JP2015117278A - Functionalized polyimide resin and epoxy resin composition including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide resin excellent in characteristics, a method for producing a polyimide resin, and an epoxy resin composition including the polyimide resin, and to provide an adhesive or a coating using an epoxy resin composition, and an article using the same.SOLUTION: An epoxy resin composition includes: (I) a polyimide resin comprising a repeating unit represented by general formula (1) and a functional group at a molecular chain terminal; (II) an epoxy resin comprising 2 or more of epoxy groups in a molecule; and (III) a curing agent capable of curing the epoxy groups of (II).

Description

  The present invention provides a novel functionalized polyimide resin, a method for producing the functionalized polyimide resin, an epoxy resin composition containing the functionalized polyimide resin, and an adhesive or coating using the epoxy resin composition , And articles using the same.

  In recent years, polyimide resins have been widely used for the purpose of reducing the size, weight, and flexibility of devices, particularly in the electric and electronic fields. This is due to the excellent heat resistance, chemical stability, and electrical insulation properties of the polyimide resin, and is intended for insulation, protection, and the like. In general, the polyimide resin used for such applications is limited to supply in a film-like state. In addition, especially in the electric and electronic fields, it is necessary to adhere to copper (Cu) foil for circuit formation, but polyimide cannot be said to have good adhesion to other materials, and there are other resin-based adhesives. It is necessary (for example, Patent Document 1), and this adhesive is thermally deteriorated at a high temperature by, for example, lead-free solder, or under a high temperature / high humidity condition (generally 85 ° C., 85% relative humidity in the electric / electronic field, The condition of 1000 hours is often required), causing a problem of hydrolysis degradation. In addition, there is a problem that resistance to the etching solution of the copper (Cu) foil is often not obtained.

  In order to avoid the above problems, generally, the main component is an epoxy resin composition that has excellent adhesiveness and can withstand relatively high temperatures and high humidity, and a polyamide resin or polyamide elastomer is added or partially reacted. Thus, a technique for obtaining flexibility has been developed (for example, Patent Documents 2 to 3). However, the resistance under high temperature and high humidity conditions and the etchant resistance are still insufficient.

JP 2010-168510 A JP 2011-46782 A JP 2012-233101A JP2013-155329A Japanese Patent Laid-Open No. 11-228691

The present inventors have developed a polyimide resin excellent in solubility in a solvent containing an aromatic tetracarboxylic acid residue and a dimer diamine residue at a certain content (Patent Document 4). However, further improvement of the polyimide resin has been expected in order to reduce the size, weight, and flexibility of devices in the electric / electronic field.
An object of the present invention is to provide a polyimide resin having excellent characteristics, a method for producing the polyimide resin, an epoxy resin composition containing the polyimide resin, an adhesive or a coating using the epoxy resin composition, and an article using the same. Is to provide.

（式中、Ｒ^１は、繰り返し単位ごとに同一又は異なり、非置換若しくは置換された炭素数０〜６６の脂肪族テトラカルボン酸残基、脂環族テトラカルボン酸残基、及び／又は芳香族テトラカルボン酸残基であり；Ｒ^２は、繰り返し単位ごとに同一又は異なり、非置換若しくは置換された炭素数２〜５６の脂肪族ジアミン残基、脂環族ジアミン残基、及び芳香族ジアミン残基からなる群から選択される少なくとも１つのジアミン残基、及び炭素数２０〜４８の重合脂肪酸から誘導されるダイマージアミン残基であり；前記ジアミン残基と前記ダイマージアミン残基との重量比が０：１００〜９０：１０であり、イミド結合の比率が５０％を超えるものである）で表される繰り返し単位を有し、分子鎖末端に官能基を有するポリイミド樹脂、（II）一分子中に２個以上のエポキシ基を有するエポキシ樹脂、及び（III）（II）のエポキシ基を硬化することのできるエポキシ樹脂硬化剤、を含有するエポキシ樹脂組成物、
［２］前記繰り返し単位のイミド結合の比率が９０％以上である、［１］に記載のエポキシ樹脂組成物、
［３］前記ポリイミド樹脂の末端官能基がカルボキシル基、フェノール性水酸基、及びアミノ基からなる群から選択される官能基である、［１］又は［２］に記載のエポキシ樹脂組成物、
［４］前記一般式（１）で表される繰り返し単位を有し、分子鎖末端に官能基を有するポリイミド樹脂
［５］前記分子鎖末端の官能基が、カルボキシル基、フェノール性水酸基、及びアミノ基からなる群から選択される官能基である、［４］に記載のポリイミド樹脂
［６］（Ｉ）一般式（２）：

（式中、Ｒ^１は、非置換若しくは置換された炭素数０〜６６の脂肪族テトラカルボン酸残基、脂環族テトラカルボン酸残基、又は芳香族テトラカルボン酸残基である）で表されるテトラカルボン酸二無水物１つ以上、（II）一般式（３）

（式中、Ｒ^２は、非置換若しくは置換された炭素数２〜５６の脂肪族ジアミン残基、脂環族ジアミン残基、及び芳香族ジアミン残基からなる群から選択される少なくとも１つのジアミン残基である）で表される脂肪族、脂環族、及び／又は芳香族ジアミン１つ以上、及び（III）炭素数２０〜４８の重合脂肪酸から誘導されるダイマージアミン１つ以上
を、前記脂肪族、脂環族、及び／又は芳香族ジアミンと、前記ダイマージアミンとの重量比が、０：１００〜９０：１０の条件で反応させ、ポリアミック酸を得る第一工程；及び前記ポリアミック酸をイミド化する第二工程；を含み、末端に官能基を導入するために、前記第一工程又は第二工程に、カルボキシル基１つ及び酸無水物基１つを含む化合物、カルボキシル基１つ及びアミノ基１つを含む化合物、カルボキシル基２つ及びアミノ基１つを含む化合物、フェノール性水酸基１つ及びアミノ基１つを含む化合物、及び２級アミノ基２つを含む化合物からなる群から選択される少なくとも１つの化合物を添加することを特徴とするポリイミド樹脂の製造方法、
［７］（Ｉ）前記一般式（２）で表されるテトラカルボン酸二無水物１つ以上、（II）前記一般式（３）で表される脂肪族、脂環族、及び／又は芳香族ジアミン１つ以上、及び（III）炭素数２０〜４８の重合脂肪酸から誘導されるダイマージアミン１つ以上、を前記脂肪族、脂環族、及び／又は芳香族ジアミンと、前記ダイマージアミンとの重量比が、０：１００〜９０：１０の条件で反応させ、ポリアミック酸を得る第一工程であって、末端に官能基を導入するために、ジアミンに対するテトラカルボン酸二無水物の当量比を０．５以上１．０未満とする第一工程；及び前記ポリアミック酸をイミド化する第二工程；
を含むことを特徴とするポリイミド樹脂の製造方法、
［８］［６］又は［７］に記載の製造方法によって製造される、ポリイミド樹脂、
［９］［１］〜［５］のいずれかに記載のエポキシ樹脂組成物を含むことを特徴とするエポキシ樹脂接着剤、
［１０］［１］〜［５］のいずれかに記載のエポキシ樹脂組成物を含むことを特徴とするエポキシ樹脂コーティング剤、及び
［１１］［９］に記載のエポキシ樹脂接着剤、又は［１０］に記載のエポキシ樹脂コーティング剤が塗布された物品、
に関する。 As a result of earnest research on the polyimide resin capable of solving the above problems, the inventor has surprisingly called a polyimide resin having a functional group at the molecular chain end (hereinafter referred to as “functionalized polyimide”). It has been found that the toughness of the cured product obtained from the polyimide resin composition is improved by incorporating (A) in the epoxy resin composition. Furthermore, the present inventors have also found that the functionalized polyimide has excellent compatibility with an epoxy resin.
The present invention is based on these findings.
Therefore, the present invention
[1] (I) General formula (1):

