TWI770178B - Curable resin composition, cured product, adhesive, adhesive film, coverlay, and printed wiring board - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition which is excellent in flow properties before curing, and which is excellent in adhesiveness, heat resistance, and bending resistance after curing. Moreover, the objective of this invention is to provide the hardened|cured material of this curable resin composition, and the adhesive agent, adhesive film, coverlay film and printed wiring board using this curable resin composition.

The curable resin composition of the present invention contains a thermosetting resin, a thermoplastic resin, and an imine oligomer, and the above-mentioned imine oligomer has a reactive functional group capable of reacting with the above-mentioned thermosetting resin.

Description

Curable resin composition, cured product, adhesive, adhesive film, coverlay, and printed wiring board

The present invention relates to a curable resin composition which is excellent in flow characteristics before curing and excellent in adhesiveness, heat resistance and bending resistance after curing. Moreover, this invention relates to the hardened|cured material of this curable resin composition, and the adhesive agent, adhesive film, coverlay film and printed wiring board using this curable resin composition.

Moreover, this invention is related with the curable resin composition which is excellent in storage stability, and can obtain the hardened|cured material excellent in low linear expansion property, adhesiveness, and long-term heat resistance. Moreover, this invention relates to the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition.

Furthermore, the present invention relates to a curable resin composition excellent in flexibility and workability before curing, and excellent in adhesiveness and heat resistance after curing. Moreover, this invention relates to the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition.

A flexible printed wiring board (FPC) generally has a structure in which copper foil or the like is bonded to one side or both sides of an insulating film such as a polyimide film via an adhesive layer. For the adhesive used in the adhesive layer of the flexible printed wiring board, it is required to have both sufficient filling properties (embedding of concavities and convexities) and excellent flow properties of anti-bleeding properties during thermocompression bonding. As such adhesives, for example, Patent Documents 1 to 3 disclose that a thermosetting component such as an epoxy resin, a thermoplastic resin such as an acrylic resin, a polyamide, and a polyester, and a flexible component such as acrylonitrile butadiene rubber are included. The curable resin composition.

On the other hand, with the recent expansion of applications in automotive applications, etc., adhesives are required to have long-term heat resistance. However, the adhesives using the curable resin compositions disclosed in Patent Documents 1 to 3 are insufficient in heat resistance.

Patent Document 4 discloses an adhesive containing a soluble polyester, a phenoxy resin, and an imidesiloxane oligomer as an adhesive excellent in heat resistance. However, the adhesive disclosed in Patent Document 4 has poor flow properties, and it is difficult to have both filling properties and anti-bleeding properties.

Curable resins such as epoxy resins that have low shrinkage and are excellent in adhesion, insulation, and chemical resistance are used in many industrial products. In particular, for use in electronic equipment, a curable resin composition that obtains good results in a reflow test for short-term heat resistance or a cooling-heat cycle test for repeated heat resistance is often used.

In recent years, in-vehicle electronic control units (ECUs) and power devices using SiC and GaN have attracted attention, and curable resin compositions used in these applications require not only short-term or repeated heat resistance, but also continuous Heat resistance when exposed to high temperature for a long time (long-term heat resistance).

Patent Document 5 discloses that by using a specific imide oligomer having a phenolic hydroxyl group or an amino group at the terminal as a curing agent, the low thermal expansion property, heat resistance, etc. of a curable resin composition are improved. However, the curable resin composition disclosed in Patent Document 5 has problems such as poor storage stability, and excellent thermal decomposition resistance of the cured product but poor long-term heat resistance.

In addition, Patent Document 6 discloses a curable resin composition using an imide oligomer curing agent having an acid anhydride structure at both ends. However, the curable resin composition disclosed in Patent Document 6 has problems such as poor adhesion, and poor long-term heat resistance and low linear expansion properties of the cured product.

Moreover, for example, the above-mentioned patent document 6 or patent document 7 discloses a curable resin composition containing an epoxy resin and an imide oligomer as a curing agent. However, in general, imide oligomers are hard and brittle at room temperature. Therefore, the curable resin compositions disclosed in Patent Documents 6 and 7 have flexibility, processability, and fluidity at room temperature. etc. there are problems.

The above-mentioned Patent Document 5 discloses a curable resin composition containing a liquid epoxy resin and an imide oligomer having a specific reactive functional group as a curable resin composition with improved processability, fluidity, and the like. However, even the curable resin composition disclosed in Patent Document 5 has insufficient fluidity, and if the content ratio of the liquid epoxy resin is increased in order to further improve the fluidity, heat resistance or adhesiveness will occur. lowering problem.

樹脂之樹脂混合物中，而提高硬化前之硬化性樹脂組成物之可撓性的方法。然而，專利文獻8中所揭示之方法存在因腈橡膠成分而導致硬化物之耐熱性劣化之問題。 In addition, Patent Document 8 discloses that a nitrile rubber component is dispersed in an imide oligomer having a specific reactive functional group, an epoxy resin, and bismaleimide-tris

A method of improving the flexibility of a curable resin composition before curing in a resin mixture of resins. However, the method disclosed in Patent Document 8 has a problem that the heat resistance of the cured product is deteriorated due to the nitrile rubber component.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2006-232984

Patent Document 2: Japanese Patent Laid-Open No. 2009-167396

Patent Document 3: Japanese Patent Laid-Open No. 2008-308686

Patent Document 4: Japanese Patent Application Laid-Open No. 5-306386

Patent Document 5: Japanese Patent Laid-Open No. 2007-91799

Patent Document 6: Japanese Patent Laid-Open No. 61-270852

Patent Document 7: Japanese Patent Publication No. 2004-502859

Patent Document 8: Japanese Patent Application Laid-Open No. 7-224269

An object of the present invention is to provide a curable resin composition which is excellent in flow characteristics before curing and excellent in adhesiveness, heat resistance and bending resistance after curing. Moreover, the objective of this invention is to provide the hardened|cured material of this curable resin composition, and the adhesive agent, adhesive film, coverlay film and printed wiring board using this curable resin composition.

Moreover, the objective of this invention is to provide the curable resin composition which is excellent in storage stability, and can obtain the hardened|cured material excellent in low linear expansion property, adhesiveness, and long-term heat resistance. Moreover, the objective of this invention is to provide the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition.

Furthermore, the objective of this invention is to provide the curable resin composition which is excellent in flexibility and workability before hardening, and is excellent in adhesiveness and heat resistance after hardening. Moreover, the objective of this invention is to provide the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition.

The present invention 1 is a curable resin composition comprising a thermosetting resin, a thermoplastic resin and an imide oligomer, wherein the imine oligomer has a reactive functional group capable of reacting with the thermosetting resin .

The present invention 1 will be described in detail below.

The inventors of the present invention studied, in a curable resin composition containing a thermosetting resin, a thermoplastic resin, and an imide oligomer, to use, as the imide oligomer, a compound having a compound capable of reacting with the thermosetting resin. Imide oligomers with reactive functional groups. As a result, the inventors found that a curable resin composition excellent in flow characteristics before curing and excellent in adhesiveness, heat resistance, and bending resistance after curing can be obtained, thereby completing the present invention 1.

The curable resin composition of the present invention 1 contains a thermosetting resin.

As said thermosetting resin, an epoxy resin is used suitably.

As said epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'- diallyl are mentioned, for example. base bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, thioether ring Oxygen resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, stilbene type epoxy resin, naphthyl ether type epoxy resin, phenol novolak type epoxy resin, O-cresol novolak epoxy resin, dicyclopentadiene novolak epoxy resin, biphenyl novolac epoxy resin, naphthol novolak epoxy resin, glycidylamine epoxy resin, alkyl Polyol-type epoxy resins, rubber-modified epoxy resins, Phenol-type epoxy resins, glycidyl ester compounds, etc. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. E-type epoxy resin, resorcinol-type epoxy resin and other liquid epoxy resins at room temperature. The above epoxy resins may be used alone or in combination of two or more.

The preferable lower limit of the number average molecular weight of the above-mentioned thermosetting resin is 90, and the preferable upper limit is 3000. When the said number average molecular weight of the said thermosetting resin is this range, the adhesiveness and heat resistance of the curable resin composition obtained are more excellent. A more preferable lower limit of the number average molecular weight of the above-mentioned thermosetting resin is 100, and a more preferable upper limit is 2500.

In addition, in this specification, the said "number average molecular weight" is the value calculated|required in polystyrene conversion by measuring by gel permeation chromatography (GPC). As a column used for measuring the number average molecular weight in terms of polystyrene by GPC, for example, JAIGEL-2H-A (manufactured by Nippon Kagaku Kogyo Co., Ltd.) and the like can be mentioned.

The preferable lower limit of the content of the above-mentioned thermosetting resin in 100 parts by weight of the total of the thermosetting resin, the thermoplastic resin and the imide oligomer is 10 parts by weight, and the preferable upper limit is 90 parts by weight. When the content of the above-mentioned thermosetting resin is 10 parts by weight or more, the adhesiveness or heat resistance of the obtained curable resin composition is more excellent. When the content of the above-mentioned thermosetting resin is 90 parts by weight or less, the flow characteristics of the obtained curable resin composition are more excellent. A more preferable lower limit of the content of the above thermosetting resin is 20 parts by weight, and a more preferable upper limit is 80 parts by weight.

The curable resin composition of the present invention 1 contains a thermoplastic resin.

By using the above-mentioned thermoplastic resin, the curable resin composition of the present invention 1 is excellent in flow characteristics, easily has both filling properties and anti-bleeding properties during thermocompression bonding, and is excellent in bending resistance after curing.

As said thermoplastic resin, a phenoxy resin, a polyamide, an acrylic resin, polyester, etc. are mentioned. Among them, phenoxy resins and polyamides are preferable from the viewpoint of heat resistance, and phenoxy resins are more preferable from the viewpoints of anti-bleeding properties and workability during thermocompression bonding.

As said phenoxy resin, bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol E type phenoxy resin, bisphenol A-bisphenol F type phenoxy resin, for example are mentioned. , acetophenone-biphenyl type phenoxy resin, bisphenol S type phenoxy resin, phosphorus-containing phenoxy resin, trimethylcyclohexane skeleton phenoxy resin, bisphenol phenoxy resin, etc. . Among them, bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, and bisphenol A-bisphenol F type phenoxy resin are preferable.

The preferable lower limit of the weight average molecular weight of the thermoplastic resin is 3,000, and the preferable upper limit is 200,000. When the above-mentioned weight average molecular weight of the above-mentioned thermoplastic resin is in this range, the obtained curable resin composition is more excellent in the flow characteristics and the bending resistance after hardening. A more preferable lower limit of the weight-average molecular weight of the thermoplastic resin is 5,000, a more preferable upper limit is 150,000, and a further preferable upper limit is 100,000.

Furthermore, in the case of use in applications requiring a higher level of bending resistance, the preferable lower limit of the weight average molecular weight of the thermoplastic resin is 10,000.

In addition, in this specification, the said "weight average molecular weight" is the value calculated|required in polystyrene conversion by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. As a column used for measuring the weight average molecular weight in terms of polystyrene by GPC, for example, JAIGEL-2H-A (manufactured by Nippon Kagaku Kogyo Co., Ltd.) and the like can be mentioned.

The preferable lower limit of the content of the thermoplastic resin in the total of 100 parts by weight of the thermosetting resin, the thermoplastic resin and the imide oligomer is 1 part by weight, and the preferable upper limit is 60 parts by weight. When the content of the thermoplastic resin is 1 part by weight or more, the obtained curable resin composition is more excellent in flow properties and bending resistance after curing. When the content of the thermoplastic resin is 60 parts by weight or less, the obtained curable resin composition is more excellent in adhesiveness or heat resistance. A more preferable lower limit of the content of the above thermosetting resin is 3 parts by weight, and a more preferable upper limit is 50 parts by weight.

The curable resin composition of the present invention 1 contains an imide oligomer.

The above-mentioned imide oligomer has a reactive functional group capable of reacting with the above-mentioned thermosetting resin. By using an imide oligomer having a reactive functional group capable of reacting with the above-mentioned thermosetting resin, the curable resin composition of the present invention 1 not only maintains the effects of both filling and anti-bleeding properties during thermocompression bonding , and bending resistance after curing, and excellent adhesion and heat resistance after curing.

The reactive functional groups possessed by the above-mentioned imide oligomers vary depending on the type of the thermosetting resin used. In the case of using an epoxy resin as the thermosetting resin, acid anhydride groups and/or anhydride groups are preferred. or phenolic hydroxyl.

The above-mentioned imide oligomer preferably has the above-mentioned reactive functional group at the end of the main chain, more preferably at both ends.

As a method for producing an imide oligomer having an acid anhydride group as the above-mentioned reactive functional group, for example, an acid dianhydride represented by the following formula (1) and a diamine represented by the following formula (2) can be mentioned. reaction method, etc.

