composition. The third step is a step of thermocompression bonding (the bonding pressure is preferably 2 to 200 N / cm and the bonding temperature is preferably 40 to 200 °C) a metal foil to the adhesive using a heating roll or the like on the electrical insulating film on which the crosslinkable resin composition has been B-staged. In addition, if sufficient adhesion performance is obtained through the above three steps, it may be ended here, but if complete adhesion performance is required, it is preferably post-cured under the conditions of 100 to 200 °C for 1 to 24 hours. The thickness of the resin composition layer after final curing is preferably in the range of 5 to 100 μm.

[0188] 5. Build-up substrate Examples of the method for obtaining a build-up substrate from the composition of the present invention include the following steps. First, a step of applying the above composition appropriately blended with rubber, filler, etc. to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then curing it (step 1). After that, if necessary, after drilling holes such as a predetermined through-hole portion, treating with a roughening agent, and forming unevenness by hot washing the surface, a step of plating a metal such as copper (step 2). Such operations are sequentially repeated as desired to form a resin insulation layer and a conductor layer of a predetermined circuit pattern by alternately building them up (step 3). Note that the drilling of the through-hole portion is performed after the formation of the outermost resin insulation layer. In addition, the build-up substrate of the present invention can also be produced by heat-pressure bonding a copper foil with resin obtained by semi-curing the resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 °C, forming a roughened surface, and omitting the plating process.

[0189] 6. Build-up film As a method for obtaining a build-up film from the composition of the present invention, the composition is applied to the surface of a support film (Y) as a base material, and then the organic solvent is dried by heating or blowing hot air, etc., to form a layer (X) of the composition.

[0190] Examples of the organic solvent used here include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. It is preferable to use them, and it is also preferable to use them in a proportion such that the non-volatile content is 30 to 60% by mass.

[0191] The thickness of the formed layer (X) is usually set to be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer preferably has a thickness of 10 to 100 μm. Note that the layer (X) of the above composition in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent adhesion of dust or scratches to the surface of the resin composition layer.

[0192] Examples of the above-mentioned support film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate; polycarbonate, polyimide; and further, release paper, copper foil, metal foils such as aluminum foil, etc. Note that the support film and the protective film may be subjected to a mat treatment, a corona treatment, or a release treatment in addition to these. The thickness of the support film is not particularly limited, but it is usually 10 to 150 μm, and preferably used in the range of 25 to 50 μm. Also, the thickness of the protective film is preferably 1 to 40 μm.

[0193] The above-mentioned support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the curable resin composition layer constituting the build-up film is heat cured, it is possible to prevent the adhesion of dust and the like during the curing process. When peeling off after curing, usually, the support film is previously subjected to a release treatment.

[0194] A multilayer printed circuit board can be manufactured using the build-up film obtained as described above. For example, when the layer (X) is protected by a protective film, after peeling these off, the layer (X) is laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch type or a continuous roll type. Further, if necessary, the build-up film and the circuit board may be heated (preheated) as necessary before lamination. The lamination conditions preferably have a crimping temperature (lamination temperature) of 70 to 140°C, a crimping pressure of 1 to 11 kgf / cm2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0195] 7. Conductive paste As a method for obtaining a conductive paste from the composition of the present invention, for example, a method of dispersing conductive particles in the composition can be mentioned. The above-mentioned conductive paste can be a circuit connection paste resin composition or an anisotropic conductive adhesive depending on the type of conductive particles used.

Examples

[0196] Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The present invention is not limited thereby.

[0197] 1 H and 1313C-NMR, FD-MS spectra, and GPC were measured under the following conditions.

[0198] 1 1H-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE Magnetic field strength: 600 MHz Number of integrations: 32 times Solvent: DMSO-d 6 Sample concentration: 30 mass%

[0199] 13 13C-NMR: "JNM-ECA600" manufactured by JEOL RESONANCE Magnetic field strength: 150 MHz Number of integrations: 320 times Solvent: DMSO-d 6 Sample concentration: 30 mass%

[0200] FD-MS: "JMS-T100GC AccuTOF" manufactured by JEOL Ltd. Measurement range: m / z = 50.00 - 2000.00 Rate of change: 25.6 mA / min Final current value: 40 mA Cathode voltage: -10 kV

[0201] GPC: "HLC-8320GPC" manufactured by Tosoh Corporation Column: "TSK-GEL G2000HXL" + "TSK-GEL G3000HXL" + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Measurement conditions: 40 °C Mobile phase: Tetrahydrofuran Flow rate: 1 ml / min Standard: "PStQuick A", "PStQuick B", "PStQuick E", "PStQuick F" manufactured by Tosoh Corporation

[0202] Regarding the epoxy equivalent of the synthesized epoxy resin, measurement was carried out in accordance with JIS K7236, and the epoxy equivalent (g / eq) was calculated.

