KR20190140895A - Imide oligomers, curing agents, adhesives, and methods for producing imide oligomers - Google Patents

Abstract

An object of this invention is to provide the imide oligomer which can be used for the hardened | cured material excellent in long-term heat resistance. Moreover, an object of this invention is to provide the hardening agent which consists of this imide oligomer, and the adhesive agent using this hardening agent. Moreover, an object of this invention is to provide the manufacturing method of this imide oligomer. This invention is an imide oligomer which has a content rate of the imide oligomer which has an ester bond as 7% or less as an imide oligomer which has a phenolic hydroxyl group.

Description

Imide oligomers, curing agents, adhesives, and methods for producing imide oligomers

This invention relates to the imide oligomer which can be used for the hardened | cured material excellent in long-term heat resistance. Moreover, this invention relates to the hardening agent which consists of this imide oligomer, and the adhesive agent using this hardening agent. Moreover, this invention relates to the manufacturing method of this imide oligomer.

Curable resins, such as an epoxy resin with low shrinkage and excellent adhesiveness, insulation, and chemical resistance, are used for many industrial products. Especially in the electronic device use, the curable resin composition which obtains a favorable result in the solder reflow test regarding short-time heat resistance or the cold heat cycle test regarding repetitive heat resistance is used a lot.

In recent years, attention has been paid to on-vehicle electric control units (ECUs), power devices using SiC, GaN, and the like, but curable resin compositions used in these applications have been exposed to high temperatures continuously for a long period of time, rather than for a short time or repeated heat resistance. Heat resistance (long term heat resistance) at the time is required.

As a hardening | curing agent used for curable resin composition, although the imide oligomer hardening | curing agent which has the acid anhydride structure in both terminals is disclosed by patent document 1, since the compatibility with curable resins, such as an epoxy resin, is inadequate, the curable resin composition obtained There was a problem that the long-term heat resistance became inferior.

On the other hand, in patent documents 2 and 3, in order to improve compatibility with curable resin, curable resin composition which used the polyimide which introduce | transduced flexible silicone skeleton and alicyclic skeleton as a hardening | curing agent is disclosed. However, when the silicon skeleton and the alicyclic skeleton are introduced, the glass transition temperature of the cured product to be obtained tends to be lowered, resulting in inferior mechanical strength and long-term heat resistance at operating temperatures such as ECUs and power devices. In addition, Patent Document 4 discloses that by using a specific imide oligomer having a phenolic hydroxyl group or the like at both terminals as a curing agent, it is possible to improve the adhesiveness, heat resistance, and the like of the thermosetting resin composition, but using such an imide oligomer In some cases, the long-term heat resistance may be lowered.

Japanese Laid-Open Patent Publication No. 61-270852 Japanese Unexamined Patent Publication No. 2016-20437 Japanese Laid-Open Patent Publication 2012-227534 International Publication No. 2005/100433

An object of this invention is to provide the imide oligomer which can be used for the hardened | cured material excellent in long-term heat resistance. Moreover, an object of this invention is to provide the hardening agent which consists of this imide oligomer, and the adhesive agent using this hardening agent. Moreover, an object of this invention is to provide the manufacturing method of this imide oligomer.

This invention is an imide oligomer which has a content rate of the imide oligomer which has an ester bond as 7% or less as an imide oligomer which has a phenolic hydroxyl group.

The present invention is described in detail below.

The inventors of the present invention found that the one having an ester bond in the imide oligomer having a phenolic hydroxyl group lacks the effect of improving the long-term heat resistance of the cured product when used as a curing agent, and has an phenolic hydroxyl group and has no ester bond. The use of oligomers was examined. However, even when the imide oligomer which has a phenolic hydroxyl group and does not have an ester bond was used, the long-term heat resistance of hardened | cured material was not fully improved. The inventors of the present invention could not sufficiently improve the long-term heat resistance of the cured product because some of the imide oligomers having ester bonds as impurities were present in the imide oligomers having phenolic hydroxyl groups used as those having no ester bonds. Thought. Therefore, the present inventors earnestly examined and found that by using the imide oligomer which has phenolic hydroxyl group which made the content rate of the imide oligomer which has an ester bond which is an impurity 7% or less, the hardened | cured material excellent in long-term heat resistance can be obtained. It was found out and completed this invention.

The imide oligomer of this invention has a phenolic hydroxyl group.

