TW201843137A - Imide oligomer, curing agent, adhesive and method for producing imide oligomer - Google Patents

Abstract

A purpose of the present invention is to provide an imide oligomer which is able to be used for a cured product that has excellent long-term heat resistance. Another purpose of the present invention is to provide: a curing agent which is composed of the imide oligomer; and an adhesive which is obtained using the curing agent. Another purpose of the present invention is to provide a method for producing the imide oligomer. The present invention is an imide oligomer which has a phenolic hydroxyl group, and wherein the content ratio of an imide oligomer having an ester bond is 7% or less.

Description

   Perylene imine oligomer, hardener, adhesive, and method for producing perylene imine oligomer   

The present invention relates to a sulfonimide oligomer which can be used for a hardened material having excellent long-term heat resistance. Moreover, this invention relates to the hardening | curing agent which consists of this fluorene imine oligomer, and the adhesive agent which uses this hardening | curing agent. Furthermore, this invention relates to the manufacturing method of this fluorene imine oligomer.

Hardening resins such as epoxy resins with low shrinkage and excellent adhesion, insulation, and chemical resistance are used in many industrial products. In particular, in the field of electronic equipment, a hardening resin composition that can obtain a good result in a reflow soldering test about short-term heat resistance or a cold-heat cycle test about repeated heat resistance is often used.

In recent years, electronic control units (ECUs) for vehicles, or power devices using SiC and GaN have attracted much attention, but the curable resin composition used in these applications does not require short-term or repeated heat resistance. Rather, heat resistance (long-term heat resistance) is required for continuous and long-term exposure to high temperatures.

As a hardener for a curable resin composition, Patent Document 1 discloses a fluorene imine oligomer hardener having an acid anhydride structure at both ends. However, it is incompatible with curable resins such as epoxy resins. Sufficiently, there is a problem that the obtained curable resin composition becomes poor in long-term heat resistance.

On the other hand, in Patent Documents 2 and 3, it is disclosed that a polyimide introduced with a flexible polysiloxane skeleton or an alicyclic skeleton is used as a curing agent in order to improve the compatibility with the curable resin. Sexual resin composition. However, if a polysiloxane skeleton or an alicyclic skeleton is introduced, there is a problem that the glass transition temperature of the obtained hardened product is liable to decrease, and the mechanical strength or long-term heat resistance at the operating temperature of the ECU or power device is poor. By. In addition, Patent Document 4 discloses that by using a specific sulfonium oligomer having a phenolic hydroxyl group or the like at both ends as a curing agent, the adhesion or heat resistance of a thermosetting resin composition is improved. However, when such a fluorene imine oligomer is used, long-term heat resistance may be reduced.

    Prior art literature         Patent literature    

Patent Document 1: Japanese Patent Application Laid-Open No. 61-270852

Patent Document 2: Japanese Patent Application Laid-Open No. 2016-20437

Patent Document 3: Japanese Patent Application Publication No. 2012-227534

Patent Document 4: International Publication No. 2005/100433

An object of the present invention is to provide a fluorene imine oligomer which can be used for a hardened product excellent in long-term heat resistance. Another object of the present invention is to provide a hardener composed of the fluorene imine oligomer, and an adhesive agent using the hardener. Furthermore, the objective of this invention is to provide the manufacturing method of this fluorene imine oligomer.

The present invention relates to a fluorene imine oligomer, which has a phenolic hydroxyl group and an ester bond, and the content ratio of the fluorene imine oligomer is 7% or less.

Hereinafter, the present invention will be described in detail.

The present inventors have found that among fluorene imine oligomers having a phenolic hydroxyl group, those having an ester bond, when used as a hardener, do not have the effect of improving the long-term heat resistance of the hardened material, and thus have a poor effect on use. Phenylimine oligomers with phenolic hydroxyl groups and no ester linkages were investigated. However, even when a fluorene imine oligomer having a phenolic hydroxyl group and no ester bond is used, the long-term heat resistance of the cured product cannot be sufficiently improved. The present inventors believe that the reason why the long-term heat resistance of the hardened material cannot be sufficiently improved is that a fluorene imine oligomer having a phenolic hydroxyl group used as a person having no ester bond has a small amount of an ester bond as an impurity醯 Imine oligomer. Therefore, the present inventors conducted intensive studies and found that by using a fluorene imine oligomer having a phenolic hydroxyl group with a content ratio of fluorene imino oligomer having an ester bond as an impurity to 7% or less A hardened body excellent in long-term heat resistance can be obtained, and the present invention has been completed.

The fluorene imine oligomer of the present invention has a phenolic hydroxyl group.

The fluorene imine oligomer of the present invention has a content of fluorene imine oligomer having an ester bond of 7% or less. When the content ratio of the fluorene imine oligomer having an ester bond as described above is 7% or less, the fluorene imine oligomer of the present invention has an effect of improving the long-term heat resistance of the obtained cured product when used as a curing agent. Outstanding. The content of the fluorene imine oligomer having an ester bond is preferably 5% or less, and most preferably 0%, that is, the fluorene imine oligomer having an ester bond is not included.