[0203] As a method for calculating the number of repeating units, examples include calculation from appropriate various instrumental analysis results such as GPC molecular weight measurement, FD-MS, and NMR.

[0204] (Synthesis Example 1) To a flask equipped with a thermometer and a stirrer, 11.7 g (0.05 mol) of resorcinol diglycidyl ether ("Denacol EX-201" manufactured by Nagase ChemteX: epoxy equivalent 117 g / eq) and 18.9 g (0.1 mol) of 4-hydroxyphenylmaleimide were added. After heating up to 140 °C over 30 minutes, 1.5 g of a 4% aqueous sodium hydroxide solution was added. Then, it took 30 minutes to heat up to 150 °C, and the reaction was further carried out at 150 °C for 15 hours. Then, sodium phosphate in the neutralization amount was added to obtain 29.6 g of the maleimide compound (A-1).

[0205] [Chemical formula]

[0206] (Example 1) "Synthesis of Diels-Alder adduct (D-1)" To a flask equipped with a thermometer, a stirrer, and a condenser, 38.6 g (0.2 mol) of 2-aminoanthracene, 60.1 g (0.1 mol) of the maleimide compound (A-1) obtained by the method of Synthesis Example 1, and 347 g of toluene were charged. After nitrogen substitution, the reaction was carried out at 100 °C for 6 hours. Then, the temperature was raised to 150 °C and toluene was distilled off under reduced pressure, and after cooling to room temperature, 97.2 g of the Diels-Alder adduct (D-1) was obtained. For this Diels-Alder adduct (D-1), a peak of M+ = 987 was obtained in the mass spectrum, and the formation of the target compound was confirmed.

[0207] [Chemical formula]

[0208] (Synthesis Example 2) 10.1 g (0.05 mol) of diglycidyl ether of 1,4 - butanediol and 18.9 g (0.1 mol) of 4 - hydroxyphenylmaleimide were added to a flask equipped with a thermometer and a stirrer, and the temperature was raised to 140°C over 30 minutes. Then, 1.5 g of a 4% aqueous sodium hydroxide solution was added. Thereafter, the temperature was raised to 150°C over 30 minutes and further reacted at 150°C for 20 hours. Then, sodium phosphate in an amount for neutralization was added to obtain 28.5 g of maleimide compound (A - 2).

[0209] [Chemical Formula]

[0210] (Example 2) "Synthesis of Diels - Alder adduct (D - 2)" 38.6 g (0.2 mol) of 1 - aminoanthracene, 58.1 g (0.1 mol) of maleimide compound (A - 2) obtained by the method of Synthesis Example 2, and 347 g of toluene were charged into a flask equipped with a thermometer, a stirrer, and a condenser tube. After nitrogen substitution, the mixture was reacted at 100°C for 6 hours. Then, the temperature was raised to 150°C and toluene was distilled off under reduced pressure. After cooling to room temperature, 95.0 g of Diels - Alder adduct (D - 2) was obtained. This Diels - Alder adduct (D - 2) gave a peak of M+ = 967 in the mass spectrum, confirming the formation of the target compound.

[0211] [Chemical Formula]

[0212] (Synthesis Example 3) To a flask equipped with a thermometer and a stirrer, 13.5 g (0.05 mol) of diglycidyl ether of 1,6 - hexanediol (Denacol EX - 212L manufactured by Nagase ChemteX: epoxy equivalent 135 g / eq) and 18.9 g (0.1 mol) of 4 - hydroxyphenyl maleimide were added. After heating up to 140 °C over 30 minutes, 1.5 g of a 4% aqueous sodium hydroxide solution was added. Then, it took 30 minutes to heat up to 150 °C and the reaction was further carried out at 150 °C for 20 hours. Thereafter, sodium phosphate in the neutralization amount was added to obtain 31.4 g of maleimide compound (A - 3).