(In the formula, R ¹ is the same or different for each repeating unit, and is an unsubstituted or substituted aliphatic tetracarboxylic acid residue having 0 to 66 carbon atoms, an alicyclic tetracarboxylic acid residue, and / or aromatic. A tetracarboxylic acid residue; R ² is the same or different for each repeating unit, and is an unsubstituted or substituted aliphatic diamine residue having 2 to 56 carbon atoms, an alicyclic diamine residue, and an aromatic diamine residue. At least one diamine residue selected from the group consisting of a group and a dimer diamine residue derived from a polymerized fatty acid having 20 to 48 carbon atoms; the weight ratio of the diamine residue to the dimer diamine residue is A polyimide resin having a repeating unit represented by 0: 100 to 90:10 and having a ratio of imide bonds exceeding 50%, and having a functional group at the molecular chain terminal, (II ) An epoxy resin composition comprising: an epoxy resin having two or more epoxy groups in one molecule; and an epoxy resin curing agent capable of curing the epoxy groups of (III) and (II).
[2] The epoxy resin composition according to [1], wherein the ratio of the imide bond of the repeating unit is 90% or more,
[3] The epoxy resin composition according to [1] or [2], wherein the terminal functional group of the polyimide resin is a functional group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an amino group.
[4] Polyimide resin having a repeating unit represented by the general formula (1) and having a functional group at the molecular chain terminal. [5] The functional group at the molecular chain terminal is a carboxyl group, a phenolic hydroxyl group, and an amino group. The polyimide resin according to [4], which is a functional group selected from the group consisting of groups [6] (I) General formula (2):

Wherein R ¹ is an unsubstituted or substituted aliphatic tetracarboxylic acid residue having 0 to 66 carbon atoms, an alicyclic tetracarboxylic acid residue, or an aromatic tetracarboxylic acid residue. One or more tetracarboxylic dianhydrides, (II) general formula (3)

Wherein R ² is at least one diamine selected from the group consisting of unsubstituted or substituted aliphatic diamine residues having 2 to 56 carbon atoms, alicyclic diamine residues, and aromatic diamine residues. One or more aliphatic, alicyclic, and / or aromatic diamines represented by (residues) and (III) one or more dimer diamines derived from polymerized fatty acids having 20 to 48 carbon atoms, A first step of obtaining a polyamic acid by reacting an aliphatic, alicyclic and / or aromatic diamine with the dimer diamine in a weight ratio of 0: 100 to 90:10; and the polyamic acid. A compound containing one carboxyl group and one acid anhydride group in the first step or the second step, in order to introduce a functional group at the terminal, 1 amino group At least one selected from the group consisting of: a compound containing 2; a compound containing 2 carboxyl groups and 1 amino group; a compound containing 1 phenolic hydroxyl group and 1 amino group; and a compound containing 2 secondary amino groups. A method for producing a polyimide resin, comprising adding two compounds,
[7] (I) One or more tetracarboxylic dianhydrides represented by the general formula (2), (II) aliphatic, alicyclic, and / or aromatic represented by the general formula (3) One or more aromatic diamines and (III) one or more dimer diamines derived from polymerized fatty acids having 20 to 48 carbon atoms, the aliphatic, alicyclic and / or aromatic diamines and the dimer diamines In the first step of obtaining a polyamic acid by reacting at a weight ratio of 0: 100 to 90:10, the equivalent ratio of tetracarboxylic dianhydride to diamine is set to introduce a functional group at the terminal. A first step of 0.5 or more and less than 1.0; and a second step of imidizing the polyamic acid;
A method for producing a polyimide resin, comprising:
[8] A polyimide resin produced by the production method according to [6] or [7],
[9] An epoxy resin adhesive comprising the epoxy resin composition according to any one of [1] to [5],
[10] An epoxy resin coating agent comprising the epoxy resin composition according to any one of [1] to [5], and an epoxy resin adhesive according to [11] [9], or [10 ] An article coated with the epoxy resin coating agent according to
About.

According to the epoxy resin composition containing the functionalized polyimide resin of the present invention, in addition to being excellent in adhesion and heat resistance to various base materials, which is a feature of the epoxy resin composition, it is often a problem in the epoxy resin field. Can be toughened. In addition, deterioration due to thermal decomposition, hydrolysis and the like does not occur even under conditions of high temperature and high humidity required particularly in the electric / electronic field. In addition, since the functionalized polyimide resin of the present invention is soluble in a general-purpose solvent, it can be dissolved in a solvent together with an epoxy resin and an epoxy resin curing agent by a common solvent method, and a coating film can be easily prepared by wet coating. The excellent properties of polyimide can be imparted to the epoxy resin composition.
Furthermore, in the polyimide resin described in Patent Document 4, aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride could not be used as the tetracarboxylic acid residue component. In the functionalized polyimide resin of the invention, an aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride can be used. Compared with aromatic tetracarboxylic dianhydride, when using aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride as a tetracarboxylic acid residue component, solvent solubility of polyimide, And epoxy compatibility is further improved. Moreover, when the polyimide which has these tetracarboxylic acid residues is used for an epoxy resin composition, the improvement effect of the toughness of an epoxy hardened | cured material is excellent. Furthermore, the base-material adhesiveness of an epoxy resin composition is improved.

[1] Functionalized polyimide resin The functionalized polyimide resin of the present invention has a repeating unit represented by the general formula (1) and has a functional group at the end of the molecular chain.
The functionalized polyimide resin of the present invention can be obtained by a method for producing a functionalized polyimide resin described later. However, the polyimide resin of this invention is not limited to what was obtained by the manufacturing method of the polyimide resin mentioned later.
In the present specification, the “residue” of the tetracarboxylic acid residue and the “residue” of the diamine residue are the residues of R ¹ bonded to the four carbon atoms of the general formula (1), respectively. And a residue of R ² bonded to two nitrogen atoms of the general formula (1).

  The number of repeating units contained in the functionalized polyimide resin of the present invention is not particularly limited. In addition, the number average molecular weight of the functionalized polyimide resin of the present invention is not particularly limited. However, the number average molecular weight is preferably 2,000 to 50,000 in GPC (gel permeation chromatography). More preferably, it is 3,000 to 40,000, and most preferably 5,000 to 25,000. In other words, since the functionalized polyimide resin of the present invention has functional groups at both ends, the acid value, hydroxyl value, or amine value is preferably 2 to 50, more preferably 3 to 40, and most preferably 5 to 5. 25. When the molecular weight is less than 2,000, the mechanical properties of the functionalized polyimide resin obtained, particularly the tensile strength and elongation, that is, the brittleness may be extremely lowered. On the other hand, when the molecular weight exceeds 50,000, when the functionalized polyimide resin obtained is dissolved with a solvent, the amount of the solvent to be diluted becomes too large to be practical, and an epoxy resin composition is obtained. There is a tendency that the compatibility is sometimes lowered, which is not preferable. Further, when the epoxy resin composition is used as an adhesive or coating, there may be a problem that only a very thin adhesive layer or coating film can be obtained.

The molecular weight by GPC is a device; Shodex GPC system-21H manufactured by Showa Denko KK
Column; Shodex KF-G / KF-805L, series connection detector, manufactured by Showa Denko KK; RI (refractive index)
Eluent: chloroform sample concentration containing 0.5 wt% diethanolamine; 0.4 wt%
It was measured by.

(Tetracarboxylic acid residue)
R ¹ contained in the repeating unit of the functionalized polyimide resin of the present invention is a tetravalent organic acid, and can react with diamine to form an imide bond, an aliphatic, alicyclic, or aromatic tetracarboxylic acid. Residues of acids, their dianhydrides, or their derivatives.

《Aliphatic tetracarboxylic acid residue》
The aliphatic tetracarboxylic acid residue is a tetracarboxylic acid residue having a hydrocarbon group that does not contain an alicyclic group and an aromatic group.
In the case of an aliphatic tetracarboxylic acid residue, the carbon number thereof is 4 to 12, preferably 4 to 6. For example, 1,2,3,4-butanetetracarboxylic acid, 1,2, 3,4-pentanetetracarboxylic acid, 1,2,4,5-pentanetetracarboxylic acid, 1,2,3,4-hexanetetracarboxylic acid, 1,2,5,6-hexanetetracarboxylic acid, etc. It is done. When the carbon number of the aliphatic tetracarboxylic acid residue exceeds 8, the Tg (glass transition temperature) of the functionalized polyimide resin of the present invention becomes too low, and the mechanical properties of the final epoxy resin composition, Especially when the tensile strength and elongation, that is, the brittleness is extremely reduced, the crystallinity of the functionalized polyimide resin is excessively increased, the solvent solubility is reduced, or the compatibility when the epoxy resin composition is reduced There is.

  As the aliphatic tetracarboxylic acid, one kind or two or more kinds can be used, but preferably only one kind is used. When two or more types are used, although the solubility of the functionalized polyimide resin of the present invention in a general-purpose solvent and / or epoxy resin is improved, Tg (glass transition temperature) becomes too low and the final epoxy is used. The mechanical properties of the resin composition, particularly tensile strength and elongation, that is, brittleness may be extremely reduced.