In addition, the content ratio of the above-mentioned fluorene imine oligomer having an ester bond can be obtained by using Gel Permeation Chromatography (GPC) to separate each peak, and then by Fourier transform infrared spectroscopy (FT-IR) The weight ratio of the absorbed compound of the ester bond was calculated | required. Specifically, first, tetrahydrofuran (THF) was used in the free solution, and a HPLC (manufactured by Japan Analytical Industry Co., Ltd.) was used for the separation of HPLC (manufactured by Japan Analytical Industry Co., Ltd.) using a GPC column (eg, "JAIGEL-2H" manufactured by Japan Analytical Industry Corporation). Take each wave crest. Thereafter, the compound obtained by removing the free liquid by heating or the like is measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (for example, "UMA600" manufactured by Agilent Technologies, etc.). Based on the obtained measurement results, the weight ratio of the compound having a peak (1159 cm ^-1 ) derived from an ester bond to the weight ratio of all the peak compounds was derived.

From the viewpoint of the long-term heat resistance of the obtained cured product, the fluorene imine oligomer of the present invention preferably has a phenolic hydroxyl group at the terminal of the main chain, and more preferably has a phenolic hydroxyl group at both terminals.

The preferred lower limit of the number average molecular weight of the fluorene imine oligomer of the present invention is 400, and the preferred upper limit is 4200. When the above number average molecular weight is within this range, the cured product obtained when the fluorene imine oligomer of the present invention is used as a curing agent is excellent in long-term heat resistance. A more preferable lower limit of the number average molecular weight of the fluorene imine oligomer of the present invention is 420, and a more preferable upper limit is 4,000.

In addition, in this specification, the said "number average molecular weight" is the value calculated | required by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent, and calculated | required by polystyrene conversion. Examples of the column used when measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Analytical Industries, Ltd.).

Specifically, the fluorene imine oligomer of the present invention preferably contains a fluorene imine oligomer represented by the following formula (1-1) and / or a fluorene imine represented by the following formula (1-2) An amine oligomer is used as a main component.

In addition, in this specification, the said "main component" means the content rate is 60 mol% or more.

In the formulae (1-1) and (1-2), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted, and X is a bonding bond, an oxygen atom, or may be A substituted divalent hydrocarbon group. In the formula (1-2), Y is a bonding bond, an oxygen atom, or a divalent hydrocarbon group which may be substituted.

As a method for producing the fluorene imine oligomer of the present invention, a method can be preferably used in which the amount of the monoamine having a phenolic hydroxyl group used as a raw material is excessive.

The method for producing fluorene imine oligomer is also one of the present invention. The method for producing fluorene imine oligomer includes a step of reacting a compound having an acid anhydride group with a monoamine having a phenolic hydroxyl group, and the above-mentioned phenol having a phenol The use amount of the monoamine of the hydroxyl group is 1.5 equivalent or more with respect to the acid anhydride group of the compound having an acid anhydride group. According to the method for producing a fluorene imine oligomer of the present invention, it is possible to easily produce a fluorene imine oligomer of the present invention in which the content ratio of the fluorene imine oligomer having an ester bond generated as a by-product is 7% or less. Polymer.

The specific example of the manufacturing method of the fluorene imine oligomer of this invention is shown below.

First, a monoamine having a phenolic hydroxyl group is previously dissolved in a solvent (for example, N, N-dimethylformamide, etc.) that can dissolve the ammonium oligomer obtained by the reaction. An acid dianhydride was added to the solution, and it was made to react, and the ammonium oligomer solution was obtained. Next, the following operations were performed several times: the obtained phosphoamino acid oligomer solution was added to hydrochloric acid or the like, and the precipitate was recovered. The obtained imide is heated to cause the amidine imidization reaction to proceed, whereby an amidine imide oligomer having a phenolic hydroxyl group can be obtained. In the case of using this method, by using the amount of the monoamine having a phenolic hydroxyl group as described above to be 1.5 equivalents or more with respect to the acid anhydride group of the acid dianhydride, the oligoimine having an ester bond can be made The content of the polymer is set to 7% or less.

Moreover, another specific example of the manufacturing method of the fluorene imine oligomer of this invention is shown below.

First, a diamine is dissolved in a solvent (e.g., N, N-dimethylformamide, etc.) which can dissolve the ammonium oligomer obtained by the reaction, and an acid diamine is added to the obtained solution. Anhydride is allowed to react to obtain a solution of amidinic acid oligomer (A) having acid anhydride groups at both ends. A monoamine having a phenolic hydroxyl group is added to a solution of the obtained oligoamic acid oligomer (A) and reacted to obtain a solution of the oligoamino acid oligomer (B). Then, the following operation was performed several times: the solution of the obtained ammonium oligomer (B) was added to hydrochloric acid or the like, and the precipitate was recovered. By heating the obtained precipitate to cause the amidine imidization reaction to proceed, a amidine imide oligomer having a phenolic hydroxyl group can be obtained. In the case of using this method, the amount of the monoamine having a phenolic hydroxyl group is set to 1.5 equivalents or more with respect to the acid anhydride group of the amino acid oligomer (A). The content ratio of fluorene imine oligomer is set to 7% or less.