In addition, as a method for producing an imide oligomer having a phenolic hydroxyl group as the reactive functional group, for example, an acid dianhydride represented by the following formula (1) and an acid dianhydride represented by the following formula (3) can be mentioned. A method for reacting a phenolic hydroxyl group-containing monoamine, and the like. In addition, after reacting an acid dianhydride represented by the following formula (1) with a diamine represented by the following formula (2), and further reacting with a phenolic hydroxyl group-containing compound represented by the following formula (3) Methods of reacting monoamines, etc.

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

In the formula (2), B is a divalent group represented by the following formula (5-1) or the following formula (5-2), and R ¹ to R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group.

In formula (3), Ar is a divalent aromatic group which may be substituted, and R ⁵ and R ⁶ are each independently a hydrogen atom or a monovalent hydrocarbon group.

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

In formula (5-1) and formula (5-2), * is a bonding position, and in formula (5-1), Y is bonding bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, and bonding position A linear or branched divalent hydrocarbon group which may have an oxygen atom, or a divalent group which has an aromatic ring which may have an oxygen atom at a bonding position. A part or all of the hydrogen atoms of a phenylene group in the formula (5-1) and the formula (5-2) may be substituted with a hydroxyl group or a monovalent hydrocarbon group.

A specific example of the method of reacting the acid dianhydride represented by the above formula (1) and the diamine represented by the above formula (2) will be disclosed below.

First, the diamine represented by the above formula (2) is previously dissolved in a solvent capable of dissolving the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide, dimethicone, etc.). methylacetamide, etc.), the acid dianhydride represented by the above formula (1) is added to the obtained solution, and the reaction is carried out to obtain an amide acid oligomer solution. Then, the amide acid oligomer is recovered by removing the solvent from the obtained amide acid oligomer solution by heating or decompression, or by pouring it into a poor solvent such as water, methanol, and hexane for reprecipitation, thereby recovering the amide acid oligomer, Furthermore, the imidization reaction is carried out by heating at a temperature of about 200° C. or more for 1 hour or more. By adjusting the molar ratio of the acid dianhydride represented by the above formula (1) and the diamine represented by the above formula (2), and the imidization conditions, it is possible to obtain a desired number average molecular weight and have both ends. An imide oligomer with an acid anhydride group as a reactive functional group.

A specific example of the method of reacting the acid dianhydride represented by the above formula (1) and the phenolic hydroxyl group-containing monoamine represented by the above formula (3) will be disclosed below.

First, the phenolic hydroxyl group-containing monoamine represented by the formula (3) is previously dissolved in a solvent (for example, N-methylpyrrolidone, etc.) that can dissolve the amide acid oligomer obtained by the reaction, and the obtained To the obtained solution, the acid dianhydride represented by the above formula (1) is added and reacted to obtain an amide acid oligomer solution. Then, the amide acid oligomer is recovered by removing the solvent from the obtained amide acid oligomer solution by heating or decompression, or by pouring it into a poor solvent such as water, methanol, and hexane for reprecipitation, thereby recovering the amide acid oligomer, Furthermore, the imidization reaction is carried out by heating at a temperature of about 200° C. or more for 1 hour or more. By adjusting the molar ratio and imidization conditions of the acid dianhydride represented by the above formula (1) and the phenolic hydroxyl group-containing monoamine represented by the above formula (3), the desired number average molecular weight can be obtained. , and an imide oligomer having phenolic hydroxyl groups as reactive functional groups at both ends.

The following discloses a method of reacting the acid dianhydride represented by the above formula (1) with the diamine represented by the above formula (2), and then reacting with the phenolic hydroxyl group-containing monoamine represented by the above formula (3). specific example.

First, the diamine represented by the above formula (2) is previously dissolved in a solvent capable of dissolving the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide, dimethicone, etc.). (methylacetamide, etc.), the acid dianhydride represented by the above formula (1) is added to the obtained solution and reacted to obtain a solution of an amide acid oligomer (A) having acid anhydride groups at both ends. Then, the solvent is removed from the solution of the obtained aramidic acid oligomer (A) by heating or depressurizing, or the aramidic acid is reprecipitated by pouring into a poor solvent such as water, methanol, and hexane, thereby recovering the aramidic acid. The oligomer (A) is further heated at a temperature of about 200° C. or more for 1 hour or more to undergo an imidization reaction.

The thus-obtained imide oligomer having acid anhydride groups as reactive functional groups at both ends is redissolved in a solvent (such as N-methylpyrrolidone, dimethylformamide, dimethylformamide, etc.) acetamide, etc.), the phenolic hydroxyl group-containing monoamine represented by the above formula (3) is added and reacted to obtain a solution of an amide acid oligomer (B). The aramidic acid oligomer (B) is recovered by removing the solvent from the obtained solution of the aramidic acid oligomer (B) by heating or reducing pressure, or by pouring it into a poor solvent such as water, methanol, and hexane for reprecipitation, thereby recovering the aramidic acid oligomer The compound (B) is further heated at a temperature of about 200° C. or more for 1 hour or more, and the imidization reaction is carried out. By adjusting the molar ratio and imidization of the acid dianhydride represented by the above formula (1), the diamine represented by the above formula (2), and the phenolic hydroxyl group-containing monoamine represented by the above formula (3) Under certain conditions, an imide oligomer having a desired number average molecular weight and having phenolic hydroxyl groups as reactive functional groups at both ends can be obtained.

Examples of the acid dianhydride represented by the above formula (1) include pyromellitic dianhydride, 3,3'-oxydiphthalic acid dianhydride, and 3,4'-oxydiphthalic acid dihydride. Anhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-bis( 3,4-Dicarboxyphenoxy) diphenyl ether, p-phenylene bis(trimellitic anhydride), 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' - Biphenyltetracarboxylic dianhydride, 4,4'-carbonyl diphthalic dianhydride, etc. Among them, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 3,4'- '-oxydiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-carbonyl diphthalic dianhydride.

As the diamine represented by the above formula (2), for example, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane can be mentioned. Diphenylmethane, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenediamine, 1 ,3-Phenylenediamine, 1,4-Phenylenediamine, 3,3'-Diaminodiphenylene, 4,4'-Diaminodiphenylene, Bis(4-(3-aminodiphenyl) Phenoxy) phenyl) benzene, bis(4-(4-aminophenoxy)phenyl) benzene, 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'-dihydroxyphenylmethane, 4,4'-diamino-3,3'-dihydroxybenzene Methane, 3,3'-diamino-4,4'-dihydroxyphenyl ether, bisaminophenyl fluoride, bis-toluidine fluoride, 4,4'-bis(4-aminophenoxy)biphenyl Benzene, 4,4'-diamino-3,3'-dihydroxyphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-2 , 2'-dihydroxybiphenyl, etc. Among them, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenedi Amine, 1,3-phenylenediamine, 1,4-phenylenediamine, bis(4-(3-aminophenoxy)phenyl)benzene, bis(4-(4-aminophenoxy)benzene base) benzene, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis( 2-(4-aminophenyl)-2-propyl)benzene, 3,3'-dihydroxybenzidine.

Examples of the phenolic hydroxyl group-containing monoamine represented by the above formula (3) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-o-cresol, and 4-amino-o-cresol. -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-diphenylphenol, etc. Among them, 3-aminophenol, 4-aminophenol, and 4-amino-o-methyl are preferred in terms of excellent availability and storage stability, and the fact that a cured product having a high glass transition temperature can be obtained. Phenol, 5-amino-o-cresol.

The preferable lower limit of the imidization rate of the above-mentioned imide oligomer is 70%. With the above-mentioned imidization ratio of 70% or more, a cured product having more excellent mechanical strength at high temperature and long-term heat resistance can be obtained. The more preferable lower limit of the above-mentioned imidization rate is 75%, and the more preferable lower limit is 80%. In addition, there is no particularly preferable upper limit for the imidization rate of the above-mentioned imide oligomer, and the upper limit is substantially 98%.

In addition, the said "imidization rate" can be calculated|required by Fourier transform infrared spectroscopy (FT-IR). Specifically, it can be measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrometer (for example, "UMA600" manufactured by Agilent Technologies, Inc.), and it can be measured from the vicinity of 1660 cm ^-1 of the carbonyl group derived from amide acid. The peak absorbance area is derived from the following formula. In addition, the "peak absorbance area of the aramidic acid oligomer" in the following formula is the absorbance of the aramidic acid oligomer obtained by evaporating the solvent without carrying out the imidization step in the above-mentioned production method. area.

Imidization rate (%)=100×(1-(Peak absorbance area after imidization)/(Peak absorbance area of imidized oligomer))

The above-mentioned imide oligomers may be used alone or in combination of two or more.

The preferable lower limit of the number average molecular weight of the above-mentioned imide oligomer is 400, and the preferable upper limit is 5000. When the above-mentioned number average molecular weight is in this range, the long-term heat resistance of the obtained cured product is more excellent. A more preferable lower limit of the number average molecular weight of the above-mentioned imide oligomer is 500, and a more preferable upper limit is 4000.

The preferable upper limit of the softening point of the above-mentioned imide oligomer is 250°C. When the softening point of the above-mentioned imide oligomer is 250° C. or lower, the obtained cured product is more excellent in adhesiveness and long-term heat resistance. A more preferable upper limit of the softening point of the above-mentioned imide oligomer is 200°C.

There is no particularly preferred lower limit for the softening point of the above-mentioned imide oligomer, and the lower limit is substantially 60°C.

In addition, the softening point of the said imide oligomer can be calculated|required by the ring and ball method based on JISK2207.

The preferable lower limit of the content of the above-mentioned imide oligomer in 100 parts by weight of the total of the thermosetting resin, the thermoplastic resin and the imide oligomer is 10 parts by weight, and the preferable upper limit is 90 parts by weight. When the content of the above-mentioned imide oligomer is in this range, the cured product of the obtained curable resin composition is more excellent in mechanical strength at high temperature, adhesiveness, and long-term heat resistance. A more preferable lower limit of the content of the above-mentioned imide oligomer is 20 parts by weight, and a more preferable upper limit is 80 parts by weight.

The curable resin composition of this invention 1 may contain other hardening|curing agents other than the said imide oligomer in the range which does not impair the objective of this invention.

As said other hardening agent, a phenol type hardening agent, a thiol type hardening agent, an amine type hardening agent, an acid anhydride type hardening agent, a cyanate ester type hardening agent, an active ester type hardening agent, etc. are mentioned, for example. Among them, a phenol-based curing agent, an acid anhydride-based curing agent, a cyanate-based curing agent, and an active ester-based curing agent are preferred.

When the curable resin composition of the present invention 1 contains the other curing agents, the preferable upper limit of the content ratio of the other curing agents in the total 100 parts by weight of the above-mentioned imide oligomer and the other curing agents is 70 parts by weight, the more preferred upper limit is 50 parts by weight, and the more preferred upper limit is 30 parts by weight.

The curable resin composition of the present invention 1 preferably contains a curing accelerator. By containing the above-mentioned hardening accelerator, hardening time can be shortened and productivity can be improved.

Examples of the above-mentioned curing accelerator include imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, phosphorus-based curing accelerators, photobase generators, perylene salt-based curing accelerators, and the like. Among them, an imidazole-based hardening accelerator is preferable in that it is excellent in storage stability.

About content of the said hardening accelerator, a preferable lower limit is 0.01 weight part with respect to 100 weight part of said thermosetting resins, and a preferable upper limit is 10 weight part. When the content of the above-mentioned hardening accelerator is in this range, not only excellent adhesiveness is maintained, but also the effect of shortening the hardening time is more excellent. A more preferable lower limit of the content of the above hardening accelerator is 0.05 parts by weight, and a more preferable upper limit is 5 parts by weight.

The curable resin composition of the present invention 1 may contain an inorganic filler in order to reduce the coefficient of linear expansion after curing to reduce warpage, or to improve adhesion reliability. In addition, the above-mentioned inorganic fillers can also be preferably used as flow regulators.

Examples of the inorganic filler include fumed silica, silica such as colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, glass frit, glass frit, glass Fiber, carbon fiber, inorganic ion exchanger, etc.

About content of the said inorganic filler, a preferable upper limit is 500 weight part with respect to 100 weight part of said thermosetting resins. When the content of the above-mentioned inorganic filler is 500 parts by weight or less, not only the excellent workability and the like are maintained, but also the effects of improving the bonding reliability or performing the flow adjustment are more excellent. The more preferable upper limit of the content of the above-mentioned inorganic filler is 400 parts by weight.

The curable resin composition of the present invention 1 may contain an organic filler in order to relieve stress, impart toughness, and the like.

Examples of the organic filler include silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, and benzoguanidine. Amine particles and such core-shell particles, etc. Among them, polyamide particles, polyamide imide particles, and polyimide particles are preferred.

The content of the above-mentioned organic filler is preferably 500 parts by weight relative to 100 parts by weight of the above-mentioned thermosetting resin. When the content of the above-mentioned organic filler is 500 parts by weight or less, not only excellent adhesiveness and the like are maintained, but also the toughness and the like of the obtained cured product are more excellent. The more preferable upper limit of the content of the above-mentioned organic filler is 400 parts by weight.

The curable resin composition of this invention 1 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 two or more reactive functional groups in 1 molecule is preferable from a viewpoint of adhesive reliability.

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

The curable resin composition of the present invention 1 may further contain additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, an anti-bleeding agent, and a flux.