[0213] [Chemical formula]

[0214] (Example 3) "Synthesis of Diels - Alder adduct (D - 3)" To a flask equipped with a thermometer, a stirrer, and a condenser, 38.6 g (0.2 mol) of 2 - aminoanthracene, 60.9 g (0.1 mol) of the maleimide compound (A - 3) obtained by the method of Synthesis Example 3, and 347 g of toluene were charged. After nitrogen substitution, the reaction was carried out at 100 °C for 6 hours. Then, the temperature was raised to 150 °C and toluene was distilled off under reduced pressure. After cooling to room temperature, 98.5 g of Diels - Alder adduct (D - 3) was obtained. This Diels - Alder adduct (D - 3) gave a peak of M+ = 995 in the mass spectrum, and the formation of the target compound was confirmed.

[0215] [Chemical formula]

[0216] (Synthesis Example 4) Into a flask equipped with a thermometer, a cooling tube, and a stirrer, 10.1 g (0.05 mol) of 1,3-dibromopropane, 18.8 g (0.1 mol) of 4-hydroxyphenylmaleimide, 143 g of dehydrated acetone, and 55.2 g of fine powder potassium carbonate were charged. After nitrogen substitution, the mixture was reacted at 55 °C for 24 hours. It was cooled to room temperature and filtered off. 210 g of toluene was added, and the insoluble matter was removed by filtration. 210 g of water was added, and liquid separation was performed three times. After the organic layer was dehydrated with sodium sulfate, toluene was distilled off under reduced pressure using an evaporator to obtain 20.2 g of maleimide compound (A-4).

[0217]

Chemical formula

[0218] (Example 4) "Synthesis of Diels-Alder adduct (D-4)" Into a flask equipped with a thermometer, a stirrer, and a cooling tube, 38.6 g (0.2 mol) of 1-aminoanthracene, 41.8 g (0.1 mol) of maleimide compound (A-4) synthesized by the method of Synthesis Example 4, and 347 g of toluene were charged. After nitrogen substitution, the mixture was reacted at 100 °C for 6 hours. Then, the temperature was raised to 150 °C and toluene was distilled off under reduced pressure. It was cooled to room temperature to obtain 78.3 g of Diels-Alder adduct (D-4). This Diels-Alder adduct (D-4) gave a peak of M+ = 805 in the mass spectrum, confirming the formation of the target compound.

[0219]

Chemical formula

[0220] (Synthesis Example 5) Into a flask equipped with a thermometer, a cooling tube, and a stirrer, 16.4 g (0.05 mol) of 1,12-dibromododecane, 18.8 g (0.1 mol) of 4-hydroxyphenylmaleimide, 143 g of dehydrated acetone, and 55.2 g of fine powder potassium carbonate were charged. After purging with nitrogen, the mixture was reacted at 55 °C for 24 hours. After cooling to room temperature, the mixture was filtered, 210 g of toluene was added, and the insoluble matter was removed by filtration. 210 g of water was added, and liquid separation was performed three times. After dehydrating the organic layer with sodium sulfate, toluene was distilled off under reduced pressure using an evaporator to obtain 20.2 g of maleimide compound (A-5).

[0221] [Chemical formula]

[0222] (Example 5) "Synthesis of Diels-Alder adduct (D-5)" Into a flask equipped with a thermometer, a stirrer, and a cooling tube, 38.6 g (0.2 mol) of 1-aminoanthracene, 54.5 g (0.1 mol) of maleimide compound (A-5) synthesized by the method of Synthesis Example 5, and 347 g of toluene were charged. After purging with nitrogen, the mixture was reacted at 100 °C for 6 hours. Then, the temperature was raised to 150 °C, and toluene was distilled off under reduced pressure. After cooling to room temperature, 91.8 g of Diels-Alder adduct (D-5) was obtained. For this Diels-Alder adduct (D-5), a peak of M+ = 931 was obtained in the mass spectrum, and the formation of the target compound was confirmed.