<< alicyclic tetracarboxylic acid residue >>
The alicyclic tetracarboxylic acid residue is not limited as long as it has an alicyclic group in the residue. For example, in addition to an alicyclic group, a heterocycle containing an oxygen atom, a nitrogen atom, and / or a sulfur atom in addition to a carbon atom may be included. Moreover, an aromatic ring can also be included besides an alicyclic group. Further, these rings may be bonded by an alkylene group. That is, the alicyclic tetracarboxylic acid may contain an oxygen atom, a sulfur atom, and / or a nitrogen atom in addition to the carbon atom, and may contain an aromatic ring in addition to the portion constituting the alicyclic ring. The carbon number, oxygen number and nitrogen number of the alicyclic part of the alicyclic tetracarboxylic acid are 4 to 20, preferably 4 to 16, more preferably 6 to 14, and the number of alicyclic rings is not particularly limited. In general, the number is 1 to 4, preferably 1 to 2. When the number of alicyclic rings exceeds 4, the heat resistance (thermal decomposition temperature), which is a characteristic of polyimide, is reduced, although it is excellent in solubility, flexibility and base material adhesion for general-purpose solvents that are the object of the present invention. May be impractical. For example, cyclobutane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, cyclohexane-1,2,3,4-tetracarboxylic acid, cyclohexane- 1,2,4,5-tetracarboxylic acid, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid, 3-carboxymethyl-1,2,4-cyclopentanetricarboxylic acid, rel-dicyclohexyl-3, 3 ′, 4,4′-tetracarboxylic acid, tricyclo [4.2.2.0 ^2,5 ] dec-9-ene-3,4,7,8-tetracarboxylic acid, 5-carboxymethylbicyclo [2 2.1] heptane-2,3,6-tricarboxylic acid, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] octa-7 -Ene-2,3,6,7-tetracarboxylic acid, bicyclo [3.3.0] octane-2,4,6,7-tetracarboxylic acid, 7,8-diphenylbicyclo [2.2.2] Octa-7-ene-2,3,5,6-tetracarboxylic acid, 4,8-diphenyl-1,5-diazabicyclooctane-2,3,6,7-tetracarboxylic acid, 9-oxatricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid, 9,14-dioxopentacyclo [8.2.1 ^1,11 . 1 ^4,7 . 0 ^2,10 . 0 ^3,8 ] cyclodecane-5,6,12,13-tetracarboxylic acid and other cyclo, bicyclo and tricyclotetracarboxylic acids; 2,8-dioxaspiro [4.5] decane-1,3,7,9- Spiro ring-containing tetracarboxylic acid such as terotene; 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1, 3-dione etc. are mentioned. An alicyclic tetracarboxylic acid having a carbon number of less than 4 is excluded because it is not considered structurally. When the carbon number exceeds 20, the concentration of the imide group becomes too thin. There are cases in which the characteristics as are not expressed.

  Although 1 type (s) or 2 or more types can be used as an alicyclic tetracarboxylic acid, Preferably only 1 type is used. When two or more types are used, although the solubility of the functionalized polyimide resin of the present invention in a general-purpose solvent and / or epoxy resin is improved, the mechanical strength of the final epoxy resin composition, particularly tensile strength, is improved. Elongation and Tg (glass transition temperature) become too low, and the mechanical properties of the final epoxy resin composition, particularly tensile strength and elongation, that is, brittleness may be extremely reduced.

《Aromatic tetracarboxylic acid residue》
An aromatic tetracarboxylic acid residue contains an aromatic ring in the residue. The tetravalent binding site is not limited, but is preferably present on the aromatic ring.
In the case of an aromatic tetracarboxylic acid, the number of carbon atoms in the aromatic moiety is 6, 10, 14, 18, 22 or the like according to the Huckle rule, but is preferably 6, 10, 14, more preferably 6, 10 It is. The type of aromatic ring of the aromatic tetracarboxylic acid residue is not particularly limited, and examples thereof include a benzene nucleus, a naphthalene nucleus, a biphenyl nucleus, an anthracene nucleus, a perylene nucleus, and a fluorene nucleus. The tetravalent binding site is not limited, but is preferably present on the aromatic ring. These binding sites are divided into two sets of binding sites for imide bonds, and the binding sites for imide bonds are preferably located at the ortho or peri position of the aromatic ring. Further, the two sets of imide bonds are not limited, but may be located on the same aromatic ring or may be located on two or more aromatic rings.

（式中、
芳香環は、場合により炭素数１〜４の直鎖又は分枝鎖のアルキル基又はトリフルオロメチル基で置換されていてもよく、
Ａは、単結合、場合により１個以上のメチル基で置換されることのある炭素数１〜４のアルキレン基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、−Ｃ（ＣＦ_３）_２−、又は−ＣＯ−Ｏ−（ＣＨ_２）ｎ−Ｏ−ＣＯ−であって、ｎは１〜４の整数である）からなる群から選択される一般式で表される芳香族テトラカルボン酸残基を挙げることができる。 As a specific example of the aromatic tetracarboxylic acid residue, R ¹ is represented by the general formulas (2-a) to (2-h):

(Where
The aromatic ring may optionally be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group,
A represents a single bond, an alkylene group having 1 to 4 carbon atoms which may be optionally substituted with one or more methyl groups, —O—, —CO—, —S—, —SO ₂ —, —C ( CF ₃ ) ₂ —, or —CO—O— (CH ₂ ) n—O—CO—, where n is an integer of 1 to 4. Group tetracarboxylic acid residues can be mentioned.

  The aromatic tetracarboxylic acid residue may be substituted or unsubstituted. Although it does not specifically limit as a substituent, A C1-C4 alkyl group, a C1-C5 alkyl group, a C1-C4 alkenyl group, a C3-C8 cycloalkyl group, Mention may be made of trifluoroalkyl groups having 1 to 4 carbon atoms. For example, pyromellitic acid, 1,2,3,4-benzenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, 2,3,3', 4'-diphenylsulfonetetracarboxylic acid, 3,3 ', 4,4'-diphenylsulfidetetracarboxylic acid, 2,3,3 ', 4-diphenyl sulfide tetracarboxylic acid, 4,4'-oxydiphthalic acid, 4,4'-isopropylidene diphthalic acid, 4,4'-hexafluoroisopropylidene Phthalic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7- Anthracene tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 4,4-bis (2,3-dicarboxyphenoxy) diphenylmethane, ethylene glycol bisanhydro trimellitate, etc. From the viewpoint of improving the solubility in general-purpose solvents and improving the mechanical properties of the resulting polyimide resin, 4,4′-oxydiphthalic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,3 ′, 4, 4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid, 4,4′-isopropylidene diphthalate Acid, preferably 4,4′-hexafluoroisopropylidenediphthalic acid, and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid It is particularly preferable to use one or more of the above.

  As the aromatic tetracarboxylic acid, one kind or two or more kinds can be used, but preferably only one kind is used. When two or more types are used, although the solubility of the functionalized polyimide resin of the present invention in a general-purpose solvent and / or epoxy resin is improved, Tg (glass transition temperature) becomes too low and the final epoxy is used. The mechanical properties of the resin composition, particularly tensile strength and elongation, that is, brittleness may be extremely reduced.

  The aliphatic, alicyclic, and aromatic tetracarboxylic acid residues contained in the functionalized polyimide resin of the present invention are free aliphatic, alicyclic, aromatic tetracarboxylic acid, and dianhydrides thereof as described above. Or their derivatives, such as alkyl ester derivatives, but it is preferred to use dianhydrides.

(Dimeramine residue)
R ² contained in the repeating unit of the functionalized polyimide resin of the present invention is a divalent residue of a diamine capable of reacting with the tetracarboxylic dianhydride to form an imide bond. Is a dimer diamine residue. Although a dimer diamine residue is not limited, the thing derived from a dimer diamine having 20 to 48 carbon atoms can be used. Dimer diamine can be obtained by amidating two carboxyl groups of a polymerized fatty acid and subjecting it to a reduction reaction.

  The polymerized fatty acid is specifically obtained by Diels-Alder reaction of a monobasic unsaturated fatty acid having one or more double bonds or triple bonds having 10 to 24 carbon atoms. Soybean fatty acid, tall oil fatty acid, rapeseed oil fatty acid, rice bran oil fatty acid, safflower oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid obtained by hydrolyzing vegetable oil, and oleic acid, linoleic acid, which are refined these Polymerized fatty acids obtained by Diels-Alder reaction using linolenic acid, erucic acid or the like as raw materials are used.

(Diamine residue)
R ² contained in the repeating unit of the functionalized polyimide resin of the present invention is a divalent residue of a diamine that can react with tetracarboxylic dianhydride to form an imide bond, but the dimer In addition to the diamine residue, it may be an aliphatic, alicyclic, and / or aromatic diamine residue. That is, in the functionalized polyimide resin of the present invention, a dimer diamine residue and an aliphatic, alicyclic, and / or aromatic diamine residue may coexist.