As a method for producing the curable resin composition of the present invention 1, for example, a method of mixing a thermosetting resin, thermoplastic Resin, hardener, and other hardeners, hardening accelerators, inorganic fillers (flow modifiers), etc., which are added as needed, are mixed.

The preferred lower limit of the minimum melt viscosity of the curable resin composition of the present invention 1 is 5 kPa·s, and the preferred upper limit is 300 kPa·s. Since the said minimum melt viscosity is this range, the curable resin composition of this invention 1 has more excellent flow characteristics. A more preferable lower limit of the above-mentioned minimum melt viscosity is 10 kPa·s, a more preferable upper limit is 200 kPa·s, and a further preferable upper limit is 150 kPa·s.

Furthermore, the above-mentioned minimum melt viscosity can be obtained by using a rotary rheometer device (such as "VAR-100" manufactured by Reologica, etc.), under the conditions of a heating rate of 10°C/min, a frequency of 1Hz, and a strain of 1%, at a temperature of 60°C. The measurement is carried out within the measurement temperature range of ℃ to 300 ℃, and it is obtained from the lowest value of the complex viscosity at this time.

The curable resin composition of the present invention 1 can be used in a wide range of applications, and can be preferably used in electronic material applications that require particularly high heat resistance. For example, it can be used as a die bonding agent in electronic control unit (ECU) applications for aviation and in-vehicle use, or in power device applications using SiC and GaN. In addition, it can also be used for, for example, adhesives for power overlay packages, adhesives for printed wiring boards, adhesives for cover films of flexible printed wiring boards, copper-clad laminates, adhesives for semiconductor bonding, Interlayer insulating films, prepregs, sealants for LEDs, adhesives for structural materials, etc. Among them, it is suitable for use as an adhesive, and is especially suitable for use as an adhesive for a coverlay film of a flexible printed wiring board.

The adhesive which consists of the curable resin composition of this invention 1 (henceforth "the adhesive agent of this invention 1") is also one of this invention. The adhesive agent of this invention 1 can form an adhesive film (curable resin composition film) by methods, such as apply|coating to a mold release film, and drying, and hardening this adhesive film can obtain a hardened|cured material. The hardened|cured material of the curable resin composition of this invention 1 is also one of this invention.

The adhesive film formed using the adhesive agent of this invention 1 is also one of this invention. Moreover, the cover film (henceforth "cover film of this invention 1") which has an adhesive layer which consists of the hardened|cured material of the curable resin composition of this invention 1, and an insulating film is also one of this invention. Furthermore, the flexible printed wiring board which has the coverlay film of this invention 1 is also one of this invention.

The present invention 2 is a curable resin composition containing a curable resin, an imide oligomer, and a curing accelerator, wherein the imide oligomer is represented by the following formula (6).

In formula (6), X is a tetravalent group represented by the following formula (7-1), (7-2) or (7-3), and Y is the following formula (8-1), (8-2) ), (8-3) or (8-4) represented by the divalent base.

In formulas (7-1) to (7-3), * is the bonding position. The hydrogen atoms of the aromatic rings in the formulas (7-1) to (7-3) may be substituted.

In formulas (8-1) and (8-2), Z is a bonding bond, an oxygen atom, a sulfonyl group, a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a bonding A divalent group having an aromatic ring which may have an oxygen atom at the position. The hydrogen atoms of the aromatic rings in the formulae (8-1) and (8-2) may be substituted. In formulas (8-3) and (8-4), R ⁷ to R ¹⁴ represent a hydrogen atom or a monovalent hydrocarbon group, which may be the same or different. In formulas (8-1) to (8-4), * is the bonding position.

The present invention 2 will be described in detail below.

The inventors of the present invention found that, in a curable resin composition containing a curable resin, an imide oligomer, and a curing accelerator, by using a curable resin composition having a specific structure as the imide oligomer, storage stability is achieved. The present invention 2 was completed by obtaining a cured product having excellent properties and excellent low linear expansion, adhesiveness, and long-term heat resistance.

The curable resin composition of the present invention 2 contains an imide oligomer.

The above-mentioned imide oligomer is represented by the above-mentioned formula (6). Hereinafter, the imide oligomer represented by the above formula (6) is also referred to as the imide oligomer of the present invention 2. By containing the imide oligomer of the present invention 2, the curable resin composition of the present invention 2 is excellent in storage stability, and a cured product excellent in low linear expansion, adhesiveness, and long-term heat resistance can be obtained.

The preferred lower limit of the number average molecular weight of the imide oligomer of the present invention 2 is 400, and the preferred upper limit is 5000. When the said number average molecular weight is this range, the adhesiveness and long-term heat resistance of the hardened|cured material obtained are more excellent. A more preferable lower limit of the number average molecular weight of the imide oligomer of the present invention 2 is 500, and a more preferable upper limit is 4000.

In addition, in this specification, the said "number average molecular weight" is the value calculated|required in polystyrene conversion by measuring by gel permeation chromatography (GPC). As a column used for measuring the number average molecular weight in terms of polystyrene by GPC, for example, JAIGEL-2H-A (manufactured by Nippon Kagaku Kogyo Co., Ltd.) and the like can be mentioned.

The preferable upper limit of the softening point of the imide oligomer of the present invention 2 is 250°C. When the softening point of the imide oligomer of the present invention 2 is 250°C or lower, the obtained cured product is more excellent in adhesiveness and long-term heat resistance.

The more preferable upper limit of the softening point of the imide oligomer of the present invention 2 is 200°C.

There is no particularly preferred lower limit for the softening point of the imide oligomer of the present invention 2, and the lower limit is substantially 60°C.

In addition, the said softening point can be calculated|required by the ring and ball method based on JISK2207.

As a method of producing the imide oligomer of the present invention 2, for example, a method of reacting an acid dianhydride represented by the following formula (9) and a diamine represented by the following formula (10) may be mentioned.

In the formula (9), X is the same tetravalent group as X in the above-mentioned formula (6).

In the formula (10), Y is the same divalent group as Y in the above-mentioned formula (6), and R ¹⁵ to R ¹⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group.

A specific example of the method of reacting the acid dianhydride represented by the above formula (9) and the diamine represented by the above formula (10) will be disclosed below.

First, the diamine represented by the above formula (10) is previously dissolved in a solvent capable of dissolving the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide, dimethicone, etc.). (methylacetamide, etc.), the acid dianhydride represented by the above-mentioned formula (9) is added to the obtained solution and reacted to obtain an amide acid oligomer solution. Then, the amide acid oligomer is recovered by removing the solvent from the obtained amide acid oligomer solution by heating or decompression, or by pouring it into a poor solvent such as water, methanol, and hexane for reprecipitation, thereby recovering the amide acid oligomer, Furthermore, the imidization reaction is carried out by heating at a temperature of about 200° C. or more for 1 hour or more. By adjusting the molar ratio of the acid dianhydride represented by the above formula (9) and the diamine represented by the above formula (10) and the imidization conditions, the desired amount of the acid dianhydride represented by the above formula (6) can be obtained. The average molecular weight of imide oligomers.

As the acid dianhydride represented by the above formula (9), specifically, 3,4'-oxydiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, '-(4,4'-isopropylidenediphenoxy)diphthalic anhydride.

As the diamine represented by the above formula (10), for example, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane can be mentioned. Diphenyl ether, 4,4'-diaminodiphenyl ether, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3'-diaminodiphenylene, 4,4'- Diaminodiphenyl bis(4-(3-aminophenoxy)phenyl) bis(4-(4-aminophenoxy)phenyl) bis(4-(4-aminophenoxy)phenyl) bis(4-(4-aminophenoxy)phenyl) , 1,3-bis( 3-Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis(4-(4-amine) phenoxy)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, bisaminophenyl benzene, 4,4'-bis(4-aminophenoxy base) biphenyl, diethyltoluenediamine, etc. Among them, 1,3-bis(3-aminophenoxy)benzene and 1,3-bis(4-aminophenoxy) are preferred in terms of excellent solubility, heat resistance, and availability. Benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3'-diaminodiphenylene, 4,4 '-Diaminodiphenyl bismuth, bis(4-(3-aminophenoxy) phenyl) bismuth, bis(4-(4-aminophenoxy) phenyl) bismuth, diethyltoluene Diamine, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane. Moreover, 1, 3-bis (4-aminophenoxy) benzene is especially preferable at the point which is excellent in low linear expansion property.

The preferable lower limit of the imidization rate of the imide oligomer of the present invention 2 is 70%. With the above-mentioned imidization ratio of 70% or more, a cured product having more excellent mechanical strength at high temperature and long-term heat resistance can be obtained. The more preferable lower limit of the above-mentioned imidization rate is 75%, and the more preferable lower limit is 80%. In addition, there is no particularly preferable upper limit for the imidization rate of the imide oligomer of the present invention 2, and the upper limit is substantially 98%.

In addition, the said "imidization rate" can be calculated|required by Fourier transform infrared spectroscopy (FT-IR). Specifically, it can be measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrometer (for example, "UMA600" manufactured by Agilent Technologies, Inc.), and it can be measured from the vicinity of 1660 cm ^-1 of the carbonyl group derived from amide acid. The peak absorbance area is derived from the following formula. In addition, the "peak absorbance area of the amide acid oligomer" in the following formula is obtained by reacting the acid dianhydride represented by the above formula (9) and the diamine represented by the above formula (10), The absorbance area of the amide oligomer obtained by evaporating the solvent by performing the imidization step.

Imidization rate (%)=100×(1-(Peak absorbance area after imidization)/(Peak absorbance area of imidized oligomer))

The preferred lower limit of the content of the imide oligomer of the present invention 2 in 100 parts by weight of the curable resin, the imide oligomer and the curing accelerator is 20 parts by weight, and the preferred upper limit is 90 parts by weight. When the content of the imide oligomer of the present invention 2 is in this range, the cured product of the obtained curable resin composition is more excellent in mechanical strength at high temperature, adhesiveness and long-term heat resistance. A more preferable lower limit of the content of the imide oligomer of the present invention 2 is 30 parts by weight, and a more preferable upper limit is 80 parts by weight.

The curable resin composition of the present invention 2 may contain other imide oligomers or other curing agents other than the imide oligomer of the present invention 2 within a range that does not impair the object of the present invention.

As said other imide oligomer, the imide oligomer etc. which have an imide group and a reactive functional group in a molecule|numerator other than the imide oligomer of this invention 2 are mentioned, for example.

As said other hardening agent, a phenol type hardening agent, a thiol type hardening agent, an amine type hardening agent, an acid anhydride type hardening agent, a cyanate ester type hardening agent, an active ester type hardening agent, etc. are mentioned, for example. Among them, a phenol-based curing agent, an acid anhydride-based curing agent, a cyanate-based curing agent, and an active ester-based curing agent are preferred.

When the curable resin composition of the present invention 2 contains the above-mentioned other imide oligomers or the above-mentioned other hardeners, the content ratio of the above-mentioned other imide oligomers or the above-mentioned other hardeners in the whole hardener A preferable upper limit is 70% by weight, a more preferable upper limit is 50% by weight, and a further preferable upper limit is 30% by weight.

The curable resin composition of this invention 2 contains a curable resin.

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

As said epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl are mentioned, for example. base bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, thioether ring Oxygen resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, stilbene type epoxy resin, naphthyl ether type epoxy resin, phenol novolak type epoxy resin, O-cresol novolak epoxy resin, dicyclopentadiene novolak epoxy resin, biphenyl novolac epoxy resin, naphthol novolak epoxy resin, glycidylamine epoxy resin, alkyl Polyol-type epoxy resins, rubber-modified epoxy resins, Phenol-type epoxy resins, glycidyl ester compounds, etc. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. E-type epoxy resin, resorcinol-type epoxy resin, etc., liquid epoxy resin at room temperature. The above epoxy resins may be used alone or in combination of two or more.

The curable resin composition of this invention 2 contains a hardening accelerator. By containing the above-mentioned curing accelerator, not only the curing time can be shortened, the productivity can be improved, but also the long-term heat resistance of the cured product can be improved.

The above-mentioned curing accelerator is preferably an alkaline catalyst, and examples thereof include a curing accelerator having an imidazole skeleton (imidazole-based curing accelerator), a tertiary amine-based curing accelerator, a phosphorus-based curing accelerator, and a photobase generator. . Among them, a hardening accelerator having an imidazole skeleton is more preferable in terms of excellent storage stability.

、2,4-二胺基-6-(2'-十一烷基咪唑基-(1'))-乙基對稱三

、2,4-二胺基-6-(2'-乙基-4'-甲基咪唑基-(1'))-乙基對稱三

、2,4-二胺基-6-(2'-甲基咪唑基-(1'))-乙基對稱三

異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-甲基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等。 Examples of the curing accelerator having an imidazole skeleton include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and 2-benzene Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyano Ethylethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino -6-(2'-Methylimidazolyl-(1'))-ethyl symmetric tris

, 2,4-diamino-6-(2'-undecylimidazolyl-(1'))-ethyl symmetric tri

, 2,4-Diamino-6-(2'-ethyl-4'-methylimidazolyl-(1'))-ethyl symmetric tri

, 2,4-Diamino-6-(2'-methylimidazolyl-(1'))-ethyl symmetric tri

Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.