[0223] [Chemical formula]

[0224] (Synthesis Example 6) N-(4-aminophenyl)maleimide (APM) was prepared. That is, 5.35 g (49.5 mmol) of p-phenylenediamine and 97 mL of tetrahydrofuran (THF) were added to a 300 mL eggplant flask, and while stirring, 4.85 g (49.5 mmol) of maleic anhydride dissolved in 36 mL of THF was added dropwise at room temperature over 1 hour. After completion of the dropwise addition, stirring (r.t. / 12 h) was carried out, and the precipitate formed was collected by suction filtration and dried under reduced pressure (r.t. / 12 h) to obtain 9.49 g of APMA (yellow solid). Subsequently, 9.47 g (45.9 mmol) of APMA was added to a 200 mL two-necked flask. After purging the system with argon, 36 mL of N,N-dimethylformamide (DMF) and 9.60 mL (68.9 mmol) of triethylamine (NEt 3 ) were added, and the mixture was stirred and dissolved at room temperature. The flask was cooled in ice, 10.6 mL (46.0 mmol) of di-tert-butyl dicarbonate (Boc 2 O) was added, and the mixture was stirred for 15 minutes and then stirred at room temperature for 17 hours. The resulting solution was poured into 257 mL of pure water (0 °C), and a precipitate was formed by adjusting the pH to 4.5 - 5.5 with dilute hydrochloric acid. This precipitate was collected by suction filtration and dried under reduced pressure (70 °C / 12 h) to obtain 13.5 g of a pale yellow solid. Of this pale yellow solid, 13.2 g was added to a 1000 mL eggplant flask together with 133 mL of acetic anhydride (Ac 2 O), and the temperature was raised to 95 °C. Then, 3.88 g (47.3 mmol) of sodium acetate (AcONa) was added and stirring (95 °C / 2 h) was carried out. After completion of stirring, the pale yellow solid precipitated by standing at room temperature for 12 h was stirred (r.t. / 10 min) after adding 800 mL of pure water, and then recovered by suction filtration and washing with saturated aqueous sodium hydrogen carbonate solution and pure water. The obtained solid was dissolved in dichloromethane, washed with pure water and saturated brine, and then dried over sodium sulfate, filtered, the solvent was distilled off, and dried under reduced pressure (r.t. / 12 h) to obtain 10.2 g of Boc-APM (pale yellow solid). Subsequently, dichloromethane (CH 2 Cl2 ) 56 mL was added, and after adding 68.5 g (0.601 mol) of trifluoroacetic acid (CF 3 COOH) under an ice bath, stirring (r.t. / 2 h) was carried out. After the reaction was completed, the solvent was distilled off, and the residue was dissolved in pure water, and extraction was performed 3 times with dichloromethane / saturated aqueous sodium hydrogen carbonate solution. After the obtained organic layer was washed with pure water and saturated brine, drying with sodium sulfate, filtration, solvent distillation, and drying under reduced pressure (r.t. / 12 h) were carried out to obtain a crude product (5.84 g) of APM. This crude product was purified by silica gel column chromatography (developing solvent: chloroform / ethyl acetate = 20 / 1) to obtain 4.66 g of APM (red solid). The yield was 52% in four steps.

[0225] (Synthesis Example 7) A flask equipped with a thermometer, a stirrer, and a condenser was charged with 19.3 g (0.1 mol) of 2-aminoanthracene, 18.8 g (0.1 mol) of APM obtained by the method of Synthesis Example 6, and 174 g of toluene. After purging with nitrogen, the reaction was carried out at 100 °C for 10 hours. Then, the temperature was raised to 150 °C, and toluene was distilled off under reduced pressure. After cooling to room temperature, 37.0 g of the Diels-Alder reaction product (D-6) was obtained.

[0226] (Synthesis Example 8) A flask equipped with a thermometer and a stirrer was charged with 210 g (0.5 mol) of diglycidyl ether of 1,12-dodecanediol (manufactured by Yokkaichi Synthesis Co., Ltd.: epoxy equivalent 210 g / eq) and 119.7 g (0.53 mol) of bisphenol A (hydroxyl equivalent 114 g / eq). After heating to 140 °C over 30 minutes, 3.2 g of 20% aqueous sodium hydroxide solution was charged. Then, it took 30 minutes to raise the temperature to 150 °C, and the reaction was further carried out at 150 °C for 16 hours. Then, a neutralizing amount of sodium phosphate was added to obtain 320 g of the hydroxy compound (Ph-1).