In the imide oligomer of this invention, the content rate of the imide oligomer which has an ester bond is 7% or less. When the content rate of the imide oligomer which has the said ester bond is 7% or less, the imide oligomer of this invention becomes excellent in the effect which improves the long-term heat resistance of the hardened | cured material obtained when used as a hardening | curing agent. It is preferable that the content rate of the imide oligomer which has the said ester bond is 5% or less, and it is most preferable that it is 0%, ie, it does not contain the imide oligomer which has the said ester bond.

In addition, since the content rate of the imide oligomer which has the said ester bond collects each peak using a gel permeation chromatography (GPC), absorption derived from an ester bond by Fourier transform infrared spectroscopy (FT-IR) It can obtain | require from the weight ratio of the compound which has. Specifically, first, recycle preparative HPLC (made by Nihon Analysis Industry Co., Ltd.) equipped with a GPC column (for example, Nippon Analysis Industry Co., Ltd., "JAIGEL-2H", etc.) using tetrahydrofuran (THF) as a glass liquid. Aliquot each peak using. Then, the compound obtained by removing a glass liquid by heating etc. is measured by the total reflection measurement method (ATR method) using a Fourier transform infrared spectrophotometer (for example, "UMA600" by Agilent Technologies). From the obtained measurement result, it can derive by calculating | requiring the weight ratio with respect to all the peak compounds of the weight of the compound which has the peak (1159 cm <^-1> ) derived from ester bond.

It is preferable to have a phenolic hydroxyl group in the terminal of a principal chain from a viewpoint of the long-term heat resistance of the hardened | cured material obtained, and, as for the imide oligomer of this invention, it is more preferable to have it in both terminals.

The minimum with preferable preferable number average molecular weight of the imide oligomer of this invention is 400, and a preferable upper limit is 4200. When the said number average molecular weight is this range, the hardened | cured material obtained when the imide oligomer of this invention is used as a hardening | curing agent becomes what is excellent in long-term heat resistance. The minimum with more preferable number average molecular weight of the imide oligomer of this invention is 420, and a more preferable upper limit is 4000.

In addition, in this specification, said "number average molecular weight" is the value measured using tetrahydrofuran as a solvent in gel permeation chromatography (GPC), and is calculated | required by polystyrene conversion. As a column used when measuring the number average molecular weight by polystyrene conversion by GPC, JAIGEL-2H-A (made by Nippon Analysis Co., Ltd.) etc. is mentioned, for example.

Specifically, it is preferable that the imide oligomer of this invention contains the imide oligomer represented by following formula (1-1) and / or the imide oligomer represented by following formula (1-2) as a main component.

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

[Formula 1]

In formulas (1-1) and (1-2), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group which may be substituted, and X represents a bond, an oxygen atom, Or a divalent hydrocarbon group which may be substituted, and in Formula (1-2), Y is a bond, an oxygen atom, or a divalent hydrocarbon group which may be substituted.

As a method of manufacturing the imide oligomer of this invention, the method of making the quantity of the monoamine which has a phenolic hydroxyl group used as a raw material into an excess amount preferable is used.

Preparation of the imide oligomer which has the process of making the compound which has an acid anhydride group, and the monoamine which has a phenolic hydroxyl group react, and the usage-amount of the monoamine which has the said phenolic hydroxyl group is 1.5 equivalent or more with respect to the acid anhydride group of the compound which has the said acid anhydride group. The method is also one of the present inventions. According to the manufacturing method of the imide oligomer of this invention, the imide oligomer of this invention which made 7% or less of the content rate of the imide oligomer which has an ester bond which arises as a by-product can be manufactured easily.

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

First, the monoamine having a phenolic hydroxyl group is previously dissolved in a solvent (eg, N, N-dimethylformamide, etc.) in which the amic acid oligomer obtained by the reaction is soluble, and an acid dianhydride is added to the obtained solution. Reaction gives an amic acid oligomer solution. Next, the obtained amic acid oligomer solution is added to hydrochloric acid or the like, and the operation of recovering the precipitate is performed several times. The imide oligomer which has phenolic hydroxyl group can be obtained by heating the obtained precipitate and advancing imidation reaction. When using this method, the content rate of the imide oligomer which has an ester bond can be made into 7% or less by making the usage-amount of the monoamine which has the said phenolic hydroxyl group into 1.5 equivalent or more with respect to the acid anhydride group which the said acid dianhydride has. Can be.

Moreover, the other specific example of the manufacturing method of the imide oligomer of this invention is shown below.