As other hardening accelerators other than the hardening accelerator which has the said imidazole skeleton, a tertiary amine type hardening accelerator, a phosphine type hardening accelerator, a photobase generator, a perylene salt type hardening accelerator etc. are mentioned, for example.

The preferable lower limit of the content of the above-mentioned hardening accelerator in 100 parts by weight of the total of the curable resin, the imide oligomer and the hardening accelerator is 0.8 parts by weight, and the preferable upper limit is 10 parts by weight. When the content of the above-mentioned curing accelerator is 0.8 parts by weight or more, the obtained curable resin composition is more excellent in the adhesiveness or long-term heat resistance of the cured product. When the content of the above-mentioned curing accelerator is 10 parts by weight or less, the obtained curable resin composition is more excellent in storage stability. A more preferable lower limit of the content of the above hardening accelerator is 1 part by weight, and a more preferable upper limit is 9 parts by weight.

The curable resin composition of the present invention 2 may contain an inorganic filler in order to reduce the coefficient of linear expansion after curing to reduce warpage, or to improve adhesion reliability. In addition, the above-mentioned inorganic fillers can also be preferably used as flow regulators.

Examples of the above-mentioned inorganic filler include silica such as fumed silica and colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, and carbon fiber. , inorganic ion exchangers, etc.

The content of the above-mentioned inorganic filler is preferably 300 parts by weight relative to 100 parts by weight of the above-mentioned curable resin. When the content of the above-mentioned inorganic filler is 300 parts by weight or less, not only excellent workability and the like are maintained, but also the effects of improving adhesion reliability and flow adjustment are more excellent. A more preferable upper limit of the content of the above-mentioned inorganic filler is 200 parts by weight.

The curable resin composition of the present invention 2 may contain an organic filler in order to relieve stress, impart toughness, and the like.

Examples of the organic filler include polysiloxane rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamide imide particles, polyimide particles, benzoguanamine particles, and Such core-shell particles, etc. Among them, polyamide particles, polyamide imide particles, and polyimide particles are preferred.

About content of the said organic filler, a preferable upper limit is 300 weight part with respect to 100 weight part of said curable resin. When the content of the above-mentioned organic filler is 300 parts by weight or less, not only excellent adhesion and the like are maintained, but also the toughness and the like of the obtained cured product are further excellent. A more preferable upper limit of the content of the above organic filler is 200 parts by weight.

The curable resin composition of this invention 2 may contain a polymer compound in the range which does not impair the objective of this invention. The above-mentioned polymer compound functions as a film-forming component.

The above-mentioned polymer compound may have a reactive functional group.

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

The curable resin composition of this invention 2 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 two or more reactive functional groups in 1 molecule is preferable from a viewpoint of adhesive reliability.

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

The curable resin composition of the present invention 2 may further contain additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, an anti-bleeding agent, a flux, a leveling agent, and a flame retardant.

As a method of producing the curable resin composition of the present invention 2, for example, a method of mixing the curable resin, the present The imide oligomer of 2, the curing accelerator, and other curing agents or inorganic fillers (flow conditioners), etc. added as needed are mixed.

Furthermore, by applying the curable resin composition of the present invention 2 on a film and drying it, a film composed of the curable resin composition of the present invention 2 can be obtained, and by curing the curable resin composition film , and hardened material can be obtained. The cured product of the curable resin composition of the present invention 2 (hereinafter also referred to as "the cured product of the present invention 2") is also one of the present inventions.

From the viewpoint of reducing warpage or improving adhesion reliability, the average linear expansion coefficient of the cured product of the present invention 2 in the temperature range of 40°C to 80°C is preferably 60 ppm or less, more preferably 55 ppm or less. The above-mentioned average linear expansion coefficient is preferably as small as possible.

In addition, the said average linear expansion coefficient can be measured using the thermomechanical analyzer with respect to the hardened|cured material of thickness about 400 micrometers. Specifically, under the conditions of a load of 5g and a heating rate of 10°C/min, the hardened product with a length of 1 cm of the sample can be heated from 0°C to 300°C, then cooled for a while, and then heated again from 0°C to 300°C under the same conditions , based on the temperature and dimensional change data obtained in the second measurement, to obtain the average coefficient of linear expansion in the temperature range of 40°C to 80°C.

The cured product for which the average linear expansion coefficient is measured can be obtained by heating the above-mentioned curable resin composition film at 190° C. for 30 minutes or more.

As said thermomechanical analysis apparatus, TMA/SS-6000 (made by Hitachi High-Tech Science Corporation) etc. are mentioned, for example.

The curable resin composition of the present invention 2 can be used in a wide range of applications, and can be preferably used in electronic material applications that require particularly high heat resistance. For example, it can be used as a die adhesive for electronic control unit (ECU) applications for aviation and automotive vehicles, or for power device applications using SiC and GaN. In addition, it can also be used for, for example, adhesives for power cover encapsulation, adhesives for printed wiring boards, adhesives for covering flexible printed circuit boards, copper-clad laminates, adhesives for semiconductor bonding, interlayer insulating films, pre- Immersion body, sealant for LED, adhesive for construction material, etc. Among them, it is suitable for use as an adhesive.

The adhesive which consists of the curable resin composition of this invention 2 is also one of this invention.

Moreover, the adhesive film formed using the curable resin composition of this invention 2 is also one of this invention.

The third aspect of the present invention is a curable resin composition comprising a curable resin and an imide oligomer, wherein the curable resin is in a liquid state at 25°C, and the imide oligomer is in a solid particle state at 25°C dispersion. The present invention 3 will be described in detail below.

The inventors of the present invention studied, in a curable resin composition containing a curable resin and an imine oligomer, using a curable resin in a liquid state at 25° C., and making the imine oligomer Disperse in the form of solid particles at 25°C. As a result, the inventors found that a curable resin composition excellent in flexibility and workability before curing and excellent in adhesiveness and heat resistance after curing can be obtained, thereby completing the present invention 3.

The curable resin composition of this invention 3 contains a curable resin.

The said curable resin is liquid at 25 degreeC. Since the said curable resin is liquid at 25 degreeC, the curable resin composition of this invention 3 is excellent in fluidity and workability. Moreover, in order to disperse|distribute the following imide oligomer in a solid particle form, the thing which does not melt|dissolve this imide oligomer at 25 degreeC was used as said curable resin.

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

As said epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl are mentioned, for example. base bisphenol A epoxy resin, hydrogenated bisphenol epoxy resin, propylene oxide addition bisphenol A epoxy resin, resorcinol epoxy resin, biphenyl epoxy resin, thioether ring Oxygen resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, stilbene type epoxy resin, naphthyl ether type epoxy resin, phenol novolak type epoxy resin, O-cresol novolak epoxy resin, dicyclopentadiene novolak epoxy resin, biphenyl novolac epoxy resin, naphthol novolak epoxy resin, glycidylamine epoxy resin, alkyl Polyol-type epoxy resins, rubber-modified epoxy resins, Phenol-type epoxy resins, glycidyl ester compounds, etc. Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. E-type epoxy resin, resorcinol-type epoxy resin, etc., liquid epoxy resin at room temperature. The above epoxy resins may be used alone or in combination of two or more.

The curable resin composition of the present invention 3 contains an imide oligomer. In the curable resin composition of the present invention 3, the above-mentioned imide oligomer is dispersed in the form of solid particles at 25°C. By dispersing the above-mentioned imide oligomer in the form of solid particles, the curable resin composition of the present invention 3 not only maintains excellent fluidity and processability, but also obtains a product with excellent flexibility, excellent adhesion and heat resistance. hardened material.

Furthermore, the above-mentioned so-called "dispersed in the form of solid particles" means that there is no dissolution but exists in the form of particles, and most of the particles are dispersed with each other and are not agglomerated. Confirmed by direct observation.

It is preferable that the said imide oligomer has a reactive functional group which can react with the said curable resin.

The reactive functional group described above varies depending on the type of curable resin used, but when an epoxy resin is used as the curable resin, it is preferably an acid anhydride group and/or a phenolic hydroxyl group.

The above-mentioned imide oligomer preferably has the above-mentioned reactive functional group at the end of the main chain, more preferably at both ends.

As a method for producing an imide oligomer having an acid anhydride group as the above reactive functional group, for example, an acid dianhydride represented by the following formula (11) and a diamine represented by the following formula (12) can be mentioned. reaction method, etc.

Moreover, as the method of producing the imide oligomer which has a phenolic hydroxyl group as the said reactive functional group, the following method etc. are mentioned, for example.

That is, a method of reacting an acid dianhydride represented by the following formula (11) and a phenolic hydroxyl group-containing monoamine represented by the following formula (13); or a method of reacting an acid dianhydride represented by the following formula (11) After the acid dianhydride is reacted with the diamine represented by the following formula (12), the method of further reacting with the phenolic hydroxyl group-containing monoamine represented by the following formula (13), etc.

In the formula (11), A is a tetravalent group represented by the following formula (14-1) or the following formula (14-2).

In formula (12), B is a divalent group represented by the following formula (15-1) or the following formula (15-2), and R ¹⁹ to R ²² are each independently a hydrogen atom or a monovalent hydrocarbon group.

In formula (13), Ar is a divalent aromatic group which may be substituted, and R ²³ and R ²⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group.

In formula (14-1) and formula (14-2), * is a bonding position, and in formula (14-1), Z is a bonding bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, and bonding position A linear or branched divalent hydrocarbon group which may have an oxygen atom, or a divalent group which has an aromatic ring which may have an oxygen atom at a bonding position. The hydrogen atom of the aromatic ring in the formula (14-1) and the formula (14-2) may be substituted.

In formula (15-1) and formula (15-2), * is the bonding position, and in formula (15-1), Y is bonding bond, oxygen atom, carbonyl group, sulfur atom, sulfonyl group, bonding position A linear or branched divalent hydrocarbon group which may have an oxygen atom, or a divalent group which has an aromatic ring which may have an oxygen atom at a bonding position. A part or all of the hydrogen atoms of a phenylene group in the formula (15-1) and the formula (15-2) may be substituted with a hydroxyl group or a monovalent hydrocarbon group.

A specific example of the method of reacting the acid dianhydride represented by the above formula (11) and the diamine represented by the above formula (12) will be disclosed below.

First, the diamine represented by the above formula (12) is previously dissolved in a solvent capable of dissolving the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide, dimethicone, etc.). (methylacetamide, etc.), the acid dianhydride represented by the above formula (11) is added to the obtained solution and reacted to obtain an amide acid oligomer solution. Then, the amide acid oligomer is recovered by removing the solvent from the obtained amide acid oligomer solution by heating or decompression, or by pouring it into a poor solvent such as water, methanol, and hexane for reprecipitation, thereby recovering the amide acid oligomer, Furthermore, the imidization reaction is carried out by heating at a temperature of about 200° C. or more for 1 hour or more. By adjusting the molar ratio and imidization conditions of the acid dianhydride represented by the above formula (11) and the diamine represented by the above formula (12), it is possible to obtain a compound having a desired number average molecular weight and having both ends. An imide oligomer with an acid anhydride group as a reactive functional group.

A specific example of the method of reacting the acid dianhydride represented by the above formula (11) and the phenolic hydroxyl group-containing monoamine represented by the above formula (13) will be disclosed below.

First, the phenolic hydroxyl group-containing monoamine represented by the formula (13) is previously dissolved in a solvent (for example, N-methylpyrrolidone, etc.) that can dissolve the amide acid oligomer obtained by the reaction, and the The acid dianhydride represented by the above formula (11) is added to the obtained solution and reacted to obtain an amide acid oligomer solution. Then, the amide acid oligomer is recovered by removing the solvent from the obtained amide acid oligomer solution by heating or decompression, or by pouring it into a poor solvent such as water, methanol, and hexane for reprecipitation, thereby recovering the amide acid oligomer, Furthermore, the imidization reaction is carried out by heating at a temperature of about 200° C. or more for 1 hour or more. By adjusting the molar ratio of the acid dianhydride represented by the above formula (11) and the phenolic hydroxyl group-containing monoamine represented by the above formula (13) and the imidization conditions, the desired number average molecular weight can be obtained. , and an imide oligomer having phenolic hydroxyl groups as reactive functional groups at both ends.

The acid dianhydride represented by the above formula (11) and the diamine represented by the above formula (12) are disclosed below.

A specific example of the method of further reacting with the phenolic hydroxyl group-containing monoamine represented by the above formula (13) after the reaction is performed.

First, the diamine represented by the above formula (12) is previously dissolved in a solvent capable of dissolving the amide acid oligomer obtained by the reaction (for example, N-methylpyrrolidone, dimethylformamide, dimethicone, etc.). (methylacetamide, etc.), the acid dianhydride represented by the above formula (11) is added to the obtained solution and reacted to obtain a solution of an amide acid oligomer (A) having acid anhydride groups at both ends. Then, the solvent is removed from the solution of the obtained aramidic acid oligomer (A) by heating or depressurizing, or the aramidic acid is reprecipitated by pouring into a poor solvent such as water, methanol, and hexane, thereby recovering the aramidic acid. The oligomer (A) is further heated at a temperature of about 200° C. or more for 1 hour or more to undergo an imidization reaction.