As the monoamine having a phenolic hydroxyl group, a compound represented by the following formula (2) can be preferably used.

Specific examples of the monoamine having a phenolic hydroxyl group include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4- Amino-2,3-xylenol, 4-amino-2,5-xylenol, 4-amino-2,6-xylenol, 4-amino-1-naphthol, 5-amine 2-naphthol, 6-amino-1-naphthol, 4-amino-2,6-diphenylphenol, and the like. Among these, 3-aminophenol, 4-aminophenol, and 4-amino-o-methyl are preferred in terms of obtaining a hardened product having excellent acquisition and storage stability and a high glass transition temperature. Phenol, 5-amino-o-cresol.

In formula (2), Ar is a divalent aromatic group which may be substituted, and R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group which may be substituted.

As the acid dianhydride, a compound represented by the following formula (3) can be preferably used.

Specific examples of the acid dianhydride include pyromelite dianhydride, 3,3'-oxybisphthalic dianhydride, 3,4'-oxybisphthalic dianhydride, and 4 , 4'-oxybisphthalic dianhydride, 4,4 '-(4,4'-isopropylidene diphenoxy) bisphthalic anhydride, 4,4'-bis (3,4 -Dicarboxyphenoxy) diphenyl ether, p-phenylene bis (trimellitic anhydride), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Tetracarboxylic dianhydride, 4,4'-carbonylbisphthalic dianhydride, etc. Among them, 4,4 '-(4,4'-isopropylidenediphenoxy) bisphthalic anhydride, 3, 4'-oxybisphthalic dianhydride, 4,4'-oxybisphthalic dianhydride, 4,4'-carbonylbisphthalic dianhydride.

In the formula (3), A is a tetravalent group represented by the following formula (4-1) or the following formula (4-2).

In the formula (4-1) and the formula (4-2), * is a bonding position, and in the formula (4-1), Z is a bonding bond, an oxygen atom, a carbonyl group, or may be substituted at the bonding position. A divalent hydrocarbon group having an oxygen atom. The hydrogen atom of the aromatic ring in the formula (4-1) and the formula (4-2) may be substituted.

As the diamine, a compound represented by the following formula (5) can be preferably used.

Specific examples of the diamine include 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3 , 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenediamine, 1,3-phenylenediamine , 1,4-phenylenediamine, 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylphosphonium, bis (4- (3-aminophenoxy) phenyl ) Fluorene, bis (4- (4-aminophenoxy) phenyl) fluorene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) ) Benzene, 1,4-bis (4-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) methane, 2,2-bis (4- (4-amino Phenoxy) phenyl) propane, 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene, 1,4-bis (2- (4-aminophenyl)- 2-propyl) benzene, 3,3'-diamino-4,4'-dihydroxydiphenylmethane, 4,4'-diamino-3,3'-dihydroxydiphenylmethane, 3,3 '-Diamino-4,4'-dihydroxydiphenyl ether, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-hydroxy-4-amino Phenyl) propane, bisaminophenylphosphonium, dimethyltoluidine, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diamino-3,3'-di Hydroxydiphenyl ether, 3,3'- Diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxydi Benzene, 4,4'-bis (4-aminobenzamide) -3,3'-dihydroxybiphenyl, 4,4'-bis (3-aminobenzamide) -3,3 ' -Dihydroxybiphenyl and the like. Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 1,2-benzene are preferred in terms of excellent solubility, heat resistance, and availability. Diamine, 1,3-phenylenediamine, 1,4-phenylenediamine, bis (4- (3-aminophenoxy) phenyl) fluorene, bis (4- (4-aminophenoxy) Phenyl) fluorene, 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene, 1,4-bis (2- (4-aminophenyl) -2-propyl )benzene.

In the formula (5), B is a divalent group represented by the following formula (6-1) or the following formula (6-2), and R ⁵ to R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group.

In formula (6-1) and formula (6-2), * is a bonding position, and in formula (6-1), Y is a bonding bond, an oxygen atom, or a divalent hydrocarbon group which may be substituted. The phenylene group in the formula (6-1) and the formula (6-2) may be substituted with a part or all of the hydrogen atoms by a hydroxyl group.

The lower limit of the fluorene imidization rate of the fluorene imine oligomer of the present invention is 70%. With the above imidation ratio of 70% or more, when used as a hardener, a hardened product having better mechanical strength at high temperatures and long-term heat resistance can be obtained. The lower limit of the above fluorene imidization rate is 75%, and the lower limit is more preferably 80%. In addition, the fluorene imidization rate of the fluorene imine oligomer of the present invention does not have a particularly preferable upper limit, but the practical upper limit is 98%.