First, diamine is previously dissolved in a solvent in which the amic acid oligomer obtained by the reaction is an soluble solvent (for example, N, N-dimethylformamide, etc.), and an acid dianhydride is added to the resulting solution to react with each other. The solution of the amic acid oligomer (A) which has an acid anhydride group is obtained. A monoamine having a phenolic hydroxyl group is added to the solution of the obtained amic acid oligomer (A) and reacted to obtain a solution of the amic acid oligomer (B). Next, the solution of the obtained amic-acid oligomer (B) is added to hydrochloric acid etc., and the operation which collect | recovers a precipitate is performed several times. The imide oligomer which has phenolic hydroxyl group can be obtained by heating the obtained precipitate and advancing imidation reaction. When using this method, the content rate of the imide oligomer which has an ester bond is 7% by making the usage-amount of the monoamine which has the said phenolic hydroxyl group into 1.5 equivalent or more with respect to the acid anhydride group of the said amic acid oligomer (A). It can be set as follows.

As a monoamine which has the said phenolic hydroxyl group, the compound represented by following formula (2) is used preferably.

As monoamine which has the said phenolic hydroxyl group, Specifically, 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-amino-2-naphthol, 6-amino- 1-naphthol, 4-amino-2, 6- diphenyl phenol, etc. are mentioned. Among them, 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, and 5-amino-o-cresol are excellent in availability and storage stability, and a cured product having a high glass transition temperature is obtained. This is preferred.

[Formula 2]

In Formula (2), Ar is a bivalent aromatic group which may be substituted, and R <^3> and R <^4> is a hydrogen atom or the monovalent hydrocarbon group which may be substituted each independently.

As said acid dianhydride, the compound represented by following formula (3) is used preferably.

Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3'-oxydiphthalic dianhydride, 3,4'-oxydiphthalic dianhydride, and 4,4'-oxydiphthalic acid. Dianhydrides, 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 4,4'-bis (3,4-dicarboxylphenoxy) diphenylether, p-phenylene Bis (trimelitate anhydride), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4 ' Carbonyl diphthalic dianhydride etc. are mentioned. Among them, 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride, 3,4'-oxydiphthalic dianhydride, 4,4 in terms of excellent solubility, heat resistance and availability Preferred are '-oxydiphthalic dianhydride and 4,4'-carbonyldiphthalic dianhydride.

[Formula 3]

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

[Formula 4]

In Formulas (4-1) and (4-2), * is a bond position, and in Formula (4-1), Z may be a bond, an oxygen atom, a carbonyl group, or may be substituted, and at a bond position. It is a bivalent hydrocarbon group which may have an oxygen atom. The hydrogen atom of the aromatic ring in Formulas (4-1) and (4-2) may be substituted.

As said diamine, the compound represented by following formula (5) is used preferably.

Specific examples of the diamine include 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane and 3,3'- Diaminodiphenylether, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylene Diamine, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) Phenyl) sulfone, 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-aminophenoxy) 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- To 3,3'-dihydroxydiphenylmethane, 3,3'-diamino-4,4'-dihydroxydiphenyl Ter, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, bisaminophenylfluorene, bistoluidinefluorene, 4 , 4'-bis (4-aminophenoxy) biphenyl, 4,4'-diamino-3,3'-dihydroxydiphenylether, 3,3'-diamino-4,4'-dihydro Oxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-bis (4 -Aminobenzamide) -3,3'- dihydroxybiphenyl, 4,4'-bis (3-aminobenzamide) -3,3'- dihydroxybiphenyl, etc. are mentioned. Among them, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenediamine, 1,3-phenylene in view of excellent solubility, heat resistance and availability. Diamine, 1,4-phenylenediamine, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 1,3-bis (2- (4 -Aminophenyl) -2-propyl) benzene and 1,4-bis (2- (4-aminophenyl) -2-propyl) benzene are preferred.

[Formula 5]

In Formula (5), B is a bivalent group represented by following formula (6-1) or following formula (6-2), and R <^5> -R <^8> is a hydrogen atom or a monovalent hydrocarbon group each independently.

[Formula 6]

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

The minimum with preferable imidation ratio of the imide oligomer of this invention is 70%. When the said imidation ratio is 70% or more, when using as a hardening | curing agent, the hardened | cured material excellent in the mechanical strength and long-term heat resistance at high temperature can be obtained. The minimum with said more preferable imidation ratio is 75%, and a more preferable minimum is 80%. There is no particular upper limit for the imidation ratio of the imide oligomer of the present invention, but the upper practical limit is 98%.