[0227] (Synthesis Example 9) Into a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, while purging with nitrogen gas, 200 g of the hydroxy compound Ph-1 obtained in Synthesis Example 6, 437 g (4.72 mol) of epichlorohydrin, and 118 g of n-butanol were charged and dissolved. After raising the temperature to 65°C, the pressure was reduced to the azeotropic pressure, and 6.66 g (0.08 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hour under the same conditions. During this time, the distillate distilled off by azeotropy was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer into the reaction system. Then, unreacted epichlorohydrin was distilled off by distillation under reduced pressure. 150 g of methyl isobutyl ketone and 150 g of n-butanol were added to and dissolved in the resulting crude epoxy resin. Further, 10 g of a 10% aqueous sodium hydroxide solution was added to this solution, and the mixture was reacted at 80°C for 2 hours, and then washed three times with 50 g of water until the pH of the washing liquid became neutral. Next, the system was dehydrated by azeotropy, and after passing through fine filtration, the solvent was distilled off under reduced pressure to obtain 190 g of an epoxy compound Ep-1. The epoxy equivalent of the obtained epoxy compound Ep-1 was 2320 g / eq.

[0228] "Preparation of Composition and Cured Product" (Examples 6 to 14, Comparative Example 1) In a 300 mL eggplant-shaped flask, according to the formulation shown in Table 1 (the numbers in the table are based on mass), each compound and acetone were added, and stirring (room temperature / 30 minutes) was carried out. Then, it was concentrated by evaporation and dried under reduced pressure (room temperature / overnight) to obtain a curable resin composition. Next, each curable resin composition was heat-cured under predetermined conditions in a vacuum press to obtain a cured product with a thickness of 0.5 mm.

[0229] (Comparative Example 2) A curable resin composition was obtained by mixing each compound uniformly in a mixer (Thinky Corporation's "Awatori Rentaro ARV-200") according to the formulation in Table 1 (the numbers in the table are by weight). This curable resin composition was sandwiched between aluminum mirror plates (Engineering Test Service Corporation's "JIS H 4000 A1050P") using a silicon tube as a spacer, and heat curing was performed under specified conditions to obtain a cured product with a thickness of 0.5 mm.

[0230] Comparative Example 3 A curable resin composition was obtained by melt-kneading each compound in the formulation shown in Table 1 (the numbers in the table are by mass). This curable resin composition was cured in a vacuum press at 150°C for 10 minutes, and then after-cured at 175°C for 5 hours to obtain a cured product having a thickness of 0.5 mm.

[0231] <Visual observation before and after remolding> The prepared hardened product was freeze-pulverized. 0.07 g of the pulverized hardened product was placed in a 10 mm square, 0.5 mm thick mold and vacuum-pressed under specified conditions. The appearance of the obtained hardened product was visually observed. The evaluation criteria were as follows: A: The seams disappeared and the hardened material became one piece. B: Some of the seams are visible to the naked eye, but the hardened material has become one piece. C: It had a solidified shape and broke apart when light pressure was applied.

[0232] <Tensile test before and after remolding> The prepared cured product was punched out into a dumbbell shape (JIS K 7161-2-1BA) with a punching blade to prepare a test piece. Using a tensile tester (Shimadzu Corporation's "Autograph AG-IS"), the breaking stress and tensile elongation were evaluated in a measurement environment of 23°C in accordance with JIS K 7162-2 (test speed: 2 mm / min). The freeze-pulverized cured product was vacuum pressed under specified conditions, and the prepared cured product was punched out into a dumbbell shape with a punching blade, and a tensile test was similarly performed and evaluated. Regarding the obtained breaking stress and tensile elongation rate, the recovery rate (%) was calculated based on the formula of (value after recovery / initial value) × 100%.

Table 1

[0233] In addition, each formulation shown in the table is as follows. EPICLON-850S: Bisphenol A liquid epoxy resin (manufactured by DIC Corporation, epoxy equivalent 188 g / eq) Denacol EX-201: (manufactured by Nagase ChemteX Corporation, epoxy equivalent 117 g / eq) TD-2131: Phenol novolac type phenol resin (manufactured by DIC Corporation, hydroxyl equivalent 104 g / eq) 4,4'-Diaminodiphenylmethane (manufactured by Kanto Chemical Co., Inc.) TPP: Triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.)