  In the case of the aliphatic diamine, an oxygen atom may be contained in addition to the carbon atom, and the carbon number and / or the oxygen number is 2 to 18, preferably 2 to 12. For example, ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-tetraethylenediamine, neopentanediamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1, Examples include 10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, and the like. Examples of those containing oxygen atoms include 4-oxaheptane-1,7-diamine, 4,9-dioxadodecane-1,12-diamine, 4,7,10-trioxatridecane-1, 13-diamine etc. are mentioned. The aliphatic diamine having a carbon number of less than 2, that is, 1 is excluded because it is not considered structurally. When the carbon number exceeds 18, the Tg (glass transition of the functionalized polyimide resin of the present invention is used. When the temperature is too low, the strength of the final epoxy resin composition is significantly reduced, the crystallinity of the functionalized polyimide resin is too high, and the solvent solubility is reduced. Compatibility may be reduced.

  As aliphatic diamine, 1 type (s) or 2 or more types can be used, However, Preferably only 1 type is used. When two or more types are used, although the solubility of the functionalized polyimide resin of the present invention in a general-purpose solvent and / or epoxy resin is improved, Tg (glass transition temperature) becomes too low and the final epoxy is used. The mechanical properties of the resin composition, particularly tensile strength and elongation, that is, brittleness may be extremely reduced.

  In the case of an alicyclic diamine, the alicyclic moiety has 3 to 15 carbon atoms, preferably 6 to 15 carbon atoms, and the number of alicyclic rings is not particularly limited, but is generally 1 to 4 carbon atoms, Preferably it is 1-2. For example, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bisaminocyclohexane, isophorone diamine, norbornene diamine, 4,4′-diaminodicyclohexyl methane, 3 , 3′-dimethyl-4,4′-diaminodicyclohexylmethane and the like. Since the alicyclic diamine cannot have 2 carbon atoms, it is excluded. When the carbon number exceeds 15, the solubility, flexibility, and base material adhesion to the general-purpose solvent that is the object of the present invention are included. Although excellent, mechanical strength, particularly tensile strength, is greatly reduced and is not practical.

  As the alicyclic diamine, one type or two or more types can be used, but preferably only one type is used. When two or more types are used, although the solubility of the functionalized polyimide resin of the present invention in a general-purpose solvent and / or epoxy resin is improved, Tg (glass transition temperature) becomes too low and the final epoxy is used. The mechanical properties of the resin composition, particularly tensile strength and elongation, that is, brittleness may be extremely reduced.

  In the case of an aromatic diamine, the carbon number of the aromatic moiety is 6, 10, 14, 18, 22, etc., preferably 6, 10, 14, more preferably 6, 10, according to the Huckle rule. . Moreover, the number of aromatic rings is 1-6, Preferably it is 1-5, More preferably, it is 1-4. Although the aromatic rings contained are 1 to 6, the mechanical properties of the final epoxy resin composition, in particular, although they are excellent in solubility, flexibility, and substrate adhesion to general-purpose solvents that are the object of the present invention, The tensile strength and elongation, that is, the brittleness may be extremely lowered, which is not practical. The type of aromatic ring of the aromatic diamine is not particularly limited, and examples thereof include a benzene nucleus, a naphthalene nucleus, a biphenyl nucleus, an anthracene nucleus, a perylene nucleus, and a fluorene nucleus. In addition, although the divalent binding site is not limited, it preferably exists on an aromatic ring and may be located on the same aromatic ring or may be located on two aromatic rings.

（式中、
芳香環は、場合により炭素数１〜４の直鎖又は分枝鎖のアルキル基又はトリフルオロメチル基で置換されていてもよく、
Ａは、単結合、場合により１個以上のメチル基で置換されることのある炭素数１〜４のアルキレン基、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ_２−、又は−Ｃ（ＣＦ_３）_２−である）からなる群から選択される一般式で表される芳香族ジアミン残基を挙げることができる。 Specific examples of the aromatic diamine residue include general formulas (3-a) to (3-h).

(Where
The aromatic ring may optionally be substituted with a linear or branched alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group,
A represents a single bond, an alkylene group having 1 to 4 carbon atoms which may be optionally substituted with one or more methyl groups, —O—, —CO—, —S—, —SO ₂ —, or —C. An aromatic diamine residue represented by the general formula selected from the group consisting of (CF ₃ ) ₂ —.

  The aromatic diamine may be substituted or unsubstituted, but in the present specification, the substituent in the aromatic diamine residue means that present in the aromatic ring. Although it does not specifically limit as a substituent, A C1-C4 alkyl group, a C1-C5 alkyl group, a C1-C4 alkenyl group, a C3-C8 cycloalkyl group, Mention may be made of trifluoroalkyl groups having 1 to 4 carbon atoms. For example, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 2,2-bis [ 4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone 3,3′-diaminodiphenylsulfone, 1,3-bis (3-aminophenoxy Benzene, 1,4-bis (4-aminophenoxy) benzene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (trifluoromethyl) ) -4,4′-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,3-bis [2- (4-aminophenyl) -2-propyl] Examples include benzene.

  As the aromatic diamine, one kind or two or more kinds can be used, but preferably only one kind is used. When two or more types are used, although the solubility of the functionalized polyimide resin of the present invention in a general-purpose solvent and / or epoxy resin is improved, Tg (glass transition temperature) becomes too low and the final epoxy is used. The strength of the resin composition may be significantly reduced.

(Weight ratio of the aliphatic, alicyclic and aromatic diamine residues to the dimer diamine residue)
The weight ratio of the aliphatic, alicyclic, aromatic diamine residue and dimer diamine residue in the functionalized polyimide resin of the present invention is 0: 100 to 90:10. That is, the dimer diamine residue is 10% by weight to 100% by weight with respect to the total weight of the aliphatic, alicyclic, aromatic diamine residue and dimer diamine residue, and the aliphatic, alicyclic, aromatic The diamine residue is 0 to 90% by weight. By containing 10% by weight or more of dimer diamine residues, excellent solubility in a general-purpose solvent is exhibited, the color of the polyimide resin becomes light, and the water absorption rate decreases. In addition, compatibility with the epoxy resin in the case of an epoxy resin composition is improved, and chemical resistance and etchant resistance of the cured epoxy resin are improved.

(Imide bond)
The repeating unit of the functionalized polyimide resin of the present invention has two imide bonds. The imide bond may be an amide bond, but the imide bond is more than 50%, preferably 70% or more, more preferably 80%, based on the total of the imide bond and the amide bond. Or more, and most preferably 90% or more. If the imide bond is 50% or less, the carboxyl group also remains in the molecule at the same ratio as the amide bond, that is, a ratio of 50% or more, so that the water absorption increases and the effect of the present invention cannot be obtained. In addition, the storage stability of the functionalized polyimide resin is inferior, that is, the imidization reaction gradually proceeds during storage and the viscosity increases. Moreover, when it uses finally as an adhesive agent or a coating, since a further dehydration reaction advances, an adhesive layer or a coating film may shrink.
The functionalized polyimide resin of the present invention has the following formula (6), (7), or (8) as long as the solubility of the functionalized polyimide resin in a general-purpose solvent (for example, cyclohexanone) is not significantly reduced. However, these repeating units are less than 50%, preferably less than 30%, more preferably, based on the entire repeating unit of the polyimide resin. Is less than 20%, most preferably less than 10%.

[2] Method for Producing Functionalized Polyimide Resin The functionalized polyimide resin of the present invention can be produced by the method for producing a functionalized polyimide resin of the present invention. According to the method for producing a functionalized polyimide resin of the present invention, a functionalized polyimide resin can be produced using the tetracarboxylic dianhydride and the dimer diamine. In addition, according to the method for producing a functionalized polyimide resin of the present invention, a functionalized polyimide using the aromatic tetracarboxylic dianhydride, the dimer diamine, and the aliphatic, alicyclic, or aromatic diamine. Resins can also be produced. The functionalized polyimide resin produced by the production method of the present invention is characterized in that it does not stop at the stage of the amic acid by the addition reaction, but reacts to a polyimide stage exceeding the imidation rate of 50% by a condensation reaction. In the method for producing a polyimide resin of the present invention, in order to introduce a functional group at the terminal, “method of adding the fourth component” and “method of changing the equivalent ratio of tetracarboxylic dianhydride / diamine” There are one embodiment. Each embodiment will be described below.