In addition, said "imidation ratio" can be calculated | required by Fourier transform infrared spectroscopy (FT-IR). Specifically, a Fourier transform infrared spectrophotometer 1660 ㎝ to perform the measurement by the total reflection measuring method (ATR method) by using the (for example, Agilent Technologies Co., Ltd., "UMA600", etc.), derived from the amic acid group ^{- From} the peak absorbance area of ¹ vicinity, it can derive by a following formula. In addition, "the peak absorbance area of an amic acid oligomer" in a following formula reacts the solvent by evaporation, without performing an imidation process, after making the compound which has an acid anhydride group, and the monoamine which has a phenolic hydroxyl group react. It is the absorbance area of the amic acid oligomer obtained by removing.

Imidation ratio (%) = 100 x (1-(peak absorbance area after imidization) / (peak absorbance area of amic acid oligomer))

As mentioned above, when the imide oligomer of this invention is used as a hardening | curing agent, the hardened | cured material excellent in long-term heat resistance can be obtained. The hardening agent which consists of the imide oligomer of this invention is also one of this invention. Moreover, the adhesive agent containing curable resin and the hardening | curing agent of this invention is also one of this invention.

As for content of the hardening | curing agent of this invention in the adhesive agent of this invention, a preferable minimum is 50 weight part and a preferable upper limit is 500 weight part with respect to 100 weight part of curable resin. When content of the hardening | curing agent of this invention is this range, the hardened | cured material of the adhesive agent obtained becomes more excellent in long-term heat resistance. The minimum with more preferable content of the hardening | curing agent of this invention is 70 weight part, and a more preferable upper limit is 400 weight part.

The adhesive of this invention may contain another hardening | curing agent in addition to the hardening | curing agent of this invention in the range which does not impair the objective of this invention, etc. in order to improve workability in an uncured state.

As said other hardening | curing agent, a phenol type hardening | curing agent, a thiol type hardening | curing agent, an amine hardening | curing agent, an acid anhydride type hardening | curing agent, a cyanate type hardening | curing agent, an active ester type hardening | curing agent, etc. are mentioned, for example. Especially, a phenol type hardening | curing agent, an acid anhydride type hardening | curing agent, a cyanate type hardening | curing agent, and an active ester type hardening | curing agent are preferable.

When the adhesive agent of this invention contains the said other hardening | curing agent, the preferable upper limit of the content rate of the said other hardening | curing agent in the whole hardening | curing agent is 70 weight%, a more preferable upper limit is 50 weight%, and a still more preferable upper limit is 30 weight%.

The adhesive agent of this invention contains curable resin.

It is preferable that the said curable resin is liquid at 25 degreeC from the viewpoint of the fluidity | liquidity and processability of the adhesive agent obtained.

As said curable resin, an epoxy resin is used preferably.

Examples of the epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol E type epoxy resins, bisphenol S type epoxy resins, 2,2'-diallyl bisphenol A type epoxy resins, and hydrogenated bisphenols. Type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin , Fluorene type epoxy resin, naphthylene ether type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, naphthalene phenol furnace Volac type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, rubber modified epoxy Resins, glycidyl ester compounds, and the like. Especially, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, and a resorcinol-type epoxy resin are preferable at the point which is low in viscosity and easy to adjust the workability in room temperature of the adhesive agent obtained.

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

As said hardening accelerator, an imidazole series hardening accelerator, a tertiary amine hardening accelerator, a phosphine type hardening accelerator, a photobase generator, a sulfonium salt type hardening accelerator, etc. are mentioned, for example. Especially, an imidazole series hardening accelerator is preferable.

As for content of the said hardening accelerator, a preferable minimum is 0.01 weight part and a preferable upper limit is 10 weight part with respect to 100 weight part of said curable resins. When content of the said hardening accelerator is this range, the effect which shortens hardening time becomes more excellent, maintaining the outstanding adhesiveness etc .. The minimum with more preferable content of the said hardening accelerator is 0.05 weight part, and a more preferable upper limit is 5 weight part.

The adhesive agent of this invention may contain an organic filler for the purpose of stress relaxation, toughness provision, flame retardance provision, etc.

Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, and core shell particles thereof. have. Especially, polyamide particle, polyamideimide particle, and polyimide particle are preferable.

As for content of the said organic filler, a preferable minimum is 10 weight part and a preferable upper limit is 500 weight part with respect to 100 weight part of said curable resins. When content of the said organic filler is this range, the hardened | cured material obtained will become more excellent in toughness etc., maintaining the outstanding adhesiveness etc .. The minimum with more preferable content of the said organic filler is 30 weight part, and a more preferable upper limit is 400 weight part.