In addition, the said "fluorene imidization rate" can be calculated | required by Fourier transform infrared spectroscopy (FT-IR). Specifically, a Fourier transform infrared spectrophotometer (e.g., "UMA600" manufactured by Agilent Technologies, etc.) can be used for measurement by total reflection measurement (ATR method). Derived from the peak absorbance area around 1660 cm ^-1 . In addition, the "peak absorbance area of amidine oligomer" in the following formula means that after a compound having an acid anhydride group is reacted with a monoamine having a phenolic hydroxyl group, the amine imidization step is not performed. The solvent was removed by evaporation, thereby obtaining the absorbance area of the amino acid oligomer.

醯 imidization rate (%) = 100 × (1- (peak absorbance area after fluorenimide) / (peak absorbance area of fluorene oligomer))

As described above, when the fluorene imine oligomer of the present invention is used as a hardener, a hardened material having excellent long-term heat resistance can be obtained. The hardener composed of the fluorene imine oligomer of the present invention is also one of the present invention. An adhesive containing a curable resin and the hardener of the present invention is also one aspect of the present invention.

Regarding the content of the hardener of the present invention in the adhesive of the present invention, the preferred lower limit is 50 parts by weight, and the preferred upper limit is 500 parts by weight based on 100 parts by weight of the curable resin. When the content of the curing agent of the present invention is within this range, the cured product of the obtained adhesive becomes more excellent in long-term heat resistance. A more preferable lower limit of the content of the hardener of the present invention is 70 parts by weight, and a more preferable upper limit is 400 parts by weight.

In order to improve workability in an unhardened state, etc., the adhesive of the present invention may contain other hardeners in addition to the hardener of the present invention within a range that does not hinder the object of the present invention.

Examples of the other hardener include a phenol-based hardener, a thiol-based hardener, an amine-based hardener, an acid anhydride-based hardener, a cyanate-based hardener, and an active ester-based hardener. Among them, a phenol-based hardener, an acid anhydride-based hardener, a cyanate-based hardener, and an active ester-based hardener are preferred.

In the case where the adhesive of the present invention contains the other hardening agent, a preferable upper limit of the content ratio of the other hardening agent in the entire hardener is 70% by weight, a more preferable upper limit is 50% by weight, and a more preferable upper limit is 30% by weight. %.

The adhesive of the present invention contains a curable resin.

From the viewpoint of fluidity and processability of the obtained adhesive, the above-mentioned curable resin is preferably liquid at 25 ° C.

As the curable resin, epoxy resin can be preferably used.

Examples of the epoxy resin include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, and 2,2'-diallyl. Bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, sulfide ring Oxygen resin, diphenyl ether epoxy resin, dicyclopentadiene epoxy resin, naphthalene epoxy resin, fluorene epoxy resin, naphthyl ether epoxy resin, phenolic phenolic epoxy resin, O-cresol novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, glycidylamine epoxy resin, alkyl polyol type ring Oxygen resin, rubber modified epoxy resin, glycidyl ester compound, etc. Among them, in terms of low viscosity and easy adjustment of the workability of the obtained adhesive at room temperature, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and resorcinol ring are preferred. Oxygen resin.

The adhesive of the present invention may contain a hardening accelerator. By containing the said hardening accelerator, the hardening time can be shortened and productivity can be improved.

Examples of the hardening accelerator include an imidazole-based hardening accelerator, a tertiary amine-based hardening accelerator, a phosphine-based hardening accelerator, a photobase generator, and a phosphonium salt-based hardening accelerator. Among these, an imidazole-based hardening accelerator is preferred.

Content of the said hardening accelerator is 0.01 weight part with a preferable minimum with respect to 100 weight part of said curable resin, and a preferable upper limit is 10 weight part. When the content of the hardening accelerator is within this range, the effect of shortening the hardening time while maintaining excellent adhesion and the like is more excellent. A more preferable lower limit of the content of the hardening accelerator is 0.05 parts by weight, and a more preferable upper limit is 5 parts by weight.

The adhesive of the present invention may contain an organic filler for the purpose of stress relaxation, toughness, and flame retardancy.

Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyimide particles, polyimide particles, polyimide particles, and benzomelamine. (Benzoguanamine) particles, and their core-shell particles. Among these, polyimide particles, polyimide particles, and polyimide particles are preferred.

The content of the organic filler is preferably 10 parts by weight and 100% by weight based on 100 parts by weight of the curable resin. When the content of the organic filler is within this range, the cured product obtained while maintaining excellent adhesiveness and the like becomes more excellent in toughness and the like. A more preferable lower limit of the content of the organic filler is 30 parts by weight, and a more preferable upper limit is 400 parts by weight.