(1) Method of Adding Fourth Component One embodiment of the method for producing a polyimide resin of the present invention is: (I) one or more tetracarboxylic dianhydrides represented by the general formula (2), (II ) One or more aliphatic, alicyclic and / or aromatic diamines represented by the general formula (3), and (III) one or more dimer diamines derived from polymerized fatty acids having 20 to 48 carbon atoms. A first step of obtaining a polyamic acid by reacting the aliphatic, alicyclic and / or aromatic diamine with the dimer diamine under a condition of 0: 100 to 90:10; and the polyamic A compound containing one carboxyl group and one acid anhydride group in the first step or the second step in order to introduce a functional group at the terminal, a carboxyl group 1; Containing one and one amino group Is to add a phenolic hydroxyl group and one amino group Compound containing one to, and at least one compound selected from the group consisting of compounds containing two secondary amino groups.
That is, this embodiment is characterized in that the fourth component is added to the first step or the second step in order to introduce a functional group at the terminal.

(1-1) When the terminal functional group is a carboxyl group As the fourth component for introducing a carboxyl group at the terminal, (A) one carboxyl group and one acid anhydride group, or (B) Mention may be made of a compound having one carboxyl group and one amino group, or (C) two carboxyl groups and one amino group. Examples of component (A) having one carboxyl group and one acid anhydride group (hereinafter sometimes abbreviated as component (A)) include trimellitic anhydride, and one carboxyl group and amino Examples of the component (B) having one group (hereinafter sometimes abbreviated as component (B)) include aminobenzoic acids such as 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid; Examples include amino acids such as glycine, alanine, leucine, isoleucine, phenylalanine, proline, and valine, and the like (component (C) having two carboxyl groups and one amino group (hereinafter may be abbreviated as component (C)). .) Includes, for example, 5-aminoisophthalic acid, 3-aminophthalic acid, 4-aminophthalic acid, 2-aminoterephthalic acid and the like.

(1-2) When the terminal functional group is a phenolic hydroxyl group The fourth component for introducing a phenolic hydroxyl group at the terminal is (D) a component having one phenolic hydroxyl group and one amino group. be able to. For example, 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are mentioned.

(1-3) When terminal functional group is amino group In order to introduce an amino group at the terminal, (E) a compound containing two secondary amino groups can be mentioned. For example, N, N′-dialkylalkylenediamines such as N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N′-dimethylhexamethylenediamine, N, N′-diethylhexamethylenediamine; piperazine Piperazines such as homopiperazine; 1,4-bis (2-imidazolyl) butane, 1,6-bis (2-imidazolyl) hexane, 1,7-bis (2-imidazolyl) heptane described in Patent Document 5; Examples thereof include bisimidazolines such as 1,8-bis (2-imidazolyl) octane, 1,10-bis (2-imidazolyl) decane, and 1,16-bis (2-imidazolyl) hexadecane.

(2) Method of changing the equivalent ratio of tetracarboxylic dianhydride / diamine Another embodiment of the method for producing a polyimide resin of the present invention is (I) General formula (2)
One or more tetracarboxylic dianhydrides represented by (II) one or more aliphatic, alicyclic, and / or aromatic diamines represented by the general formula (3), and (III) 20 to 20 carbon atoms One or more dimer diamines derived from 48 polymerized fatty acids, wherein the weight ratio of the aliphatic, alicyclic, and / or aromatic diamines to the dimer diamine is 0: 100 to 90:10. A first step of reacting to obtain a polyamic acid, wherein the equivalent ratio of tetracarboxylic dianhydride to diamine is 0.5 to less than 1.0 in order to introduce a functional group at the terminal; And a second step of imidizing the polyamic acid.
That is, the equivalent ratio of tetracarboxylic dianhydride / diamine is enriched with amine.

  In this embodiment, the reaction may be performed by adjusting the equivalent ratio of tetracarboxylic dianhydride / diamine to a desired amine value. As described above, the equivalent ratio of tetracarboxylic dianhydride to diamine may be 0.5 or more and less than 1.0, but the lower limit is preferably 0.8 or more, more preferably 0.9 or more. is there. For example, when a low amine value of about 5 amine values is desired, that is, when the equivalent ratio of tetracarboxylic dianhydride to diamine is high, an excellent toughening effect of the final epoxy resin adhesive or coating can be obtained. Can do. On the other hand, for example, when a high amine value such as an amine value of 50 is desired, that is, when the equivalent ratio of tetracarboxylic dianhydride to diamine is low, the molecular weight of the functionalized polyimide resin of the present invention inevitably decreases, This is not preferable because the final epoxy resin adhesive or the toughening effect of the coating is inferior.

As described above, the method for producing a functionalized polyimide resin of the present invention comprises (1) reacting tetracarboxylic dianhydride and diamine (dimeramine, or dimeramine and aliphatic, alicyclic, and aromatic diamines). A first step of synthesizing a polyamic acid; and (2) a second step of dehydrating the resulting polyamic acid and imidizing it. Here, in the first step (1) from which the polyamic acid was obtained, it may be once discharged, purified, etc. In general, for the purpose of improving the efficiency of the reaction step, the first step (1) and It is preferable to perform the second step (2) together. At this time, it is preferable to prevent oxidative deterioration through an inert gas such as nitrogen gas or argon gas in order to prevent unnecessary resin coloring.

The production method of the functionalized polyimide resin is
(A) a method of performing the first step (1) and the second step (2) in a solvent;
(B) A method in which the first step (1) and the second step (2) are performed without a solvent, and (c) the first step (1) is performed in a solvent, and the second step (2) is performed with a solvent and water. There is a method to perform while removing. This will be described in turn below.

  In the case of the method (a) in which the first step (1) and the second step (2) are performed in a solvent, the organic solvent does not react with the acid dianhydride and the amine under the temperature conditions to be synthesized. Any intermediate and product can be used in the first step (1) and the second step (2) so long as a reaction in a homogeneous system can be realized. Among them, an aprotic polar solvent is particularly suitable. ing. Specifically, for example, a nitrogen-containing solvent; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphorylamide, dimethylimidazolidinone Sulfur-containing solvents; dimethyl sulfoxide, dimethyl sulfone, sulfolane, lactones; γ-butyrolactone, γ-valerolactone, ε-caprolactone, alicyclic ketones; cyclopentanone, cyclohexanone, 4-methylcyclohexanone, ethers; Tetrahydrofuran, diethylene glycol methyl ether acetate, methoxybutyl acetate and the like can be mentioned, and these can be used alone or in combination. Among these, from the viewpoint of excellent solubility of the polyimide resin, relatively high boiling point, and easy dehydration reaction, a nitrogen-containing solvent is preferable, and N, N′-dimethylacetamide is particularly preferable.

  On the other hand, in the case of the method (c), similarly, there is no reaction with the acid dianhydride and amine under the temperature conditions for synthesis, and the intermediate in the first step (1) and the second step (2). As long as the product dissolves and the reaction in a homogeneous system can be realized, anything may be used, but in the case of the method (c), the solvent must be removed. preferable. Specific examples of the most preferable include tetrahydrofuran (boiling point 60 ° C.), 1,4-dioxane (boiling point 101 ° C.), cyclohexanone (boiling point 155 ° C.), and n-butyl acetate (boiling point 120 ° C.).

  The amount of the organic solvent to be used may be any amount, but usually an amount that makes the viscosity of the functionalized polyimide solution finally obtained easy to handle is used. In general, the solid content of the functionalized polyimide is 10 to 50% by weight, preferably about 15 to 40% by weight, so that the handling property is the best.

The functionalized polyimide resin of the present invention can also be synthesized without solvent. That is, the first step (1) and the second step (2) can be performed by the method (b) without a solvent. In general, when only aromatic tetracarboxylic dianhydride and aromatic diamine are used as raw materials, polyamic acid and polyimide become a solid with a high melting point and a high glass transition temperature. Synthesis is difficult. In the present invention, since dimer diamine is used, synthesis in the absence of a solvent is possible. In this case, the aromatic tetracarboxylic dianhydride, aromatic diamine, and dimer diamine are reacted at a reaction temperature of 80 ° C. or lower, preferably 70 ° C. or lower, more preferably near room temperature for 1 to 12 hours. Then, after synthesizing the polyamic acid, the mixture is heated to about 200 to 250 ° C. and reacted under reduced pressure for about 1 to 10 hours until a predetermined imidization rate is reached in order to promote the dehydration reaction.
In this case, the final functionalized polyimide resin is obtained in a solid state, and then the solution-functionalized polyimide resin is obtained by dissolving the polyimide resin in an arbitrary solvent in an arbitrary solid content.