The adhesive agent of this invention may contain an inorganic filler for the purpose of reducing the linear expansion rate after hardening, reducing curvature, giving a flame retardance, or improving adhesive reliability.

As the inorganic filler, for example, silica such as colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, aluminum hydroxide, magnesium hydroxide, glass powder, glass frit, glass fiber, carbon fiber, inorganic ion exchanger, etc. Can be mentioned.

As for content of the said inorganic filler, a preferable minimum is 10 weight part and a preferable upper limit is 1000 weight part with respect to 100 weight part of said curable resins. When content of the said inorganic filler is this range, the effect of improving adhesive reliability etc. will become more excellent, maintaining the outstanding workability etc .. The minimum with more preferable content of the said inorganic filler is 20 weight part, and a more preferable upper limit is 900 weight part.

Moreover, an inorganic filler can also be used as a flow regulator for the purpose of improving the coating property and shape retention property by a short time with respect to a to-be-adhered body.

Inorganic fillers used as flow regulators include, for example, fumed silica, layered silicates, and the like.

As for content of the inorganic filler used as the said flow regulator, a preferable minimum is 0.1 weight part and a preferable upper limit is 50 weight part with respect to 100 weight part of said curable resins. When content of the inorganic filler used as the said flow regulator is this range, the effect, such as improving the coating property and shape retention by a short time with respect to a to-be-adhered body, becomes more excellent. The minimum with more preferable content of the inorganic filler used as the said flow regulator is 0.5 weight part, and a more preferable upper limit is 30 weight part.

The adhesive agent of this invention may contain a high molecular compound in the range which does not impair the objective of this invention. The said high molecular compound plays a role as a film forming component.

The said high molecular compound may have a reactive functional group.

As said reactive functional group, an amino group, a urethane group, an imide group, a hydroxyl group, a carboxyl group, an epoxy group, etc. are mentioned, for example.

Moreover, the said high molecular compound may form a phase separation structure in hardened | cured material, and does not need to form a phase separation structure. In the case where the polymer compound does not form a phase-separated structure in the cured product, the polymer compound is preferably a polymer compound having an epoxy group as the reactive functional group because of its superior mechanical strength, long-term heat resistance, and moisture resistance at high temperatures. .

The adhesive agent of this invention may contain a reactive diluent in the range which does not impair the objective of this invention.

As said reactive diluent, the reactive diluent which has a 2 or more reactive functional group in 1 molecule from a viewpoint of adhesive reliability is preferable.

As a reactive functional group which the said reactive diluent has, the thing similar to the reactive functional group which the high molecular compound mentioned above 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-bleeding agent, a flux agent and a liquid flame retardant.

As a method of manufacturing the adhesive of the present invention, for example, using a mixer such as a homo disper, a universal mixer, a Banbury mixer, a kneader, the curable resin, the curing agent of the present invention, and another curing agent added as necessary The method of mixing a hardening accelerator, etc. are mentioned.

Moreover, the adhesive film which consists of an adhesive agent of this invention can be obtained by coating the adhesive agent of this invention on a release film, and drying.

Although the adhesive agent of this invention can be used for a wide use, it can be used suitably for the electronic material use especially where high heat resistance is calculated | required. For example, it can be used for the die attach agent etc. in the aviation, on-vehicle electric control unit (ECU) use, and the power device use using SiC, GaN. Moreover, it can be used also for adhesives for power overlay packages, adhesives for printed wiring boards, adhesives for coverlays of flexible printed circuit boards, adhesives for semiconductor bonding, adhesives for structural materials, and the like. Moreover, in addition to adhesive use, it can be used as a curable composition, for example, a sealing agent, a copper clad laminated board, an adhesive agent for semiconductor joining, an interlayer insulation film, a prepreg, etc.

According to this invention, the imide oligomer which can be used for the hardened | cured material excellent in long-term heat resistance can be provided. Moreover, according to this invention, the hardening agent which consists of this imide oligomer, and the adhesive agent using this hardening agent can be provided. Moreover, according to this invention, the manufacturing method of this imide oligomer can be provided.

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited only to these Examples.