The thus-obtained imide oligomer having acid anhydride groups as reactive functional groups at both ends is redissolved in a solvent (such as N-methylpyrrolidone, dimethylformamide, dimethylformamide, etc.) acetamide, etc.), the phenolic hydroxyl group-containing monoamine represented by the above formula (13) is added and reacted to obtain a solution of an amide acid oligomer (B). The aramidic acid oligomer (B) is recovered by removing the solvent from the obtained solution of the aramidic acid oligomer (B) by heating or reducing pressure, or by pouring it into a poor solvent such as water, methanol, and hexane for reprecipitation, thereby recovering the aramidic acid oligomer The compound (B) is further heated at a temperature of about 200° C. or more for 1 hour or more, and the imidization reaction is carried out. By adjusting the molar ratio and imidization of the acid dianhydride represented by the above formula (11), the diamine represented by the above formula (12), and the phenolic hydroxyl group-containing monoamine represented by the above formula (13) Under certain conditions, an imide oligomer having a desired number average molecular weight and having phenolic hydroxyl groups as reactive functional groups at both ends can be obtained.

Examples of the acid dianhydride represented by the above formula (11) include pyromellitic dianhydride, 3,3'-oxydiphthalic acid dianhydride, and 3,4'-oxydiphthalic acid dihydride. Anhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-bis( 3,4-Dicarboxyphenoxy) diphenyl ether, p-phenylene bis(trimellitic anhydride), 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' - Biphenyltetracarboxylic dianhydride, 4,4'-carbonyl diphthalic dianhydride, etc. Among them, 4,4'-(4,4'-isopropylidenediphenoxy is preferred in terms of controlling the softening point of the imide oligomer, solubility, heat resistance, and availability. ) diphthalic anhydride, 3,4'-oxydiphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-carbonyl diphthalic dianhydride.

As the diamine represented by the above formula (12), for example, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane can be mentioned. Diphenylmethane, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,2-phenylenediamine, 1 ,3-Phenylenediamine, 1,4-Phenylenediamine, 3,3'-Diaminodiphenylene, 4,4'-Diaminodiphenylene, Bis(4-(3-aminodiphenyl) Phenoxy) phenyl) benzene, bis(4-(4-aminophenoxy)phenyl) benzene, 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'-dihydroxyphenylmethane, 4,4'-diamino-3,3'-dihydroxybenzene Methane, 3,3'-diamino-4,4'-dihydroxyphenyl ether, bisaminophenyl fluoride, bis-toluidine fluoride, 4,4'-bis(4-aminophenoxy)biphenyl Benzene, 4,4'-diamino-3,3'-dihydroxyphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-2 , 2'-dihydroxybiphenyl, etc. Among them, 3,4'-diaminodiphenyl ether and 4,4'-diamine are preferred in terms of controlling the softening point, solubility, heat resistance, and availability of the imide oligomer Diphenyl ether, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, bis(4-(3-aminophenoxy)phenyl) bis(4-(3-aminophenoxy)phenyl) -(4-Aminophenoxy)phenyl)benzene, 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene, 1,3-bis(3-aminobenzene) oxy)benzene, 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene, 3,3'-dihydroxybenzidine.

Examples of the phenolic hydroxyl group-containing monoamine represented by the above formula (13) include 3-aminophenol, 4-aminophenol, 4-amino-o-cresol, 5-amino-o-cresol, 4-amino-o-cresol, and 4-amino-o-cresol. -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-diphenylphenol, etc. Among them, 3-aminophenol, 4-aminophenol, and 4-amino-o-methyl are preferred in terms of excellent availability and storage stability, and the fact that a cured product having a high glass transition temperature can be obtained. Phenol, 5-amino-o-cresol.

The preferable lower limit of the imidization rate of the above-mentioned imide oligomer is 70%. With the above-mentioned imidization ratio of 70% or more, a cured product having more excellent mechanical strength at high temperature and long-term heat resistance can be obtained. The more preferable lower limit of the above-mentioned imidization rate is 75%, and the more preferable lower limit is 80%. In addition, there is no particularly preferable upper limit for the imidization rate of the above-mentioned imide oligomer, and the upper limit is substantially 98%.

In addition, the said "imidization rate" can be calculated|required by Fourier transform infrared spectroscopy (FT-IR). Specifically, it can be measured by a total reflection measurement method (ATR method) using a Fourier transform infrared spectrometer (for example, "UMA600" manufactured by Agilent Technologies, Inc.), and it can be measured from the vicinity of 1660 cm ^-1 of the carbonyl group derived from amide acid. The peak absorbance area is derived from the following formula. In addition, the "peak absorbance area of the amide acid oligomer" in the following formula is obtained by reacting the acid dianhydride represented by the above formula (11) with each amine compound, without performing the amide imidization step. And the absorbance area of the amino acid oligomer obtained by removing the solvent. The above-mentioned solvents can be removed by evaporation.

Imidization rate (%)=100×(1-(Peak absorbance area after imidization)/(Peak absorbance area of imidized oligomer))

The above-mentioned imide oligomers may be used alone or in combination of two or more.

The preferable lower limit of the average particle diameter of the said imide oligomer in the curable resin composition of this invention 3 is 0.5 micrometer, and a preferable upper limit is 20 micrometers. Since the average particle diameter of the said imide oligomer is 0.5 micrometer or more, the obtained curable resin composition is excellent in flexibility and workability in the state before hardening. When the average particle diameter of the above-mentioned imide oligomer is 20 μm or less, the obtained curable resin composition is excellent in uniformity, and a cured product excellent in adhesiveness and heat resistance can be obtained. A more preferable lower limit of the average particle diameter of the above-mentioned imide oligomer is 1 μm, and a more preferable upper limit is 10 μm.

The preferable lower limit of the number average molecular weight of the above-mentioned imide oligomer is 400, and the preferable upper limit is 5000. When the said number average molecular weight is this range, the long-term heat resistance of the hardened|cured material obtained is more excellent. A more preferable lower limit of the number average molecular weight of the above-mentioned imide oligomer is 500, and a more preferable upper limit is 4000.

In addition, in this specification, the said "number average molecular weight" is the value calculated|required in polystyrene conversion by measuring by gel permeation chromatography (GPC). As a column used for measuring the number average molecular weight in terms of polystyrene by GPC, for example, JAIGEL-2H-A (manufactured by Nippon Kagaku Kogyo Co., Ltd.) and the like can be mentioned.

The preferable upper limit of the softening point of the above-mentioned imide oligomer is 250°C. When the softening point of the above-mentioned imide oligomer is 250°C or lower, the obtained cured product is more excellent in adhesiveness and long-term heat resistance. A more preferable upper limit of the softening point of the above-mentioned imide oligomer is 200°C.

There is no particularly preferred lower limit for the softening point of the above-mentioned imide oligomer, and the lower limit is substantially 60°C.

In addition, the softening point of the said imide oligomer can be calculated|required by the ring and ball method based on JISK2207.

The preferable upper limit of the melting point of the above-mentioned imide oligomer is 300°C. When the melting point of the above-mentioned imide oligomer is 300° C. or lower, the obtained curable resin composition is more excellent in adhesiveness and long-term heat resistance. A more preferable upper limit of the melting point of the above-mentioned imide oligomer is 250°C.

In addition, the melting point of the above-mentioned imide oligomer can be determined by differential scanning calorimetry or using a commercially available melting point measuring device.

The content of the above-mentioned imide oligomer is preferably 30 parts by weight and the preferred upper limit is 500 parts by weight with respect to 100 parts by weight of the above-mentioned curable resin. Since the content of the above-mentioned imide oligomer is in this range, the cured product of the obtained curable resin composition is more excellent in mechanical strength at high temperature, adhesiveness and long-term heat resistance. A more preferable lower limit of the content of the above-mentioned imide oligomer is 50 parts by weight, and a more preferable upper limit is 400 parts by weight.

The curable resin composition of the present invention 3 may contain only an imide oligomer that is insoluble in the curable resin composition at 25°C as the above-mentioned imide oligomer, or may contain a composition that is insoluble in the curable resin at 25°C The imide oligomer which is a material and the imide oligomer which is soluble in the curable resin composition at 25°C are used as the above-mentioned imine oligomer. Hereinafter, the imide oligomer that is insoluble in the curable resin composition at 25°C is also referred to as "insoluble imide oligomer", and the imide oligomer that is soluble in the curable resin composition at 25°C is also referred to as Amine oligomers are called "soluble imine oligomers". That is, in the curable resin composition of the present invention 3, a part of the imide oligomer (soluble imine oligomer) is dissolved, and the other part (insoluble imine oligomer) is solid Particle dispersion. In this case, the wettability of the above-mentioned soluble imide oligomer can show strong adhesive force, and the above-mentioned insoluble imide oligomer can impart fluidity, Processability and flexibility.

In addition, the above-mentioned "insoluble in curable resin composition" means insoluble in the above-mentioned curable resin when the following solvent is not used, and insoluble in the solvent and the above-mentioned curable resin when the following solvent is used. . In addition, the above-mentioned "soluble in the curable resin composition" means soluble in the curable resin when the following solvent is not used, and soluble in the solvent and the above-mentioned solvent when the following solvent is used. Hardening resin.

In the case of using the above-mentioned soluble imine oligomer, the content ratio of the above-mentioned soluble imine oligomer is preferably 80 parts by weight or less in 100 parts by weight of the whole imine oligomer. When the content ratio of the above-mentioned soluble imide oligomer is 80 parts by weight or less, the obtained curable resin composition not only maintains excellent flexibility, but also has more excellent adhesiveness.

Moreover, when using the said soluble type imine oligomer, it is preferable that the content rate of the said soluble type imine oligomer is 20 weight part or more.

The curable resin composition of this invention 3 may contain other hardening|curing agents other than the said imide oligomer in the range which does not impair the objective of this invention.

As said other hardening agent, a phenol type hardening agent, a thiol type hardening agent, an amine type hardening agent, an acid anhydride type hardening agent, a cyanate ester type hardening agent, an active ester type hardening agent, etc. are mentioned, for example. Among them, a phenol-based curing agent, an acid anhydride-based curing agent, a cyanate-based curing agent, and an active ester-based curing agent are preferred.

In the case where the curable resin composition of the present invention 3 contains the above-mentioned other hardeners, the preferable upper limit of the content ratio of the above-mentioned other hardeners in the total of 100 parts by weight of the above-mentioned imide oligomers and the above-mentioned other hardeners is 70 parts by weight, the more preferred upper limit is 50 parts by weight, and the more preferred upper limit is 30 parts by weight.

It is preferable that the curable resin composition of this invention 3 contains a hardening accelerator. By containing the above-mentioned hardening accelerator, hardening time can be shortened and productivity can be improved.

As said hardening accelerator, imidazole type hardening accelerator, tertiary amine type hardening accelerator, phosphine type hardening accelerator, phosphorus type hardening accelerator, photobase generator, perylene salt type hardening accelerator etc. are mentioned, for example. Among them, an imidazole-based hardening accelerator is preferred in terms of excellent storage stability.

About content of the said hardening accelerator, a preferable lower limit is 0.01 weight part with respect to 100 weight part of said curable resins, and a preferable upper limit is 10 weight part. When the content of the above-mentioned hardening accelerator is in this range, not only excellent adhesiveness is maintained, but also the effect of shortening the hardening time is more excellent. A more preferable lower limit of the content of the above hardening accelerator is 0.05 parts by weight, and a more preferable upper limit is 5 parts by weight.

The curable resin composition of the present invention 3 may contain an inorganic filler in order to reduce the coefficient of linear expansion after curing to reduce warpage, or to improve adhesion reliability. In addition, the above-mentioned inorganic fillers can also be preferably used as flow regulators.

Examples of the above-mentioned inorganic filler include silica such as fumed silica and colloidal silica, alumina, aluminum nitride, boron nitride, silicon nitride, glass powder, glass frit, glass fiber, and carbon fiber. , inorganic ion exchangers, etc.

About content of the said inorganic filler, a preferable upper limit is 500 weight part with respect to 100 weight part of said curable resins. When the content of the above-mentioned inorganic filler is 500 parts by weight or less, not only the excellent workability and the like are maintained, but also the effects of improving the bonding reliability or performing the flow adjustment are more excellent. The more preferable upper limit of the content of the above-mentioned inorganic filler is 400 parts by weight.

The curable resin composition of the present invention 3 may contain an organic filler in order to relieve stress, impart toughness, and the like.

Examples of the organic filler include polysiloxane rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamide imide particles, polyimide particles, benzoguanamine particles, and Such core-shell particles, etc. Among them, polyamide particles, polyamide imide particles, and polyimide particles are preferred.

About content of the said organic filler, a preferable upper limit is 500 weight part with respect to 100 weight part of said curable resin. When the content of the above-mentioned organic filler is 500 parts by weight or less, not only excellent adhesiveness and the like are maintained, but also the toughness and the like of the obtained cured product are more excellent. A more preferable upper limit of the content of the above-mentioned organic filler is 400 parts by weight.