  Moreover, the functionalized polyimide resin of this invention can be implemented by the method (c) which performs a 1st process (1) in a solvent and performs a 2nd process (2), removing a solvent and water. That is, the first half of the amic acid synthesis process can be carried out in a solvent, and the synthesis can be performed while simultaneously removing the solvent and the water produced in the latter half of the imidization step. In this case as well, the final functionalized polyimide resin can be obtained in a solid state. In general, in view of dissolving the raw material, the method (c) in which the amic acid synthesis process is performed in a solvent, and the solvent is removed and dehydrated at the same time is most preferable. This is because the final polyimide resin solution can be obtained in an arbitrary solid content and diluted with an arbitrary solvent regardless of the solvent type used in the synthesis process.

[3] Epoxy resin composition containing functionalized polyimide resin (epoxy resin composition)
The epoxy resin composition according to the present invention contains the aforementioned functionalized polyimide resin, epoxy resin, and epoxy resin curing agent. An epoxy resin adhesive or an epoxy resin coating agent can be easily obtained by dissolving and coating the functionalized polyimide resin, epoxy resin and epoxy resin curing agent in a common solvent.

(Epoxy resin)
The epoxy resin according to the present invention is a compound having an average of more than one epoxy group in the molecule. For example, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, tetramethylbisphenol A, tetramethyl Bisphenol F or their halogen (eg chlorine, bromine) derivatives, catechol, resorcin, hydroquinone, naphthol, trihydroxybiphenyl, bisresorcinol, bisxylenol, binaphthol, trihydroxyphenylmethane, tetrahydroxyphenylethane, phenol novolac resin And / or an epoxy resin (glycidyl ether) obtained by reacting a polyphenol such as cresol novolac resin with epichlorohydrin; glycerin, neopenty Epoxy resin (glycidyl) obtained by reacting an aliphatic polyhydric alcohol such as glycol, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, polyethylene glycol and / or polypropylene glycol with epichlorohydrin Ether); epoxy resin (glycidyl ether ester) obtained by reacting a hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid with epichlorohydrin; phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid It is obtained by reacting polychlorocarboxylic acid such as acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, trimellitic acid, and / or polymerized fatty acid with epichlorohydrin. Epoxy resin (glycidyl ester); epoxy resin (glycidylaminoglycidyl ether) obtained by reacting aminophenol such as p-aminophenol and p-aminoalkylphenol with epichlorohydrin; aniline, o-toluidine, tri Bromoaniline, m-xylylenediamine, p-xylylenediamine, 1,2-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, 4,4′-diaminodiphenylmethane, and / or 4,4′-diaminodiphenylsulfone Epoxy resin (glycidylamine) obtained by reacting an amine such as epichlorohydrin; epoxidized polyolefin, epoxidized polybutadiene, epoxidized soybean oil, glycidyl hydantoin, di- or tri Mention may be made of re-cyanurate and the like. Among them, bisphenol A type epoxy resin, naphthol type epoxy resin, phenol novolac type, because the cured product obtained by curing the epoxy resin composition of the present invention is excellent in electrical properties such as heat resistance, insulation, wet heat decomposition resistance, etc. It is particularly preferable to use an epoxy resin, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a diaminodiphenylmethane type epoxy resin, di- or triglycidyl cyanurate. The epoxy resin can be used alone or in combination of two or more.

  As an epoxy resin in the epoxy resin composition of the present invention, a monofunctional epoxy compound can be used in combination as long as the effects of the present invention are not impaired. Illustrative examples include butyl glycidyl ether, phenyl glycidyl ether, higher alcohol glycidyl ether, benzoic acid glycidyl ester, branched fatty acid glycidyl ester (Cardura E; manufactured by Momentive Performance Materials), styrene oxide, and the like. In general, since these monofunctional epoxy compounds have low viscosity, especially when using an epoxy resin composition by the common solvent method, in order to ensure the fluidity of the epoxy resin composition when trying to reduce the amount of solvent. Although effective, it may reduce the heat resistance (glass transition temperature) and wet heat decomposition resistance of the final epoxy resin adhesive or coating, so the amount used should be as small as possible. The monofunctional epoxy resin can be used alone or in combination of two or more.

(Epoxy resin curing agent)
As the epoxy resin curing agent in the epoxy resin composition of the present invention, known and conventional epoxy resin curing agents other than the cationic curing catalyst can be used, and amine curing agents, imidazole curing agents, guanidine curing agents, thiols. Examples thereof include a system curing agent, a phenol resin curing agent, and an acid anhydride curing agent. Since the epoxy resin composition of the present invention contains an imide bond and, in some cases, an amide bond in its constituent components, a cationic curing catalyst cannot be used because curing inhibition occurs.

  Examples of the amine curing agent include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 1,10-diaminodecane, 1,12. -Polyethylene polyamines such as diaminododecane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine; 1,2-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, metaxylylenediamine, norbornanediamine, Ring-containing amines such as 4,4′-diaminodicyclohexylmethane or 2,2′-dimethyl-4,4′-diaminodicyclohexylmethane 4,4′-diaminodiphenylmethane; The additional modified amines were; modified amines or the like the amines and urea denaturation and the like, which can be used in combination of two or more.

  Examples of the imidazole curing agent include imidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2 -Imidazoles such as phenyl-4-methylimidazole, 1-benzylimidazole, 1-benzyl-2-phenylimidazole, or 1-cyanoethyl-2-methylimidazole; Modification obtained by adding the epoxy resin exemplified above to the imidazoles Examples thereof include imidazoles, and these can be used alone or in combination of two or more.

  Examples of the guanidine curing agent include dicyandiamide, tetramethylguanidine, biguanide, n-butylguanidine, guanylthiourea, and the like, and these can be used alone or in combination of two or more.

  Examples of the thiol-based curing agent include butanediol bis (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris. (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, Pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptobutyryloxyethyl) isocyanurate, trimethylolethane (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), Examples include lisbutanediol bisthioglycolate, hexanediol thioglycolate, trimethylolpropane tristhioglycolate, or pentaerythritol tetrakisthioglycolate, and these can be used alone or in combination of two or more. .

  Examples of the phenol resin-based curing agent include phenol novolak resins, bisphenol novolac resins, cresol novolac resins having various molecular weights and softening points, and these may be used alone or in combination of two or more. it can.

  Examples of the acid anhydride curing agent include hexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, methyl- Monofunctional acid anhydrides such as 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, succinic anhydride, octenyl succinic anhydride; dianhydride of tetracarboxylic acid used in the production method of the present invention Adipic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, octadecanedioic acid and the like, and polyanhydrides obtained by dehydration condensation are listed. It can be used in combination kind or two or more kinds.

(Other additives)
As long as the effects of the present invention are not impaired, other components commonly used in the art can be added to the epoxy resin composition of the present invention. Specifically, for example, resins such as polyimide resins other than the functionalized polyimide resin of the present invention, polyester resins, polyamide resins, or polyamideimide resins; flame retardants, antioxidants, antifoaming agents, leveling agents, etc. Can be mentioned.

[4] Epoxy resin adhesive and epoxy resin coating agent and article provided with them The epoxy resin adhesive of the present invention contains the epoxy resin composition. Moreover, the epoxy resin coating agent of this invention contains the said epoxy resin composition.
Furthermore, the articles coated with the epoxy resin adhesive and the epoxy resin coating agent according to the present invention are an article bonded using the epoxy resin composition and an article coated with the epoxy resin composition. For example, as an adhesive agent, the adhesive agent for flexible printed circuit boards (FPC) which consists of a thin copper plate and a polyimide resin can be mentioned.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention. In the following examples, “parts” means “parts by weight” unless otherwise specified.

<Synthesis of polyimide resin>
The abbreviated names of the raw materials used and chemical substances used in the solvent solubility test are shown below.
<Aromatic tetracarboxylic dianhydride>
DSDA: Diphenylsulfone tetracarboxylic dianhydride <Aliphatic / aromatic combined tetracarboxylic dianhydride>
TDA: 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione <aliphatic tetracarboxylic Acid dianhydride>
BTCA: 1,2,3,4-butanetetracarboxylic dianhydride <aromatic tricarboxylic anhydride>
TMA: trimellitic anhydride <dimeramine>
P-1074: Preamine 1074 (manufactured by CLODA)
<Aliphatic diamine>
1,10-DDA: 1,10-diaminodecane <Aromatic amine having phenolic hydroxyl group>
4-aminophenol <solvent>
DMAC: N, N-dimethylacetamide THF: tetrahydrofuran DOX: 1,4-dioxanechloro: chloroformanone: cyclohexanone butyrate: n-butyl acetate

<Evaluation method of functionalized polyimide resin>
1. Coating film preparation method The obtained polyimide resin solution was applied to a 160 × 200 × 0.3 mm electroplated tin plate with a width of 120 mm using a 400 μm applicator, 120 ° C. × 0.5 h, and then 160 under a reduced pressure of 5 mmHg. The solvent was removed by drying at 205 ° C. for 0.5 h and then 205 ° C. for 1 h to obtain a polyimide coating film. Dry film thickness of about 50 μm.