Synthesis Example 1 (Preparation of Imide Oligomer A)

32.74 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (1.5 equivalents relative to the acid anhydride group of the reacted 3,4'-oxydiphthalic dianhydride) was dissolved in 200 ml of N, N-dimethylformamide. 31.0 weight part of 3,4'- oxydiphthalic dianhydride (made by Tokyo Chemical Industry Co., Ltd.) was added to the obtained solution, it stirred at 25 degreeC for 2 hours, and it reacted, and obtained the amic acid oligomer solution. The obtained amic acid oligomer solution was added to 2 L of 1 mol / L hydrochloric acid, and the precipitate was collect | 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 to recover the precipitate. 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 to recover the precipitate. The obtained precipitate was heated at 180 ° C. for 2 hours, and then reacted under imidization conditions heated at 300 ° C. for 2 hours to obtain imide oligomer A (94% of imidization ratio) having a phenolic hydroxyl group.

In addition, the imide oligomer A confirmed that the imide oligomer represented by the said Formula (1-1) has a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer A confirmed that the content rate of the imide oligomer which has an ester bond is 5.5%. In addition, the number average molecular weight of imide oligomer A was 506.

Synthesis Example 2 (Preparation of Imide Oligomer B)

Imide oligomer B having an phenolic hydroxyl group (imidation rate) in the same manner as in Synthesis Example 1 except that the imidization conditions of the precipitates were changed by heating at 200 ° C and 5 mmHg for 3 hours using a vacuum drying oven. 46%) was obtained.

The imide oligomer B confirmed that the imide oligomer represented by said Formula (1-1) was confirmed by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer B confirmed that the content rate of the imide oligomer which has an ester bond is 5.5%. In addition, the number average molecular weight of imide oligomer B was 510.

Synthesis Example 3 (Preparation of Imide Oligomer C)

Imide which has a phenolic hydroxyl group similarly to the synthesis example 1 except having changed the usage-amount of 3-aminophenol into 65.48 weight part (3 equivalent with respect to the acid anhydride group of 3,4'- oxydiphthalic dianhydride reacted). Oligomer C (94% of imidation ratio) was obtained.

In addition, the imide oligomer C confirmed that the imide oligomer represented by said Formula (1-1) has a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer C confirmed that the content rate of the imide oligomer which has an ester bond is 4.7%. In addition, the number average molecular weight of imide oligomer C was 506.

Synthesis Example 4 (Preparation of Imide Oligomer D)

Synthesis except that 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.) (1.5 equivalents based on the acid anhydride group of the reacted 3,4'-oxydiphthalic dianhydride) In the same manner as in Example 1, an imide oligomer D (94% of imidization ratio) having a phenolic hydroxyl group was obtained.

In addition, the imide oligomer D confirmed that the imide oligomer represented by said Formula (1-1) has a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer D confirmed that the content rate of the imide oligomer which has an ester bond is 5.3%. In addition, the number average molecular weight of imide oligomer D was 531.

Synthesis Example 5 (Preparation of Imide Oligomer E)

Instead of 31.0 parts by weight of 3,4'-oxydiphthalic dianhydride, 52.0 parts by weight of 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. In the same manner as in Synthesis example 1, imide oligomer E (93% of imidation ratio) which has a phenolic hydroxyl group was obtained. The usage-amount of 3-aminophenol is 1.5 equivalent with respect to the acid anhydride group of the 4,4 '-(4,4'-isopropylidene diphenoxy) diphthalic anhydride made to react.

In addition, the imide oligomer E confirmed that the imide oligomer represented by said Formula (1-1) has a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer E confirmed that the content rate of the imide oligomer which has an ester bond is 5.4%. In addition, the number average molecular weight of imide oligomer E was 712.

Synthesis Example 6 (Preparation of Imide Oligomer F)

34.45 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene ("Bisaniline M" manufactured by Mitsui Chemical Fine Co., Ltd.) was dissolved in 200 ml of N, N-dimethylformamide. To the obtained solution, 104.1 parts by weight of 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred at 25 ° C for 2 hours to react, resulting in acid anhydrides at both ends. The solution of the amic acid oligomer (A) which has group was obtained. 32.74 parts by weight (1.5 equivalents to the acid anhydride group of the amic acid oligomer (A) to be reacted) is added to the solution of the obtained amic acid oligomer (A) and stirred at 25 ° C. for 2 hours. And the solution of the amic acid oligomer (B) was obtained. The solution of the obtained amic acid oligomer (B) was added to 2 L of 1 mol / L hydrochloric acid, and the precipitate was collect | 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 to recover the precipitate. 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 to recover the precipitate. The obtained precipitate was heated at 180 ° C. for 2 hours, and then reacted under imidization conditions heated at 300 ° C. for 2 hours to obtain imide oligomer F (92% of imidization ratio) having a phenolic hydroxyl group.