The curable resin composition of this invention 3 may contain a polymer compound in the range which does not impair the objective of this invention. The above-mentioned polymer compound functions as a film-forming component.

The above-mentioned polymer compound may have a reactive functional group.

When the polymer compound has a reactive functional group, examples of the reactive functional group included in the polymer compound include an amino group, an urethane group, an imino group, a hydroxyl group, a carboxyl group, and an epoxy group. Wait.

The curable resin composition of this invention 3 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 two or more reactive functional groups in 1 molecule is preferable from a viewpoint of adhesive reliability.

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

The curable resin composition of the present invention 3 may further contain additives such as a solvent, a coupling agent, a dispersant, a storage stabilizer, an anti-bleeding agent, a flux, a leveling agent, and a flame retardant.

As a method of manufacturing the curable resin composition of this invention 3, the following method etc. are mentioned, for example.

Examples of the method include the following methods: after preliminarily pulverizing a solid block-shaped imide oligomer using a pulverizer such as a jet mill, a ball mill, and a bead mill, and dispersing it in a dispersion that does not dissolve the imine oligomer in the medium to obtain an imide oligomer dispersion. Then, using a mixer such as a homogeneous disperser, a universal mixer, a Banbury mixer, and a kneader, the curable resin, imide oligomer dispersion liquid, and other hardeners or hardening accelerators added as needed Or inorganic fillers (flow conditioners), etc. are mixed.

The curable resin composition of the present invention 3 can be used in a wide range of applications, and can be preferably used in electronic material applications that require particularly high heat resistance. For example, it can be used as a die adhesive for electronic control unit (ECU) applications for aviation and automotive vehicles, or for power device applications using SiC and GaN. In addition, it can also be used for, for example, adhesives for power cover encapsulation, adhesives for printed wiring boards, adhesives for covering flexible printed circuit boards, copper-clad laminates, adhesives for semiconductor bonding, interlayer insulating films, prepregs body, sealant for LED, adhesive for construction material, etc. Among them, it is suitable for use as an adhesive.

The adhesive which consists of the curable resin composition of this invention 3 (henceforth "the adhesive agent of this invention 3") is also one of this invention. An adhesive film (curable resin composition film) can be obtained by a method such as coating the adhesive of the present invention 3 on a film, followed by drying, and a cured product can be obtained by curing the adhesive film. The hardened|cured material of the curable resin composition of this invention 3 is also one of this invention. Moreover, the adhesive film formed using the adhesive agent of this invention 3 is also one of this invention.

According to the present invention, it is possible to provide a curable resin composition which is excellent in flow characteristics before curing and excellent in adhesiveness, heat resistance and bending resistance after curing. Moreover, according to this invention, the hardened|cured material of this curable resin composition, and the adhesive agent which uses this curable resin composition, an adhesive film, a coverlay film, and a printed wiring board can be provided.

Moreover, according to this invention, it is excellent in storage stability, and can provide the curable resin composition which can obtain the hardened|cured material excellent in low linear expansion property, adhesiveness, and long-term heat resistance. Moreover, according to this invention, the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition can be provided.

Furthermore, according to this invention, it is excellent in flexibility and workability before hardening, and can provide the curable resin composition which is excellent in adhesiveness and heat resistance after hardening. Moreover, according to this invention, the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition can be provided.

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

(Synthesis example 1-1 (production of imide oligomer 1-A))

17.2 parts by weight of 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene ("BisAniline P" manufactured by Mitsui Chemicals Fine Co., Ltd.) was dissolved in N-methylpyrrolidone (FUJIFILM). Wako Pure Chemical Co., Ltd.) 200 parts by weight. To the obtained solution, 52.0 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 2 hours. This was reacted to obtain an amide acid oligomer solution. After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain amide oligomer 1-A (imidization rate 97%) ).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 1-A contains an imide oligomer represented by the following formula (16) as a main component. In addition, the softening point of the imide oligomer 1-A was 155°C.

(Synthesis example 1-2 (production of imide oligomer 1-B))

In addition to changing 17.2 parts by weight of 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene to 21.8 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) In the same manner as in Synthesis Example 1-1, imide oligomer 1-B was obtained (imide rate 96%).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 1-B contains the imide oligomer represented by the following formula (17) as a main component. In addition, the softening point of the imide oligomer 1-B was 134°C.

(Examples 1 to 9, Comparative Examples 1 and 2)

Each material was stirred and mixed so that it might become the mixing ratio described in Tables 1 and 2, and each curable resin composition of Examples 1-9 and Comparative Examples 1 and 2 was produced.

Each of the obtained curable resin compositions was applied on a mold release PET film so as to have a thickness of 20 μm, and dried to obtain an adhesive film.

In addition, each of the obtained curable resin compositions was coated on a polyimide film (“Kapton 100H” manufactured by TORAY-DUPONT Co., Ltd.) with a thickness of 25 μm so as to have a thickness of 20 μm to prepare a polyimide film having an adhesive layer. Imide film (cover film). The mold release PET film was peeled off from the obtained adhesive film, and the lamination was carried out by a laminating machine so that the thickness might be 500 μm. The minimum melt viscosity was measured under the conditions of min, frequency of 1 Hz, strain of 1%, and measurement temperature range of 60°C to 300°C, and shown in Tables 1 and 2.

<Evaluation>

The following evaluations were performed about each curable resin composition, adhesive film, or coverlay obtained in Examples 1 to 9 and Comparative Examples 1 and 2. The results are shown in Tables 1 and 2.

(Exudation resistance)

After forming a 5mmΦ hole on the cover films obtained in Examples 1 to 9 and Comparative Examples 1 and 2, they were heated and crimped to copper with L/S=100μm/100μm under the conditions of 190°C, 3MPa, and 1 hour. For the flexible copper-clad laminate of the wiring pattern, the resin length that bleeds out to the inside of the hole was measured as the bleed amount. The case where there was no exudation (the amount of exudation was less than 0.2 mm) was marked as "○", the case where the amount of exudation was 0.2 mm or more and 0.5 mm or less was marked as "△", and the case where the amount of exudation exceeded 0.5 mm was marked as "×". The anti-bleeding property was evaluated.

(filling)

The cover films obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were heated and crimped under the conditions of 190° C., 3 MPa, and 1 hour to a flexible coating having a copper wiring pattern of L/S=100 μm/100 μm. The copper laminate was observed with an optical microscope for the presence or absence of voids between the copper wiring patterns.

The case where there is no space between the wirings and the fillability is good is marked as "○", the case where there is a slight space between the wirings but the fillability is generally good is marked as "△", and the case where there are many voids between the wirings and the fillability is insufficient is marked as "△". "X", and the filling property was evaluated.

(adhesion)

The PET film was peeled off from the adhesive films obtained in Examples 1 to 9 and Comparative Examples 1 and 2, and a laminating machine was used to heat it to 70°C while laminating a polyimide substrate (TORAY-DUPONT) on both sides of the adhesive layer. "Kapton 200H" manufactured by the company, 50μmt). After hot pressing was performed under the conditions of 190° C., 3 MPa, and 1 hour to harden the adhesive layer, it was cut out to a width of 1 cm to obtain a test piece.

Using a tensile tester (“UCT-500” manufactured by ORIENTEC Corporation), T-peeling was performed at a peeling speed of 20 mm/min, and the adhesive force was measured.

The case where the bonding force is 3.4N/cm or more is marked as "○", the case where the bonding force is more than 2.0N/cm and less than 3.4N/cm is marked as "△", and the case where it is less than 2.0N/cm is marked as "×" , while assessing adherence.

(heat resistance (glass transition temperature))

The PET film was peeled off from the adhesive films obtained in Examples 1 to 9 and Comparative Examples 1 and 2, and the laminate was laminated to a thickness of 500 μm using a laminator. By heating the obtained laminated film at 190 degreeC for 30 minutes, it was hardened, and the hardened|cured material was produced. About the obtained cured product, using a thermomechanical analyzer (“TMA/SS-6000” manufactured by Hitachi High-Tech Science Co., Ltd.), under the conditions of a load of 5 g, a heating rate of 10° C./min, and a sample length of 1 cm, the temperature was changed from 0° C. The temperature was raised to 300°C, and the inflection point of the SS curve obtained at this time was obtained as the glass transition temperature.

(Heat resistance (5% weight reduction temperature))

The PET film was peeled off from the adhesive films obtained in Examples 1 to 9 and Comparative Examples 1 and 2, and the laminate was laminated to a thickness of 500 μm using a laminator. The obtained laminated film was heated at 190 degreeC for 30 minutes, and it hardened, and produced the hardened|cured material.

About the obtained cured product, 5% by weight was measured at a temperature range of 30°C to 500°C and a temperature rise of 10°C/min using a thermogravimetric measuring device ("TG/DTA6200" manufactured by Hitachi High-Tech Science Corporation). Reduce temperature.

(heat resistance (long-term heat resistance))

A test piece was obtained in the same manner as in the above-mentioned "(adhesion)", which was subjected to heat treatment at 175° C. for 1000 hours. For the test piece after the heat treatment, the adhesive force was measured by the same measurement method as the above-mentioned "(adhesion)".

The case where the bonding force is 3.4N/cm or more is marked as "○", the case where the bonding force is more than 2.0N/cm and less than 3.4N/cm is marked as "△", and the case where it is less than 2.0N/cm is marked as "×" , and the heat resistance (long-term heat resistance) was evaluated.

(bending resistance)

The pattern of the bending resistance test sample disclosed in JIS C 6471 was made on the polyimide flexible copper-clad substrate, and the pattern of the test sample for bending resistance disclosed in JIS C 6471 was heated and crimped on it under the conditions of 190 ° C, 3 MPa, and 1 hour. Example 1~ 9 and the cover films obtained in Comparative Examples 1 and 2 to obtain test pieces. Using an FPC high-speed bending tester (manufactured by Shin-Etsu Engineering Co., Ltd.), the change in resistance value was measured under the conditions of a vibration frequency of 1500 cpm, a stroke of 20 mm, a curvature of 2.5 mmR, and the outer side of the coating layer. When cracks such as cracks are generated in the copper foil due to bending, a reduction in volume and an increase in resistance are caused, and the bending characteristics were evaluated using this point. The number of times required to increase the resistance value by 20% or more was measured, and the case of more than 300,000 times was recorded as "○", the case of more than 50,000 times and less than 300,000 times was recorded as "△", and the case of less than 50,000 times It was marked with "X", and the bending resistance was evaluated.

(Synthesis example 2-1 (production of imide oligomer 2-A))

29.2 parts by weight of 1,3-bis(3-aminophenoxy)benzene (“APB-N” manufactured by Mitsui Chemicals Fine Co., Ltd.) was dissolved in N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.) 200 parts by weight. To the obtained solution, 62.0 parts by weight of 4,4'-oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the solution was stirred at 25° C. for 2 hours to react to obtain an amide acid oligomer solution. . After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain amide oligomer 2-A (imidization rate 95.0%) ).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-A is an imide oligomer represented by the formula (6) (X is the formula (7-2). ) represented by a tetravalent group, Y is a divalent group represented by the formula (8-2) (Z is a divalent group having an aromatic ring represented by the following formula (18))) as main components. In addition, the softening point of the imide oligomer 2-A was 138°C.

In formula (18), * is a bonding position.

(Synthesis example 2-2 (production of imide oligomer 2-B))

5.4 parts by weight of 1,3-phenylenediamine (“1,3-PDA” manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 parts by weight of N-methylpyrrolidone. To the obtained solution, 52.0 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 2 hours. This was reacted to obtain an amide acid oligomer solution. After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain amide oligomer 2-B (imidization rate 93%) ).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-B is an imide oligomer represented by the formula (6) (X is the formula (7-3). ) represents a tetravalent group, and Y represents a divalent group represented by the formula (8-4) (R ¹¹ to R ¹⁴ are hydrogen atoms) as main components. In addition, the softening point of the imide oligomer 2-B was 146°C.

(Synthesis example 2-3 (production of imide oligomer 2-C))

In addition to changing 5.4 parts by weight of 1,3-phenylenediamine to 5.4 parts by weight of 1,4-phenylenediamine ("1,4-PDA" manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Synthesis Example 2- 2 The imide oligomer 2-C was obtained in the same manner (the imide rate was 94%).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-C is an imide oligomer represented by the formula (6) (X is the formula (7-3) ) represents a tetravalent group, and Y represents a divalent group represented by the formula (8-3) (R ⁷ to R ¹⁰ are hydrogen atoms) as main components. In addition, the softening point of the imide oligomer 2-C was 151°C.

(Synthesis example 2-4 (production of imide oligomer 2-D))

In addition to changing 5.4 parts by weight of 1,3-phenylenediamine to 12.4 parts by weight of 4,4'-diaminodiphenyl benzene ("DDPS" manufactured by Tokyo Chemical Industry Co., Ltd.), the same method as in Synthesis Example 2 -2 The imide oligomer 2-D was obtained in the same manner (the imide rate was 95%).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-D is an imide oligomer represented by the formula (6) (X is the formula (7-3). ) represented by a tetravalent group, Y is a divalent group represented by the formula (8-1) (Z is a sulfonyl group)) as main components. In addition, the softening point of the imide oligomer 2-D was 147°C.