The adhesive of the present invention can also contain an inorganic filler for the purpose of reducing the linear expansion coefficient after curing, reducing bending, imparting flame retardancy, and improving adhesion reliability.

Examples of the inorganic filler include silicon dioxide (silica) such as silicic acid glue, alumina, aluminum nitride, boron nitride, silicon nitride, aluminum hydroxide, magnesium hydroxide, glass frit, glass frit, Glass fiber, carbon fiber, inorganic ion exchanger, etc.

The content of the inorganic filler is preferably 10 parts by weight and 100% by weight based on 100 parts by weight of the curable resin. When the content of the inorganic filler is within this range, effects such as improvement in adhesion reliability and the like are maintained while maintaining excellent processability and the like. A more preferable lower limit of the content of the inorganic filler is 20 parts by weight, and a more preferable upper limit is 900 parts by weight.

Moreover, an inorganic filler can also be used as a flow control agent for the purpose of improving the coating property and shape retention property in a short time with respect to an adherend.

Examples of the inorganic filler used as the flow modifier include fumed silica and layered silicate.

Content of the said inorganic filler used as a flow modifier is 0.1 weight part with respect to 100 weight part of said curable resin, Preferably it is a minimum, and a preferable upper limit is 50 weight part. When the content of the inorganic filler used as the flow control agent is within this range, effects such as improvement in coating properties and shape retention properties in a short time with respect to the adherend are more excellent. A more preferable lower limit of the content of the above-mentioned inorganic filler used as the flow regulator is 0.5 part by weight, and a more preferable upper limit is 30 parts by weight.

The adhesive of the present invention may contain a polymer compound within a range that does not hinder the object of the present invention. The polymer compound functions as a film forming component.

The polymer compound may have a reactive functional group.

Examples of the reactive functional group include an amine group, an amine ester group, a fluorenimine group, a hydroxyl group, a carboxyl group, and an epoxy group.

In addition, the polymer compound may form a phase separation structure in the hardened material, or may not form a phase separation structure. In the case where the polymer compound does not form a phase separation structure in the hardened material, it is preferable that the polymer compound has excellent mechanical strength at high temperatures, long-term heat resistance, and moisture resistance. An epoxy group is a polymer compound having the above-mentioned reactive functional group.

The adhesive of the present invention may contain a reactive diluent within a range that does not hinder the object of the present invention.

The reactive diluent is preferably a reactive diluent having two or more reactive functional groups in one molecule from the viewpoint of reliability.

As a reactive functional group which the said reactive diluent has, the same thing as the reactive functional group which the said polymer compound has is mentioned.

The adhesive of the present invention may further contain additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, an anti-exudation agent, a fluxing agent, and a liquid flame retardant.

Examples of the method for producing the adhesive of the present invention include using a homomixer, a universal mixer, a Banbury mixer, a kneader, and the like to add a hardening resin, the hardener of the present invention, and if necessary, A method of mixing other hardening agents or hardening accelerators.

Furthermore, by applying the adhesive of the present invention to a release film and drying it, an adhesive film composed of the adhesive of the present invention can be obtained.

The adhesive of the present invention can be used in a wide range of applications, and in particular, it can be preferably used in electronic material applications requiring higher heat resistance. For example, it can be used as a die attach agent in aviation and automotive electronic control unit (ECU) applications, or in power device applications using SiC and GaN. Moreover, it can also be used, for example, for an adhesive for power overlay packaging, an adhesive for printed wiring boards, an adhesive for cover layers of flexible printed circuit boards, an adhesive for semiconductor bonding, and an adhesive for structural materials. Furthermore, in addition to the use of an adhesive, the curable composition can also be used in, for example, a sealant, a copper-clad laminate, an adhesive for semiconductor bonding, an interlayer insulating film, a prepreg, and the like.

According to the present invention, it is possible to provide a fluorene imine oligomer that can be used for a hardened product having excellent long-term heat resistance. Moreover, according to this invention, the hardening | curing agent which consists of this fluorene imine oligomer, and the adhesive agent using this hardening | curing agent can be provided. Furthermore, according to this invention, the manufacturing method of this fluorene imine oligomer can be provided.

Hereinafter, the present invention will be described in more detail by explaining examples, but the present invention is not limited to these examples.

(Synthesis example 1 (production of fluorene imine oligomer A))

32.74 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.5 equivalents to the anhydride group of the 3,4'-oxybisphthalic dianhydride undergoing the reaction) was dissolved in N, N-dimethyl Methylformamide in 200 mL. 31.0 parts by weight of 3,4'-oxybisphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, and the mixture was stirred at 25 ° C for 2 hours to perform a reaction to obtain amidin oligomer. Solution. The obtained ammonium oligomer solution was added to 2 L of 1 mol / L hydrochloric acid, and a precipitate was recovered. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid, and the precipitate was recovered. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid, and the precipitate was recovered. The obtained precipitate was heated at 180 ° C. for 2 hours, and then heated at 300 ° C. for 2 hours to react with sulfonimide, thereby obtaining a sulfonium imine oligomer A having a phenolic hydroxyl group. Amination rate of 94%).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer A has the fluorene imine oligomer represented by the above formula (1-1) as a main component. Furthermore, it was confirmed by GPC fractionation and FT-IR analysis that the content ratio of the fluorene imine oligomer A having an ester bond to the fluorene imine oligomer A was 5.5%. The number average molecular weight of the fluoreneimine oligomer A was 506.