In addition, the imide oligomer F confirmed that the imide oligomer represented by the said Formula (1-2) is a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer F confirmed that the content rate of the imide oligomer which has an ester bond is 5.5%. In addition, the number average molecular weight of imide oligomer F was 1548.

Synthesis Example 7 (Preparation of Imide Oligomer G)

As in Synthesis Example 6, the amount of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene was changed to 17.23 parts by weight and the amount of 3-aminophenol was changed to 49.11 parts by weight. And imide oligomer G (93% of imidation ratio) which has phenolic hydroxyl group was obtained. The usage-amount of 3-aminophenol is 1.5 equivalent with respect to the acid anhydride group of the amic-acid oligomer (A) made to react.

In addition, the imide oligomer G confirmed that the imide oligomer represented by said Formula (1-2) is a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer G confirmed that the content rate of the imide oligomer which has an ester bond is 5.4%. In addition, the number average molecular weight of imide oligomer G was 1126.

Synthesis Example 8 (Preparation of Imide Oligomer H)

34.5 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene (made by Mitsui Chemical Fine, "bisaniline M") N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd., "NMP Was dissolved in 200 ml. To the obtained solution, 104.1 parts by weight of 4,4 '-(4,4'-isopropylidenediphenoxy) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirred at 25 ° C for 2 hours for reaction to react with an amic acid oligomer solution ( A) was obtained. To the obtained amic acid oligomer solution (A), 32.74 parts by weight (1.5 equivalents to the acid anhydride group of the amic acid oligomer (A) to be reacted) was further added thereto at 25 ° C. It stirred for time and made it react, and obtained the amic acid oligomer solution (B). The solution of the obtained amic acid oligomer (B) was added to 2 L of 1 mol / L hydrochloric acid, and the precipitate was collect | 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 to recover the precipitate. 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 to recover the precipitate. About the obtained precipitate, after heating at 180 degreeC for 2 hours, the imide oligomer H (92% of imidation ratio) which has phenolic hydroxyl group was obtained by making it react on imidation conditions heated at 300 degreeC for 2 hours.

In addition, the imide oligomer H confirmed that the imide oligomer represented by said Formula (1-2) is a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer H confirmed that the content rate of the imide oligomer which has an ester bond is 5.5%. In addition, the number average molecular weight of imide oligomer H was 2720.

Synthesis Example 9 (Preparation of Imide Oligomer I)

Synthesis example except for changing 34.45 parts by weight of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene to 25.83 parts by weight of 2,2-bis (3-amino-4-hydroxyphenyl) propane In the same manner as in 6, imide oligomer I (imidization ratio 93%) having a phenolic hydroxyl group was obtained.

In addition, the imide oligomer I confirmed that the imide oligomer represented by said Formula (1-2) is a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer I confirmed that the content rate of the imide oligomer which has an ester bond is 5.4%. In addition, the number average molecular weight of imide oligomer I was 1490.

Synthesis Example 10 (Preparation of Imide Oligomer J)

Imide which has a phenolic hydroxyl group similarly to the synthesis example 1 except having changed the usage-amount of 3-aminophenol into 21.83 weight part (1 equivalent with respect to the acid anhydride group of 3,4'- oxydiphthalic dianhydride to react). Oligomer J (93% of imidation ratio) was obtained.

In addition, the imide oligomer J confirmed that the imide oligomer represented by said Formula (1-1) has a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, imide oligomer J confirmed that the content rate of the imide oligomer which has an ester bond is 8.2% by GPC fractionation and FT-IR analysis. In addition, the number average molecular weight of imide oligomer J was 543.

Synthesis Example 11 (Preparation of Imide Oligomer K)

The imide oligomer K (imidization ratio 44%) was obtained like Example 10 except having changed the imidation conditions of the precipitate by heating at 200 degreeC and 5 mmHg for 3 hours using a vacuum drying oven. .

The imide oligomer K confirmed that the imide oligomer represented by said formula (1-1) was confirmed by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer K confirmed that the content rate of the imide oligomer which has an ester bond is 8.2%. In addition, the number average molecular weight of imide oligomer K was 556.

Synthesis Example 12 (Preparation of Imide 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 imide oligomer L (92% of imidation ratio) which has a phenolic hydroxyl group. The usage-amount of 3-aminophenol is 1 equivalent with respect to the acid anhydride group of the amic-acid oligomer (A) made to react.