(Synthesis example 2-5 (production of imide oligomer 2-E))

In addition to changing 5.4 parts by weight of 1,3-phenylenediamine to 21.6 parts by weight of bis(4-(3-aminophenoxy)phenyl) bis(4-(3-aminophenoxy)phenyl) ("BAPS" manufactured by Tokyo Chemical Industry Co., Ltd.) In the same manner as in Synthesis Example 2-2, imide oligomer 2-E was obtained (imide rate 97%).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-E is an imide oligomer represented by the formula (6) (X is the formula (7-3). ), and Y is a divalent group represented by the formula (8-2) (Z is a divalent group having an aromatic ring represented by the following formula (19)) as main components. In addition, the softening point of the imide oligomer 2-E was 147°C.

In formula (19), * is a bonding position.

(Synthesis example 2-6 (production of imide oligomer 2-F))

In addition to changing 5.4 parts by weight of 1,3-phenylenediamine to 14.6 parts by weight of 1,3-bis(4-aminophenoxy)benzene (“TPE-R” manufactured by Tokyo Chemical Industry Co., Ltd.) In the same manner as in Synthesis Example 2-2, imide oligomer 2-F was obtained (imide rate 94%).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-F is an imide oligomer represented by the formula (6) (X is the formula (7-3). ) represented by a tetravalent group, Y is a divalent group represented by the formula (8-1) (Z is a divalent group having an aromatic ring represented by the above formula (18))) as main components. In addition, the softening point of the imide oligomer 2-F was 137°C.

(Synthesis example 2-7 (production of imide oligomer 2-G))

Acrylic acid was obtained in the same manner as in Synthesis Example 2-2, except that 5.4 parts by weight of 1,3-phenylenediamine was changed to 8.9 parts by weight of diethyltoluenediamine (“Ethacure 100” manufactured by Albemarle Corporation) Imine oligomer 2-G (imidization rate 98%).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-G is an imide oligomer represented by the formula (6) (X is the formula (7-3) ) represented by a tetravalent group, Y is a bivalent group represented by the formula (8-4) (one of R ¹¹ and R ¹² is a methyl group, the other is an ethyl group, R ¹³ is a hydrogen atom, R ¹⁴ is ethyl)) as the main component. In addition, the softening point of the imide oligomer 2-G was 150°C.

(Synthesis example 2-8 (production of imide oligomer 2-H))

Imide was obtained in the same manner as in Synthesis Example 2-1, except that 29.2 parts by weight of 1,3-bis(3-aminophenoxy)benzene was changed to 17.8 parts by weight of diethyltoluenediamine Oligomer 2-H (95% imidization rate).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-H is an imide oligomer represented by the formula (6) (X is the formula (7-2). ) represented by a tetravalent group, Y is a bivalent group represented by the formula (8-4) (one of R ¹¹ and R ¹² is a methyl group, the other is an ethyl group, R ¹³ is a hydrogen atom, R ¹⁴ is ethyl)) as the main component. In addition, the softening point of the imide oligomer 2-H was 183°C.

(Synthesis example 2-9 (production of imide oligomer 2-1))

In addition to changing 5.4 parts by weight of 1,3-phenylenediamine to 9.9 parts by weight of 4,4'-diaminodiphenylmethane ("DDM" manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in Synthesis Example 2 was carried out. -2 The imide oligomer 2-1 was obtained in the same manner (imide rate 95%).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-I is an imide oligomer represented by the formula (6) (X is the formula (7-3) ) represented by a tetravalent group, Y is a divalent group represented by the formula (8-1) (Z is a methylene group)) as main components. In addition, the softening point of the imide oligomer 2-I was 147°C.

(Synthesis example 2-10 (production of imide oligomer 2-J))

29.2 parts by weight of 1,3-bis(3-aminophenoxy)benzene was changed to 19.8 parts by weight of 4,4'-diaminodiphenylmethane, and 4,4'-oxydiphthalic acid was Except that 62.0 parts by weight of dianhydride was changed to 58.8 parts by weight of 4,4'-biphenyltetracarboxylic dianhydride, imide oligomer 2-J (imide Amination rate of 96%).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-J has a biphenyl skeleton in the part corresponding to X in the formula (6), and a part corresponding to Y in the formula (6). An imide oligomer of a divalent group (Z is a methylene group) represented by formula (8-1) is used as a main component. In addition, the softening point of the imide oligomer 2-J exceeded 300°C.

(Synthesis Example 2-11 (Preparation of imide oligomer 2-K))

Acrylic acid was obtained in the same manner as in Synthesis Example 2-2, except that 5.4 parts by weight of 1,3-phenylenediamine was changed to 7.7 parts by weight of norbornanediamine ("NBDA" manufactured by Mitsui Chemicals Fine Co., Ltd.) Imine oligomer 2-K (97% imidization rate).

Furthermore, by ¹ H-NMR, GPC and FT-IR analysis, it was confirmed that the imide oligomer 2-K is 4 represented by the formula (7-3) in the part corresponding to X in the formula (6). A valence group and an imide oligomer whose part corresponding to Y is a norbornane skeleton serves as a main component. In addition, the softening point of the imide oligomer 2-K was 137°C.

(Synthesis example 2-12 (production of imide oligomer 2-L))

62.0 parts by weight of 4,4'-oxydiphthalic dianhydride was changed to 26.0 parts by weight of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, except Otherwise, the imide oligomer 2-L was obtained in the same manner as in Synthesis Example 2-1 (the imide rate was 94%).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 2-L contains an imide oligomer represented by the following formula (20) as a main component. The softening point of the imide oligomer 2-L was 132°C.

(Examples 10 to 20, Comparative Examples 3 to 7)

According to the mixing ratios described in Tables 3 and 4, the respective materials were stirred and mixed to prepare the curable resin compositions of Examples 10 to 20 and Comparative Examples 3 to 7.

<Evaluation>

The following evaluations were performed on each of the curable resin compositions obtained in Examples 10 to 20 and Comparative Examples 3 to 7. The results are shown in Tables 3 and 4.

(Storage stability)

For each of the curable resin compositions obtained in Examples 10 to 20 and Comparative Examples 3 to 7, the initial viscosity immediately after production and the viscosity after storage at 25° C. for 24 hours were measured. (viscosity after storage at 25°C for 24 hours)/(initial viscosity) was used as the viscosity change rate, and the case where the viscosity change rate was less than 1.5 was marked as "○", and the case where the viscosity change rate was not less than 1.5 and less than 2.0 was marked as "△" and 2.0 or more were marked as "x", and the storage stability was evaluated.

In addition, the viscosity of a curable resin composition was measured under the conditions of 25 degreeC and a rotation speed 5rpm using the E-type viscometer ("TPE-100" by Toki Sangyo Co., Ltd.).

(Linear expansion coefficient and glass transition temperature)

An adhesive film was obtained by apply|coating each curable resin composition obtained in Examples 10-20 and Comparative Examples 3-7 on a mold release PET film, and drying it. After peeling a PET film from the obtained adhesive film, it laminated, heated at 190 degreeC for 1 hour, and hardened it, and produced the hardened|cured material of thickness 400 micrometers.

The obtained cured product was subjected to a thermomechanical analyzer (“TMA/SS-6000” manufactured by Hitachi High-Tech Science Co., Ltd.), under the conditions of a load of 5 g, a heating rate of 10° C./min, and a sample length of 1 cm from 0° C. After the temperature was raised to 300°C, the temperature was once cooled, and the temperature was again raised from 0°C to 300°C under the same conditions. Based on the temperature and dimensional change data obtained in the second measurement, the average linear expansion coefficient in the temperature range of 40°C to 80°C was obtained as the linear expansion coefficient of the sample. Moreover, the inflection point of the curve which shows the relationship between the temperature and dimensional change obtained by the 2nd measurement was calculated|required, and it was set as a glass transition temperature.

(5% weight reduction temperature)

An adhesive film was obtained by apply|coating each curable resin composition obtained in Examples 10-20 and Comparative Examples 3-7 on a mold release PET film, and drying it. The PET film was peeled off from the obtained adhesive film, and it heated at 190 degreeC for 1 hour, and hardened it, and produced the hardened|cured material.

About the obtained cured product, 5% by weight was measured at a temperature range of 30°C to 500°C and a temperature rise of 10°C/min using a thermogravimetric measuring device ("TG/DTA6200" manufactured by Hitachi High-Tech Science Corporation). Reduce temperature.

(Initial Adhesion)

Each of the curable resin compositions obtained in Examples 10 to 20 and Comparative Examples 3 to 7 was applied to a release PET film so as to have a thickness of about 20 μm, and dried to obtain an adhesive film. The PET film was peeled off from the adhesive film, heated to 70°C using a laminating machine, and a polyimide substrate (“Kapton 200H” manufactured by TORAY-DUPONT, 50 μmt) was attached to both sides of the adhesive layer. After hot pressing was performed under the conditions of 190° C., 3 MPa, and 1 hour to harden the adhesive layer, it was cut out to a width of 1 cm to obtain a test piece.

Using a tensile tester (“UCT-500” manufactured by ORIENTEC Corporation), T-peeling was performed at a peeling speed of 20 mm/min, and the adhesive force was measured.

The case where the bonding force is 3.4N/cm or more is marked as "○", the case where the bonding force is more than 2.0N/cm and less than 3.4N/cm is marked as "△", and the case where it is less than 2.0N/cm is marked as "×" , while evaluating initial adhesion.

(Long-term heat resistance)

A test piece was obtained in the same manner as in the above-mentioned "(Initial Adhesion)", which was heat-treated at 175°C for 1000 hours. The test piece after the heat treatment was subjected to T-shaped peeling at a peeling speed of 20 mm/min using a tensile tester (“UCT-500” manufactured by ORIENTEC), and the adhesive force was measured.

The case where the bonding force is 3.4N/cm or more is marked as "○", the case where the bonding force is more than 2.0N/cm and less than 3.4N/cm is marked as "△", and the case where it is less than 2.0N/cm is marked as "×" , while evaluating long-term heat resistance.

(Synthesis example 3-1 (production of imide oligomer 3-A))

10 parts by weight of 4,4′-diaminodiphenyl ether (“DDPE” manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 parts by weight of N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.). To the obtained solution, 52.0 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 2 hours. This was reacted to obtain an amide acid oligomer solution. After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain amide oligomer 3-A (imidization rate 92%) ).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 3-A contains an imide oligomer represented by the following formula (21) as a main component. In addition, the softening point of the imide oligomer 3-A was 147°C and the melting point was 168°C.

(Synthesis example 3-2 (production of imide oligomer 3-B))

In addition to changing 10 parts by weight of 4,4'-diaminodiphenyl ether to 5.4 parts by weight of 1,4-phenylenediamine ("1,4-PDA" manufactured by Tokyo Chemical Industry Co., Ltd.) In the same manner as in Synthesis Example 3-1, imide oligomer 3-B was obtained (imide rate 95%).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 3-B contains an imide oligomer represented by the following formula (22) as a main component. In addition, the softening point of the imide oligomer 3-B was 151°C and the melting point was 168°C.

(Synthesis example 3-3 (production of imide oligomer 3-C))

In 200 parts by weight of N-methylpyrrolidone, 21.6 parts by weight of bis(4-(3-aminophenoxy)phenyl) bismuth ("BAPS" manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved. To the obtained solution, 31.0 parts by weight of 4,4'-oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the solution was stirred at 25° C. for 2 hours to react to obtain an amide acid oligomer solution. . After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain amide oligomer 3-C (imidization rate 98%) ).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 3-C contains an imide oligomer represented by the following formula (23) as a main component. In addition, the softening point of the imide oligomer 3-C was 166°C and the melting point was 181°C.

(Synthesis example 3-4 (production of imide oligomer 3-D))

17.2 parts by weight of 1,4-bis(2-(4-aminophenyl)-2-propyl)benzene (“BisAniline P” manufactured by Mitsui Chemicals Fine Co., Ltd.) was dissolved in 200 parts by weight of N-methylpyrrolidone share. To the obtained solution, 32.2 parts by weight of 4,4'-carbonyldiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the solution was stirred at 25° C. for 2 hours to react to obtain an amide acid oligomer solution. . After removing N-methylpyrrolidone under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain amide oligomer 3-D (imidization rate 96%) ).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 3-D contains an imide oligomer represented by the following formula (24) as a main component. In addition, the softening point of the imide oligomer 3-D was 228°C and the melting point was 273°C.

(Synthesis example 3-5 (production of imide oligomer 3-E))

12.9 parts by weight of 4,4'-diamino-3,3'-dihydroxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 parts by weight of N-methylpyrrolidone (manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.). To the obtained solution, 52.0 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was added, and the reaction was stirred at 25°C for 2 hours to obtain acyl A solution of amino acid oligomer (A). After the N-methylpyrrolidone was removed under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain an amide imine oligomer having an acid anhydride group at the end (the amide imide ratio 95%).