(Synthesis example 2 (production of fluorene imine oligomer B))

The sulfonium imidization condition of the precipitate was changed to a vacuum drying oven, and heated at 200 ° C and 5 mmHg for 3 hours. Except that the sulfonium imine oligomer B (醯Imidization rate 46%).

By ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer B contains the fluorene imine oligomer represented by the above formula (1-1). In addition, GPC fractionation and FT-IR analysis confirmed that the content ratio of the fluorene imine oligomer B having an ester bond to the fluorene imine oligomer B was 5.5%. The number-average molecular weight of the fluoreneimine oligomer B was 510.

(Synthesis example 3 (production of fluorene imine oligomer C))

The use amount of 3-aminophenol was changed to 65.48 parts by weight (3 equivalents to the acid anhydride group of the 3,4'-oxybisphthalic dianhydride undergoing the reaction), except that the same amount was used as in Synthesis Example 1. A fluorene imine oligomer C having a phenolic hydroxyl group was obtained (94% of fluorene imine).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer C contains the fluorene imine oligomer represented by the above formula (1-1) as a main component. In addition, by GPC fractionation and FT-IR analysis, it was confirmed that the content ratio of fluorene imine oligomer C having an ester bond to fluorene imine oligomer C was 4.7%. The number average molecular weight of the fluoreneimine oligomer C was 506.

(Synthesis example 4 (production of fluorene imine oligomer D))

32.74 parts by weight of 3-aminophenol was changed to 36.95 parts by weight of 5-amino-o-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) (based on the anhydride of 3,4'-oxybisphthalic acid dianhydride undergoing the reaction) The base was 1.5 equivalents), and a fluorene imine oligomer D having a phenolic hydroxyl group (a fluorene imidization rate of 94%) was obtained in the same manner as in Synthesis Example 1.

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer D contains the fluorene imine oligomer represented by the above formula (1-1) as a main component. In addition, GPC fractionation and FT-IR analysis confirmed that the content of the fluorene imine oligomer D having an ester bond was 5.3%. The number-average molecular weight of the fluoreneimine oligomer D was 531.

(Synthesis example 5 (production of fluorene imine oligomer E))

52.0 parts by weight of 4,4 '-(4,4'-isopropylidene diphenoxy) bisphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) is added in place of 3,4'-oxybisphthalic acid A fluorene imine oligomer E having a phenolic hydroxyl group was obtained in the same manner as in Synthesis Example 1 except for 31.0 parts by weight of dianhydride (fluorine imidization rate: 93%). The amount of 3-aminophenol used is 1.5 equivalents based on the anhydride group of 4,4 '-(4,4'-isopropylidene diphenoxy) bisphthalic anhydride.

In addition, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer E has the fluorene imine oligomer represented by the above formula (1-1) as a main component. In addition, it was confirmed by GPC fractionation and FT-IR analysis that the content ratio of the fluorene imine oligomer E having an ester bond was 5.4%. The number-average molecular weight of the fluoreneimine oligomer E was 712.

(Synthesis example 6 (production of fluorene imine oligomer F))

34.45 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene ("Bisaniline M" manufactured by MITSUI FINE CHEMICALS) was dissolved in N, N-dimethylformamidine Amine in 200 mL. 104.1 parts by weight of 4,4 '-(4,4'-isopropylidene diphenoxy) bisphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, and the mixture was stirred at 25 ° C for 2 hours. And reacted to obtain a solution of amidinic acid oligomer (A) having acid anhydride groups at both ends. 32.74 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution of the obtained amino acid oligomer (A) (with respect to the acid anhydride group of the amino acid oligomer (A) to be reacted). (1.5 equivalents), stirred at 25 ° C for 2 hours, and reacted to obtain a solution of amidine oligomer (B). The obtained solution of the amidine oligomer (B) was added to 2 L of 1 mol / L hydrochloric acid, and the precipitate was recovered. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid, and the precipitate was recovered. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid, and the precipitate was recovered. The obtained precipitate was heated at 180 ° C. for 2 hours, and then heated at 300 ° C. for 2 hours to perform a reaction, thereby obtaining a fluorene imine oligomer F (醯Imidization rate 92%).

In addition, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer F contains the fluorene imine oligomer represented by the above formula (1-2) as a main component. In addition, GPC fractionation and FT-IR analysis confirmed that the content ratio of the fluorene imine oligomer having an ester bond to the fluorene imine oligomer F was 5.5%. The number-average molecular weight of the fluoreneimine oligomer F was 1,548.