In addition, the imide oligomer L confirmed that the imide oligomer represented by said Formula (1-2) is a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, the GPC fractionation and FT-IR analysis confirmed that the imide oligomer L content rate of the imide oligomer which has an ester bond is 8.0%. In addition, the number average molecular weight of imide oligomer L was 1710.

Synthesis Example 13 (Preparation of Imide Oligomer M)

Imide oligomer M (imide) having a phenolic hydroxyl group in the same manner as in Synthesis Example 6 except that the amount of 1,3-bis (2- (4-aminophenyl) -2-propyl) benzene was changed to 17.23 parts by weight. Yield 92%) was obtained. The usage-amount of 3-aminophenol is 1 equivalent with respect to the acid anhydride group of the amic-acid oligomer (A) made to react.

In addition, the imide oligomer M confirmed that it has the imide oligomer represented by said Formula (1-2) as a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, by GPC fractionation and FT-IR analysis, the imide oligomer M confirmed that the content rate of the imide oligomer which has an ester bond is 8.1%. In addition, the number average molecular weight of imide oligomer M was 1241.

Synthesis Example 14 (Preparation of Imide Oligomer N)

The imide oligomer N which has a phenolic hydroxyl group similarly to the synthesis example 9 except having changed the usage-amount of 3-aminophenol into 21.83 weight part (1 equivalent with respect to the acid anhydride group of the reacting amic acid oligomer (A)). Imidation ratio 94%) was obtained.

In addition, imide oligomer N confirmed that the imide oligomer represented by said Formula (1-2) is a main component by <^1> H-NMR, GPC, and FT-IR analysis. Moreover, GPC fractionation and FT-IR analysis confirmed that the imide oligomer N content ratio of the imide oligomer which has an ester bond is 8.4%. In addition, the number average molecular weight of imide oligomer N was 1571.

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

According to the mixing | blending ratio of Table 1, 2, each material was stirred and mixed, and each adhesive agent of Examples 1-9 and Comparative Examples 1-5 was manufactured.

<Evaluation>

The following evaluation was performed about each adhesive agent obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(5% weight loss temperature)

Each adhesive obtained by the Example and the comparative example was coated on the release film, and it dried and the adhesive film of 25 micrometers thickness was obtained.

About the adhesive film which hardened | cured by heating the obtained adhesive film at 190 degreeC for 1 hour, the temperature of 40 degreeC-450 degreeC using a thermogravimetric measuring apparatus (Sai Ai Nano Technology company make, "EXTEAR TG / DTA6200"). 5% weight loss temperature was measured on the conditions of the temperature of 10 degreeC / min in the range.

(Long-term heat resistance (adhesion))

50 micrometers thick kapton (trademark) was laminated on both surfaces of each adhesive obtained by the Example and the comparative example, and it hardened | cured and adhere | attached by heating at 190 degreeC for 1 hour, and afterwards, it turned out to be 1 cm wide single stripe. The test piece was cut out and obtained. The obtained test piece was heat-treated at 175 ° C. for 1000 hours. About the test piece after heat processing, the adhesive force was measured on the conditions of 20 mm / min of peeling rate using the tensile tester ("UCT-500" by Orientec company).

Long-term heat resistance was evaluated as "(circle)" and the case where it was less than 2.4N / cm as "(circle)" and the case where it was less than 2.4N / cm as "(circle)" when the adhesive force was 3.4N / cm or more was evaluated as "x".

Industrial availability

According to this invention, the imide oligomer which can be used for the hardened | cured material excellent in long-term heat resistance can be provided. Moreover, according to this invention, the hardening agent which consists of this imide oligomer, and the adhesive agent using this hardening agent can be provided. Moreover, according to this invention, the manufacturing method of this imide oligomer can be provided.

Claims (6)

As an imide oligomer which has a phenolic hydroxyl group,
The content rate of the imide oligomer which has an ester bond is 7% or less, The imide oligomer characterized by the above-mentioned. The method of claim 1,
The number average molecular weight is 400 or more and 4200 or less, The imide oligomer characterized by the above-mentioned. The method according to claim 1 or 2,
Imide oligomer whose imidation ratio is 70% or more. The hardening | curing agent which consists of the imide oligomer of Claim 1, 2 or 3. An adhesive comprising curable resin and the curing agent according to claim 4. It has a process of making the compound which has an acid anhydride group, and the monoamine which has a phenolic hydroxyl group react,
The usage-amount of the monoamine which has the said phenolic hydroxyl group is 1.5 equivalent or more with respect to the acid anhydride group of the compound which has the said acid anhydride group, The manufacturing method of the imide oligomer characterized by the above-mentioned.