Furthermore, 61.6 parts by weight of the obtained imide oligomer was weighed and dissolved in 200 parts by weight of N-methylpyrrolidone, and then 10.9 parts by weight of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, It was made to react by stirring at 25 degreeC for 2 hours, and the solution of an amide|amid acid oligomer (B) was obtained. After removing N-methylpyrrolidone under reduced pressure from the solution of the obtained amide acid oligomer (B), it was heated at 300° C. for 2 hours to obtain amide oligomer 3-E (amide imine oligomer 3-E). conversion rate of 93%).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 3-E was mainly composed of an imide oligomer represented by the following formula (25). In addition, the softening point of the imide oligomer 3-E was 198°C and the melting point was 223°C.

(Synthesis example 3-6 (production of imide oligomer 3-F))

10 parts by weight of 4,4'-diaminodiphenyl ether was changed to 1,3-bis(2-(4-aminophenyl)-2-propyl)benzene ("Dianiline" manufactured by Mitsui Chemicals Fine Co., Ltd. M") 17.2 parts by weight, except that, in the same manner as in Synthesis Example 3-1, an imide oligomer 3-F (94% imidization rate) was obtained.

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 3-F was mainly composed of an imide oligomer represented by the following formula (26). In addition, the softening point of the imide oligomer 3-F was 145°C and the melting point was 158°C.

(Synthesis example 3-7 (production of imide oligomer 3-G))

10.9 parts by weight of 3-aminophenol was dissolved in 200 parts by weight of N-methylpyrrolidone. To the obtained solution, 26.0 parts by weight of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was added, and the reaction was stirred at 25°C for 2 hours to obtain acyl Amino acid oligomer solution. After the N-methylpyrrolidone was removed under reduced pressure from the obtained amide acid oligomer solution, it was heated at 300° C. for 2 hours to obtain amide oligomer 3-G (imidization rate 95%) ).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 3-G contains an imide oligomer represented by the following formula (27) as a main component. In addition, the softening point of the imide oligomer 3-G was 137°C and the melting point was 155°C.

(Synthesis example 3-8 (production of imide oligomer 3-H))

In addition to changing 10 parts by weight of 4,4'-diaminodiphenyl ether to 5.4 parts by weight of 1,3-phenylenediamine ("1,3-PDA" manufactured by Tokyo Chemical Industry Co., Ltd.) In the same manner as in Synthesis Example 3-1, imide oligomer 3-H was obtained (imide rate 95%).

Furthermore, by ¹ H-NMR, GPC, and FT-IR analysis, it was confirmed that the imide oligomer 3-H was mainly composed of the imide oligomer represented by the formula (28). In addition, the softening point of the imide oligomer 3-H was 146°C and the melting point was 163°C.

(Examples 21 to 31, Comparative Examples 8 and 9)

The imide oligomers 3-A to 3-H obtained in Synthesis Examples 3-1 to 3-8 were pulverized using a jet mill, and then mixed with methyl ethyl ketone to obtain mixed solutions (each The average particle size of imide oligomer is 4 ~ 10μm). The imide oligomers 3-A~3-E and 3-H are insoluble in methyl ethyl ketone, and the imide oligomers 3-F and 3-G are soluble in methyl ethyl ketone. Next, the obtained mixed solution and the other materials were stirred and mixed so that each material became the mixing ratio described in Table 5, and each curable resin composition of Examples 21 to 31 and Comparative Examples 8 and 9 was produced.

About each obtained curable resin composition, the dispersion state of the imide oligomer at 25 degreeC was confirmed by optical microscope observation. As a result, it was confirmed that the imide oligomers in each of the curable resin compositions of Examples 21 to 31 using imide oligomers 3-A to 3-E and 3-H were dispersed in the form of solid particles. On the other hand, it was confirmed that the imide oligomer was dissolved in each of the curable resin compositions of Comparative Examples 8 and 9 using only the imide oligomer 3-F or 3-G.

<Evaluation>

The following evaluations were performed on each of the curable resin compositions obtained in Examples 21 to 31 and Comparative Examples 8 and 9. The results are shown in Table 5.

(flexible)

Each of the curable resin compositions obtained in Examples 21 to 31 and Comparative Examples 8 and 9 was coated on the mold release PET film, and dried to obtain an adhesive film. The obtained adhesive film was wound on a cylinder having a diameter of 5 mm at 25° C., and a winding test of a diameter of 5 mm was performed to confirm whether or not the adhesive film was cracked or damaged. Moreover, the obtained adhesive film was folded 180 degrees, and the 180 degree bending test was performed, and it was confirmed whether the adhesive film was cracked or damaged.

The case where there is no crack or breakage in the 5mm diameter winding test and 180-degree bending test will be marked as "○", and there is no crack or breakage in the 5mm diameter winding test but there is cracking in the 180-degree bending test. The case of breakage or breakage was marked as "△", and the case of breakage or breakage in both tests was marked as "X", and the flexibility was evaluated.

(workability)

The respective curable resin compositions obtained in Examples 21 to 31 and Comparative Examples 8 and 9 were coated on the release film and dried to obtain an adhesive film. The obtained adhesive film was punched with a Thomson Knife, and the state of the fractured surface and the presence or absence of powder drop were confirmed.

The case where the fracture surface was smooth and no powder fell was marked as "○", and the case where the fracture surface was not smooth and powder fell was marked as "x", and the workability was evaluated.

(adhesion)

Each of the curable resin compositions obtained in Examples 21 to 31 and Comparative Examples 8 and 9 was applied to a release PET film so as to have a thickness of about 20 μm, and dried to obtain an adhesive film. The PET film was peeled off from the adhesive film, heated to 70° C. using a laminating machine, and a polyimide substrate (“Kapton 200H” manufactured by TORAY-DUPONT, 50 μmt) was attached to both sides of the adhesive layer. After hot pressing was performed under the conditions of 190° C., 3 MPa, and 1 hour to harden the adhesive layer, it was cut out to a width of 1 cm to obtain a test piece.

Using a tensile tester (“UCT-500” manufactured by ORIENTEC Corporation), T-peeling was performed at a peeling speed of 20 mm/min, and the adhesive force was measured. The case where the bonding force is 6.0N/cm or more is marked as "◎", the case where the bonding force is more than 3.4N/cm and less than 6.0N/cm is marked as "○", and the case where the bonding force is more than 2.0N/cm and less than 3.4N/cm The case was marked with "△", and the case less than 2.0 N/cm was marked with "X", and the adhesion was evaluated.

(heat resistance (glass transition temperature))

Each of the curable resin compositions obtained in Examples 21 to 31 and Comparative Examples 8 and 9 was coated on a mold release PET film, and dried to obtain a curable resin composition film. The PET film was peeled off from the obtained curable resin composition film, and after laminating|stacking using a laminator, it hardened by heating at 190 degreeC for 1 hour, and produced the hardened|cured material of thickness 500micrometer. The obtained cured product was subjected to a thermomechanical analyzer (“TMA/SS-6000” manufactured by Hitachi High-Tech Science Co., Ltd.), under the conditions of a load of 5 g, a heating rate of 10° C./min, and a sample length of 1 cm from 0° C. The temperature was raised to 300°C, and the inflection point of the SS curve obtained at this time was determined as the glass transition temperature.

(Heat resistance (5% weight reduction temperature))

The adhesive films were obtained by applying the respective curable resin compositions obtained in Examples 21 to 31 and Comparative Examples 8 and 9 on a release film and drying them. By heating the obtained adhesive film at 190 degreeC for 1 hour, it was hardened, and the hardened|cured material was produced.

About the obtained cured product, 5% by weight was measured at a temperature range of 30°C to 500°C and a temperature rise of 10°C/min using a thermogravimetric measuring device ("TG/DTA6200" manufactured by Hitachi High-Tech Science Corporation). Reduce temperature.

[Industrial Availability]

According to the present invention, it is possible to provide a curable resin composition which is excellent in flow characteristics before curing and excellent in adhesiveness, heat resistance and bending resistance after curing. Moreover, according to this invention, the hardened|cured material of this curable resin composition, and the adhesive agent which uses this curable resin composition, an adhesive film, a coverlay film, and a printed wiring board can be provided.

Moreover, according to this invention, it is excellent in storage stability, and can provide the curable resin composition which can obtain the hardened|cured material excellent in low linear expansion property, adhesiveness, and long-term heat resistance. Moreover, according to this invention, the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition can be provided.

Furthermore, according to this invention, it is excellent in flexibility and workability before hardening, and can provide the curable resin composition which is excellent in adhesiveness and heat resistance after hardening. Moreover, according to this invention, the hardened|cured material of this curable resin composition, and the adhesive agent and adhesive film which use this curable resin composition can be provided.

Claims (25)

A curable resin composition comprising a thermosetting resin, a thermoplastic resin and an imide oligomer, wherein the thermosetting resin contains an epoxy resin, and the imide oligomer has the ability to react with the thermosetting resin The reactive functional group is an acid anhydride group and/or a phenolic hydroxyl group. The curable resin composition according to claim 1, wherein the thermoplastic resin contains a phenoxy resin. The curable resin composition according to claim 1 or 2, wherein the content of the thermoplastic resin in a total of 100 parts by weight of the thermosetting resin, the thermoplastic resin and the imide oligomer is 1 part by weight more than 60 parts by weight or less. The curable resin composition according to claim 1 or 2, wherein the imidization rate of the imide oligomer is 70% or more. The curable resin composition according to claim 1 or 2, which has a minimum melt viscosity of 5 kPa·s or more and 300 kPa·s or less. An adhesive comprising the curable resin composition described in claim 1, 2, 3, 4 or 5. A cured product, which is a cured product of the curable resin composition according to claim 1, 2, 3, 4 or 5. An adhesive film, which is formed by using the adhesive described in claim 6. A coverlay film comprising an adhesive layer composed of the cured product described in claim 7, and an insulating film. A flexible printed wiring board having the cover film described in claim 9. A curable resin composition comprising a curable resin, an imide oligomer and a curing accelerator, wherein the curable resin contains an epoxy resin, and the imide oligomer is represented by the following formula (6 ) represents that the softening point is 250°C or less, the imidization rate is 70% or more, and the above-mentioned hardening accelerator is an alkaline catalyst,

In formula (6), X is a tetravalent group represented by the following formula (7-1), (7-2) or (7-3), and Y is the following formula (8-1), (8-2) ), (8-3) or (8-4) represented by the divalent base,

In the formulas (7-1)~(7-3), * is the bonding position; the hydrogen atoms of the aromatic rings in the formulas (7-1)~(7-3) can be substituted;

In formulas (8-1) and (8-2), Z is a bonding bond, an oxygen atom, a sulfonyl group, a linear or branched divalent hydrocarbon group which may have an oxygen atom at the bonding position, or a bonding A divalent group having an aromatic ring which may have an oxygen atom at the position; the hydrogen atom of the aromatic ring in the formulas (8-1) and (8-2) may be substituted; in the formulas (8-3) and (8-4) , R ⁷ to R ¹⁴ represent a hydrogen atom or a monovalent hydrocarbon group, which may be the same or different; in formulas (8-1) to (8-4), * is a bonding position. The curable resin composition according to claim 11, wherein the curing accelerator has an imidazole skeleton. The curable resin composition according to claim 11 or 12, wherein the content of the hardening accelerator in 100 parts by weight of the total of the curable resin, the imide oligomer, and the hardening accelerator is 0.8 weight parts part or more and 10 parts by weight or less. A hardened product, which is a hardened product of the curable resin composition described in claim 11, 12 or 13. The cured product as claimed in claim 14, which is flat in the temperature range of 40°C to 80°C The mean linear expansion coefficient is 60 ppm or less. An adhesive comprising the curable resin composition of claim 11, 12 or 13. An adhesive film using the curable resin composition according to claim 11, 12 or 13. A curable resin composition comprising a curable resin and an imide oligomer, wherein the curable resin is liquid at 25° C., the curable resin contains an epoxy resin, and the imine oligomer is The product has a reactive functional group capable of reacting with the curable resin, the reactive functional group is an acid anhydride group and/or a phenolic hydroxyl group, and the imide oligomer is dispersed in the form of solid particles at 25°C. The curable resin composition according to claim 18, wherein the softening point of the imide oligomer is 250°C or lower. The curable resin composition according to claim 18 or 19, wherein the imidization rate of the imide oligomer is 70% or more. The curable resin composition according to claim 18 or 19, comprising an imide oligomer that is insoluble in the curable resin composition at 25°C and an imide oligomer that is soluble in the curable resin composition at 25°C The oligomer is used as the above-mentioned imide oligomer. The curable resin composition according to claim 21, wherein the content ratio of the imide oligomer soluble in the curable resin composition at 25°C is 100 parts by weight of the entire imide oligomer 80 parts by weight or less. A hardened product, which is a hardened product of the curable resin composition described in claim 18, 19, 20, 21 or 22. An adhesive comprising the curable resin composition described in claim 18, 19, 20, 21 or 22. An adhesive film, which is formed by using the adhesive described in claim 24.