(Synthesis example 7 (production of fluorene imine oligomer G))

Change the use amount of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene to 17.23 parts by weight and change the use amount of 3-aminophenol to 49.11 parts by weight, except Beyond that. In the same manner as in Synthesis Example 6, a fluorene imine oligomer G having a phenolic hydroxyl group (a fluorinated imidization rate of 93%) was obtained. The amount of the 3-aminophenol used was 1.5 equivalents based on the anhydride group of the sulfamic acid oligomer (A) to be reacted.

In addition, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer G has the fluorene imine oligomer represented by the above formula (1-2) as a main component. Furthermore, it was confirmed by GPC fractionation and FT-IR analysis that the content ratio of fluorene imine oligomer G having an ester bond to fluorene imine oligomer G was 5.4%. Furthermore, the number average molecular weight of the fluoreneimine oligomer G was 1126.

(Synthesis Example 8 (Production of fluorene imine oligomer H))

34.5 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene ("Bisaniline M" manufactured by MITSUI FINE CHEMICALS) was dissolved in N-methylpyrrolidone (and "NMP" manufactured by Kwangjon Pharmaceutical Co., Ltd.) in 200 mL. 104.1 parts by weight of 4,4 '-(4,4'-isopropylidene diphenoxy) bisphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, and the mixture was stirred at 25 ° C for 2 hours. Then, it was made to react, and the ammonium oligomer solution (A) was obtained. To the obtained amino acid oligomer solution (A), 32.74 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added (based on the anhydride group of the amino acid oligomer (A) to be reacted). (1.5 equivalents), stirred at 25 ° C for 2 hours, and reacted to obtain a phosphoric acid oligomer solution (B). A solution of the obtained ammonium oligomer (B) was added to 2 L of 1 mol / L hydrochloric acid, and the precipitate was recovered. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.5 mol / L hydrochloric acid, and the precipitate was recovered. The obtained precipitate was dissolved in 100 mL of N, N-dimethylformamide, and the obtained solution was added to 2 L of 0.1 mol / L hydrochloric acid, and the precipitate was recovered. The obtained precipitate was heated at 180 ° C. for 2 hours, and then heated at 300 ° C. for 2 hours to perform a reaction, thereby obtaining a fluorene imine oligomer H (醯Imidization rate 92%).

In addition, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer H has the fluorene imine oligomer represented by the above formula (1-2) as a main component. In addition, GPC fractionation and FT-IR analysis confirmed that the content of the fluorene imine oligomer H having an ester bond was 5.5%. The number average molecular weight of the fluoreneimine oligomer H was 2720.

(Synthesis example 9 (production of fluorene imine oligomer I))

34.45 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene was changed to 25.83 parts by weight of 2,2-bis (3-amino-4-hydroxyphenyl) propane Other than that, in the same manner as in Synthesis Example 6, a fluorene imine oligomer I having a phenolic hydroxyl group (a fluorinated imine rate of 93%) was obtained.

In addition, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer I contains the fluorene imine oligomer represented by the above formula (1-2) as a main component. In addition, GPC fractionation and FT-IR analysis confirmed that the content of the fluorene imine oligomer I having an ester bond in the fluorene imine oligomer I was 5.4%. Furthermore, the number average molecular weight of the fluoreneimine oligomer I was 1,490.

(Synthesis Example 10 (Production of fluorene imine oligomer J))

The use amount of 3-aminophenol was changed to 21.83 parts by weight (1 equivalent to the acid anhydride group of the 3,4'-oxybisphthalic dianhydride undergoing the reaction), except that the same amount was used as in Synthesis Example 1. A fluorene imine oligomer J having a phenolic hydroxyl group was obtained (93% of fluorene imine).

In addition, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer J contains the fluorene imine oligomer represented by the above formula (1-1) as a main component. In addition, GPC fractionation and FT-IR analysis confirmed that the content of the fluorene imine oligomer J having an ester bond was 8.2%. The number average molecular weight of the fluoreneimine oligomer J was 543.

(Synthesis Example 11 (Production of fluorene imine oligomer K))

The amidine imidation conditions of the precipitate were changed to a vacuum drying oven, and heated at 200 ° C and 5 mmHg for 3 hours. Except that the amidine imide oligomer K (amidation ratio 44) %).

By ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer K includes the fluorene imine oligomer represented by the above formula (1-1). In addition, by GPC fractionation and FT-IR analysis, it was confirmed that the content ratio of the fluorene imine oligomer K having an ester bond to the fluorene imine oligomer K was 8.2%. The number-average molecular weight of the fluoreneimine oligomer K was 556.

(Synthesis Example 12 (Production of fluorene imine oligomer L))

Except having changed the usage-amount of 3-aminophenol to 21.83 weight part, it carried out similarly to the synthesis example 6, and obtained the fluorene imide oligomer L which has a phenolic hydroxyl group (fluorene imidation rate 92%). The amount of 3-aminophenol used is 1 equivalent with respect to the anhydride group of the amido oligomer (A) to be reacted.