Claims

1. An amino group-containing compound represented by the following general formula (1) and having a molecular weight of less than 1,000: 【Chemistry 1】 （１） In the general formula (1), m is an integer of 1 to 10. Z １ are each independently a hydrogen atom, an amino group, a halogen atom, an alkoxy group, an aralkyloxy group, an aryloxy group, a nitro group, an amido group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group, and Z １ At least one of the groups is an amino group or a group having an amino group as a substituent. Z ３ is any of the structures represented by the following formula (2). 【Chemistry 2】 (In formula (2), R' is a divalent hydrocarbon group having 2 to 12 carbon atoms, and R １ , R ２ R″ each independently represents a hydrogen atom, a methyl group or an ethyl group, n1 represents an integer of 1 to 30, n2 represents the average number of repetitions and is 0.5 to 8, and * represents a bonding point.

2. A curable resin composition comprising, as essential components, the amino group-containing compound according to claim 1 and a compound (I) reactive with the amino group-containing compound.

3. The curable resin composition according to claim 2 , wherein a concentration of reversible bonds in the amino group-containing compound relative to the total mass of the curable components in the curable resin composition is 0.10 mmol / g or more.

4. 3. The curable resin composition according to claim 2, wherein the compound (I) reactive with the amino group-containing compound is an epoxy resin.

5. The curable resin composition according to claim 4, further comprising a curing agent for epoxy resins other than the amino group-containing compound.

6. The curable resin composition according to claim 4, wherein the epoxy resin is represented by the following formula (3) and has an epoxy equivalent of 500 to 10,000 g / eq. 【Chemistry 3】 In formula (3), each Ar is independently a structure having an unsubstituted or substituted aromatic ring, X' is a structural unit represented by the following general formula (3-1), and Y' is a structural unit represented by the following general formula (3-2): 【Chemistry 4】 [In formulas (3-1) and (3-2), Ar is the same as defined above, R １ , R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group, R' is a divalent hydrocarbon group having 2 to 12 carbon atoms; R ３ , R ４ , R ７ , R ８ each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R ５ , R ６ , R ９ , R １０ each independently represents a hydrogen atom or a methyl group, n1 is an integer from 4 to 16, n2 is the average number of repeating units and is from 2 to 30. R １１ , R １２ each independently represents a glycidyl ether group or a 2-methylglycidyl ether group, R １３ , R １４ each independently represents a hydroxyl group, a glycidyl ether group, or a 2-methylglycidyl ether group, R １５ , R １６ is a hydrogen atom or a methyl group, m3, m4, p1, p2, and q are the average values ​​of the repetitions, m3 and m4 each independently represent 0 to 25, and m3+m4≧1; p1 and p2 each independently represent 0 to 5; q is 0.5 to 5. However, the bond between X' represented by the general formula (3-1) and Y' represented by the general formula (3-2) may be random or block, and the total numbers of the structural units X' and Y' present in one molecule are m3 and m4, respectively.

7. The curable resin composition according to claim 6, wherein the epoxy resin is represented by the following formula (4): 【Chemistry 5】 [In formula (4), p1, p2, q, and m4 are average values ​​of repetition, and each independently, p1 is 0 to 5, p2 is 0 to 5, q is 0.5 to 5, and m4 is 0 to 25.]

8. The curable resin composition according to claim 2, which is a self-repairing composition or a remolding material composition.

9. A cured product obtained by curing the curable resin composition according to claim 2.

10. A laminate comprising a substrate and a layer comprising the cured product according to claim 9.

11. A heat-resistant component comprising the cured product according to claim 9.

12. A method for producing an amino group-containing compound, comprising synthesizing the amino group-containing compound represented by formula (1) in claim 1 in situ during the process of curing the compound with a compound (I) reactive with the amino group-containing compound, using a dienophilic intermediate represented by the following general formula (1)': 【Chemistry 6】

13. A cured product obtained by curing reaction of a dienophilic intermediate represented by formula (1)' in claim 12, an anthracene having an amino group, and a compound (I) reactive with the amino group-containing compound described in claim 1 as essential raw materials.

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