2. Evaluation method 2-1. Mechanical properties The obtained polyimide coating film was peeled off from the tin plate by the mercury amalgam method, cut into a width of 6 mm and a length of 60 mm to obtain a test piece. The tensile strength, elastic modulus, and elongation at break of this test piece were measured at 20 mm / min using an autograph AGS-5 kND manufactured by Shimadzu Corporation.
2-2. Thermal characteristics 2-2-1. Glass transition temperature About 10 mg of the obtained polyimide film was sampled, heated and cooled at 10 ° C./min under the following conditions using a DSC1 manufactured by METTLER TOLEDO, and the glass transition temperature (Tg) in the cooling process of 1 st run. ) The melting point (mp) was measured during the 2nd run heating process.
1st run: −30 ° C. → 300 ° C. → −30 ° C.
2nd run: −30 ° C. → 480 ° C.
2-2-2. Thermal weight reduction temperature About 10 mg of the obtained polyimide film was sampled and heated at a heating rate of 10 ° C./min in a nitrogen atmosphere using TG-DTA2000S manufactured by Mac Science, 1% weight reduction temperature (Td1), A 3% weight loss temperature (Td3) and a 5% weight loss temperature (Td5) were measured.
2-2-3. Linear Expansion Coefficient The obtained polyimide film was cut into a size of 5 mm × 10 mm, and heated at a heating rate of 5 ° C./min using TMA / SDTA841 manufactured by METTLER TOLEDO to measure the linear expansion coefficient (CTE).
2-3. Solubility The obtained polyimide film was poured into the above-mentioned various solvents at 10% by weight, tried to dissolve by shaking vigorously for several hours at room temperature, and allowed to stand at room temperature to visually check the state of the solution on the next day.
S: Complete dissolution G: Gelled I: Insoluble 2-4. Water Absorption Rate The obtained polyimide film was cut into a size of 60 mm × 20 mm, immersed in water at 23 ° C. for 7 days, and the weight increase rate was calculated by the following formula.
(Weight increase rate)% = {(weight after immersion) − (weight before immersion)} × 100 / (weight before immersion)
2-5. Yellowness When measured through the resulting polyimide film using a color difference meter manufactured by Big Chemie Japan Co., Ltd., using a copy paper (alpha eco paper Type DII manufactured by Otsuka Corporation) defined in ISO 2470; The color difference was expressed as ΔE. It means that yellowness is so small that (DELTA) E is small, ie, near colorlessness.
2-6. Epoxy compatibility The polyimide and the following epoxy resin were weighed in an aluminum pan having a diameter of 10 cm in a 1/1 ratio so that the total amount was 10 g, and then sufficiently melted and mixed on a 240 ° C. hot plate. The epoxy compatibility was evaluated by visually observing the state at the time of heat melting and returning to room temperature. A sample which became transparent at the time of heat melting and room temperature was designated as “◯”, a material which was transparent at the time of heat fusion but became cloudy at room temperature was designated as “Δ”, and a product which became cloudy or separated at the time of heat melting was designated as “X”.
(Epoxy resin used)
Epototo YD-128: Nippon Steel & Sumikin Chemical Co., Ltd., liquid bisphenol A type epoxy resin Epototo YD-011: Nippon Steel & Sumikin Chemical Co., Ltd., solid bisphenol A type epoxy resin Epicron 830: DIC Corporation, bisphenol F type epoxy resin Epicron N-660 : DIC, cresol novolac epoxy resin Epicron N-770: DIC, phenol novolac epoxy resin

<< Synthesis Example 1 >>
In Synthesis Example 1, a polyimide resin having a carboxyl group at the molecular chain end was synthesized by a production method in which the fourth component was added.
40.7 parts (0.076 mol) of P-1074 and 13.2 parts of 1,10-DDA in a 300 mL four-necked flask equipped with a nitrogen inlet tube, stirrer, thermometer, Dean Stark trap, and condenser tube (0.076 mol), 44.5 parts (0.148 mol) of TDA, 1.6 parts (0.004 mol) of TMA and 100 parts of dimethylacetamide (DMAC) as a solvent, while flowing nitrogen gas The temperature was raised to 200 ° C. over 2 hours, and distilled water and DMAC were removed from the system. After reaching 200 ° C., the pressure was reduced to about 5 Torr, and the water and DMAC distilled off were kept at 5 Torr for 2 hours to completely remove out of the system. It was discharged into a polytetrafluoroethylene vat in a molten state to obtain a functionalized polyimide resin. The distilled water was 5.4 parts, which was 98% of the theoretical amount (theoretical amount 5.5 parts). Using the functionalized polyimide resin obtained by the above method, a polyimide resin film having a film thickness of about 50 μm after drying was obtained by the method 1 described above. The above various tests were conducted, and the results are shown in Table 1.

<< Synthesis Example 2 >>
In Synthesis Example 2, a polyimide resin having an amino group at the molecular chain terminal was synthesized by a production method in which the equivalent ratio of tetracarboxylic dianhydride / diamine was changed.
Except that the acid anhydride component and the diamine component were formulated as shown in Table 1, the procedure of Example 1 was repeated to obtain a polyimide resin film. The above various tests were performed on these polyimide resin films, and the results are shown in Table 1.

<< Synthesis Example 3 >>
In Synthesis Example 3, a polyimide resin having a phenolic hydroxyl group at the molecular chain terminal was synthesized by a production method in which the fourth component was added.
Except that the acid anhydride component and the diamine component were formulated as shown in Table 1, the procedure of Example 1 was repeated to obtain a polyimide resin film. The above various tests were performed on these polyimide resin films, and the results are shown in Table 1.

<< Synthesis Example 4 >>
In Synthesis Example 4, a polyimide resin having a phenolic hydroxyl group at the molecular chain end was synthesized by a production method in which the fourth component was added.
Except that the acid anhydride component and the diamine component were formulated as shown in Table 1, the procedure of Example 1 was repeated to obtain a polyimide resin film. The above various tests were performed on these polyimide resin films, and the results are shown in Table 1.

<< Comparative Synthesis Example 1 >>
In this comparative synthesis example 1, a polyimide resin having no amino group at the molecular chain end was synthesized.
59.9 parts (0.112 mol) of P-1074 and 40.1 parts of DSDA (0.112 mol) in a 300 mL four-necked flask equipped with a nitrogen introduction tube, a stirrer, a thermometer, a Dean-Stark trap, and a cooling tube Mol) and DMAC were added, and the temperature was raised to 200 ° C. over 2 hours while flowing nitrogen gas, and the distilled water and DMAC were removed from the system. After reaching 200 ° C., the pressure was reduced to about 5 Torr, and the water and DMAC that were distilled by holding at 5 Torr for 2 hours were completely removed from the system. It was discharged into a polytetrafluoroethylene vat in a molten state to obtain a functionalized polyimide resin. The distilled water was 3.7 parts, which was 93% of the theoretical amount (theoretical amount 4.0 parts). Using the functionalized polyimide resin obtained by the above method, a polyimide resin film having a film thickness of about 50 μm after drying was obtained by the method 1 described above. The various tests described above were performed, and the results are shown in Table 1.

  As shown in Table 1, the polyimide resin films obtained in Synthesis Examples 1 to 4 showed excellent compatibility with epoxy as compared with the polyimide resin film obtained in Comparative Synthesis Example 1. Furthermore, the polyimide resin films obtained in Synthesis Examples 1 to 4 were superior in solubility to DMAC as compared to the polyimide resin film obtained in Comparative Synthesis Example 1.

<< Manufacture of epoxy resin composition >>
The raw material used for preparation of the epoxy resin composition is shown below.
<Curing agent>
Rikacid MH: Shin Nippon Rika Co., Ltd., 4-methylhexahydrophthalic anhydride tamanor 759: Arakawa Chemical Industries, Ltd., phenol novolac resin <curing accelerator>
2E4MZ: manufactured by Mitsubishi Chemical Corporation, 2-ethyl-4-methylimidazole <modifier>
Polyamide elastomer: manufactured by T & K TOKA, polyether ester amide, TPAE-826

<Evaluation method of epoxy resin composition>
1. Preparation method of cured epoxy film The varnish of the epoxy resin composition obtained in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 3 is applied to an electroplated tin plate of 160 × 200 × 0.3 mm to a width of 120 mm using a 400 μm applicator. It was applied and heated at 200 ° C. for 1 h to cure and remove the diluent, thereby obtaining an epoxy cured film. Dry film thickness of about 100 μm.