Furthermore, it was confirmed by ¹ H-NMR, GPC, and FT-IR analysis that the fluorene imine oligomer L had the fluorene imine oligomer represented by the above formula (1-2) as a main component. In addition, GPC fractionation and FT-IR analysis confirmed that the content ratio of the fluorene imine oligomer L having an ester bond to the fluorene imine oligomer L was 8.0%. The number-average molecular weight of the fluoreneimine oligomer L was 17,10.

(Synthesis example 13 (production of fluorene imine oligomer M))

Except having changed the use amount of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene to 17.23 weight part, it carried out similarly to the synthesis example 6, and obtained the fluorene which has a phenolic hydroxyl group Imine oligomer M (92% imidization). The amount of 3-aminophenol used is 1 equivalent with respect to the anhydride group of the amido oligomer (A) to be reacted.

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer M has the fluorene imine oligomer represented by the above formula (1-2) as a main component. In addition, by GPC fractionation and FT-IR analysis, it was confirmed that the content ratio of fluorene imine oligomer M having an ester bond to fluorene imine oligomer M was 8.1%. The number average molecular weight of the fluoreneimine oligomer M was 1241.

(Synthesis example 14 (production of fluorene imine oligomer N))

The used amount of 3-aminophenol was changed to 21.83 parts by weight (1 equivalent with respect to the acid anhydride group of the amido oligomer (A) to be reacted), except that the same as in Synthesis Example 9 was obtained. The fluorene imine oligomer N (94%).

In addition, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the fluorene imine oligomer N contains the fluorene imine oligomer represented by the above formula (1-2) as a main component. In addition, GPC fractionation and FT-IR analysis confirmed that the content ratio of the fluorene imine oligomer N having an ester bond to the fluorene imine oligomer N was 8.4%. The number-average molecular weight of the fluoreneimine oligomer N was 1,571.

(Examples 1 to 9, Comparative Examples 1 to 5)

Each material was stirred and mixed according to the blending ratios described in Tables 1 and 2 to prepare each of the adhesives of Examples 1 to 9 and Comparative Examples 1 to 5.

<Evaluation>

Each adhesive obtained in the examples and comparative examples was evaluated as follows. The results are shown in Tables 1 and 2.

(5% weight reduction temperature)

Each of the adhesives obtained in the examples and comparative examples was coated on a release film and dried to obtain a 25 μm-thick adhesive film.

The adhesive film obtained by curing the obtained adhesive film by heating it at 190 ° C for 1 hour uses a thermogravimetry device ("EXTEAR TG / DTA6200" manufactured by SII NanoTechnology) at a temperature of 40 ° C to 450 ° C. 5% weight reduction temperature was measured at a temperature range and a heating condition of 10 ° C / min.

(Long-term heat resistance (adhesion))

Kapton (registered trademark) having a thickness of 50 μm in the two-area layer of each of the adhesives obtained in the examples and comparative examples was cured by heating at 190 ° C. for 1 hour. Then, a short strip having a width of 1 cm was cut out. Get test strips. The obtained test piece was heat-treated at 175 ° C for 1000 hours. For the test piece after the heat treatment, a tensile tester ("UCT-500" manufactured by ORIENTEC Corporation) was used, and the adhesion was measured at a peeling speed of 20 mm / min.

A case where the adhesion force is 3.4 N / cm or more is set to "○", a case where it is less than 3.4 N / cm and is 2.4 N / cm or more is set to "△", and a case where the adhesion force is less than 2.4 N / cm is set to "×" to evaluate long-term heat resistance.

    Industrial availability    

According to the present invention, it is possible to provide a fluorene imine oligomer that can be used for a hardened product having excellent long-term heat resistance. Moreover, according to this invention, the hardening | curing agent which consists of this fluorene imine oligomer, and the adhesive agent using this hardening | curing agent can be provided. Furthermore, according to this invention, the manufacturing method of this fluorene imine oligomer can be provided.

Claims (6)

    A fluorene imine oligomer having a phenolic hydroxyl group is characterized in that the content ratio of the fluorene imine oligomer having an ester bond is 7% or less.         The fluorene imine oligomer according to claim 1, which has a number average molecular weight of 400 or more and 4,200 or less.         The fluorene imine oligomer according to claim 1 or 2 has a fluorene imine rate of 70% or more.         A hardener comprising a fluorene imine oligomer according to claim 1, 2 or 3.         An adhesive containing a curable resin and the curing agent according to claim 4.         A method for producing fluorene imine oligomers, comprising the step of reacting a compound having an acid anhydride group with a monoamine having a phenolic hydroxyl group, and the amount of use of the monoamine having a phenolic hydroxyl group relative to the above having an acid anhydride group The compound has an acid anhydride group of 1.5 equivalents or more.