2. Evaluation method 2-1. Mechanical properties The obtained epoxy cured film was peeled off from the tin plate by the mercury amalgam method, cut into a width of 6 mm and a length of 60 mm to obtain a test piece. The tensile strength, elastic modulus, and elongation at break of this test piece were measured at 20 mm / min using an autograph AGS-5 kND manufactured by Shimadzu Corporation.
2-2. Fracture toughness value The obtained epoxy cured film was cut into a size of 12.5 mm × 150 mm, a test piece was processed according to ASTM D5045 (1999), and measurement was performed using an autograph AGS-5kND manufactured by Shimadzu Corporation. . The initial precrack was introduced into the test piece by applying a razor blade cooled to liquid nitrogen temperature to the test piece and applying an impact to the razor with a hammer.
2-3. Water absorption rate The obtained epoxy cured film was cut into a size of 60 mm × 20 mm, immersed in hot water at 60 ° C. for 7 days, and the weight increase rate was calculated by the following formula.
(Weight increase rate)% = {(weight after immersion) − (weight before immersion)} × 100 / (weight before immersion)
2-4. Chemical resistance A cured epoxy film prepared in the same manner as in 2-1 was cut into a size of 60 mm × 20 mm, and 10 wt% sodium hydroxide aqueous solution, 10 wt% ammonia aqueous solution, 5 wt% hydrochloric acid aqueous solution, 5 wt% at 40 ° C. After being immersed in a sulfuric acid aqueous solution for 7 days, it was taken out, washed with water, and thoroughly wiped off with a clean dry cloth. Immediately thereafter, changes in appearance such as discoloration and swelling of the test piece were visually observed. Those with no change in appearance were evaluated as “pass”, and those with change in appearance were determined as “fail”.

2-5. Peel strength 25 μm × 125 mm cut out polyimide film with a thickness of 50 μm (Kapton 200H / V manufactured by Toray DuPont) was coated with a varnish of an epoxy resin composition using a bar coater-No. A test piece was obtained by pasting another polyimide film that had been coated at 12 and cut into the same size, and then pressure-molded at 200 ° C. for 1 hour at 10 MPa. The peel strength of this test piece was measured at 50 mm / min using an autograph AGS-5 kND manufactured by Shimadzu Corporation.

2-6. Solder heat resistance A test piece prepared in the same manner as described in 1 (in a state where it was coated on a tin plate) was immersed in a solder bath heated to 290 ° C. for 60 seconds and then evaluated by observing the appearance. Those having no appearance abnormality such as blistering or peeling were evaluated as “pass”, and those other than this were defined as “fail”.

Example 1
In this example, an epoxy resin composition was produced using a polyimide resin having a carboxyl group at the molecular end.
According to the composition described in Table 2, the epoxy resin, the curing agent, the curing accelerator, and the polyimide resin solution synthesized in Synthesis Example 1 were mixed in a glass container to prepare a varnish of an epoxy resin composition having a solid content of 60 wt%. Prepared.

Example 2
In this example, an epoxy resin composition was produced using a polyimide resin having a carboxyl group at the molecular end.
According to the composition described in Table 2, the epoxy resin, the curing agent, the curing accelerator, and the polyimide resin solution synthesized in Synthesis Example 1 were mixed in a glass container to prepare a varnish of an epoxy resin composition having a solid content of 60 wt%. Prepared.

Example 3
In this example, an epoxy resin composition was produced using a polyimide resin having an amino group at the molecular end.
According to the composition described in Table 2, the epoxy resin, the curing agent, the curing accelerator, and the polyimide resin solution synthesized in Synthesis Example 2 were mixed in a glass container to prepare a varnish of an epoxy resin composition having a solid content of 60 wt%. Prepared.

<< Examples 4 to 8 >>
In this example, an epoxy resin composition was produced using a polyimide resin having a phenolic hydroxyl group at the molecular end.
According to the composition described in Table 2, the epoxy resin, the curing agent, the curing accelerator, and the polyimide resin solution synthesized in Synthesis Example 3 or 4 were mixed in a glass container to mix the epoxy resin composition having a solid content of 60 wt%. A varnish was prepared.

<< Comparative Example 1 >>
In this comparative example, an epoxy resin composition containing no functionalized polyimide resin was produced.
According to the composition described in Table 2, an epoxy resin, a curing agent, and a curing accelerator were placed in a glass container and mixed to prepare a varnish of an epoxy resin composition having a solid content of 60 wt%. Since the epoxy resin cured product of Comparative Example 1 had no functionalized polyimide resin introduced therein, the fracture toughness value was small (brittle), and thus the peel strength was low.

<< Comparative Examples 2-3 >>
In this comparative example, an epoxy resin composition containing no functionalized polyimide resin was produced.
According to the composition described in Table 2, an epoxy resin, a curing agent, and a curing accelerator were put in a glass container and mixed to prepare a varnish of an epoxy resin composition having a solid content of 60 wt%.
In Comparative Examples 2 and 3, since the functionalized polyimide resin was not introduced, the fracture toughness value was small (brittle), and thus the peel strength was also small.

<< Comparative Example 4 >>
In this comparative example, an epoxy resin composition containing a non-functionalized polyimide resin was produced.
In accordance with the composition described in Table 2, the epoxy resin, the curing agent, the curing accelerator, and the polyimide resin solution synthesized in Comparative Synthesis Example 1 were placed in a glass container and mixed to obtain a varnish of an epoxy resin composition having a solid content of 60 wt%. Was prepared.
In Comparative Example 4, since no functional group was imparted to the introduced polyimide resin, the peel strength was relatively good, but the fracture toughness value was small.

<< Comparative Example 5 >>
In this comparative example, an epoxy resin composition containing a polyamide elastomer (polyether ester amide) was produced.
According to the composition described in Table 2, an epoxy resin, a curing agent, a curing accelerator, and a polyamide elastomer were placed in a glass container and mixed to prepare a varnish of an epoxy resin composition having a solid content of 60 wt%.
When the polyamide elastomer of Comparative Example 5 was introduced, the fracture toughness value and peel strength were sufficient, but the water absorption was high, and the alkali resistance, acid resistance, and solder heat resistance were poor.

As shown in Tables 2 and 3, the epoxy resin compositions obtained in Examples 1 to 8 exhibited superior fracture toughness values as compared with the epoxy resin compositions obtained in Comparative Examples 1 to 4. Moreover, the epoxy resin composition obtained in Examples 1-8 showed the peeling strength outstanding compared with the epoxy resin composition obtained in Comparative Examples 1-3.
The epoxy resin composition obtained in Comparative Example 5 had a high fracture toughness value and peel strength, but was impractical in chemical resistance and solder heat resistance.

  The functionalized polyimide resin in the epoxy resin composition of the present invention is a polyimide resin having a high imidization rate, but has high solubility in general-purpose solvents, and has excellent flexibility, adhesion to substrates, and low water absorption. Since it has heat resistance and heat resistance and is light in color, it can be widely applied not only in the electric / electronic field but also in the industrial paint field where the above performance is required.

Claims (11)

(I) General formula (1):

(Where
R ¹ is the same or different for each repeating unit, and is an unsubstituted or substituted aliphatic tetracarboxylic acid residue having 0 to 66 carbon atoms, an alicyclic tetracarboxylic acid residue, and / or an aromatic tetracarboxylic acid residue. A group;
R ² is the same or different for each repeating unit, and is selected from the group consisting of an unsubstituted or substituted aliphatic diamine residue having 2 to 56 carbon atoms, an alicyclic diamine residue, and an aromatic diamine residue. A dimer diamine residue derived from at least one diamine residue and a polymerized fatty acid having 20 to 48 carbon atoms;
(The weight ratio of the diamine residue to the dimer diamine residue is 0: 100 to 90:10, and the ratio of the imide bond exceeds 50%)
A polyimide resin having a repeating unit represented by
(II) an epoxy resin having two or more epoxy groups in one molecule, and (III) an epoxy resin curing agent capable of curing the epoxy group of (II),
An epoxy resin composition containing   The epoxy resin composition of Claim 1 whose ratio of the imide bond of the said repeating unit is 90% or more.   The epoxy resin composition according to claim 1 or 2, wherein a terminal functional group of the polyimide resin is a functional group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an amino group. General formula (1):

(Where
R ¹ is the same or different for each repeating unit, and is an unsubstituted or substituted aliphatic tetracarboxylic acid residue having 0 to 66 carbon atoms, an alicyclic tetracarboxylic acid residue, and / or an aromatic tetracarboxylic acid residue. A group;
R ² is the same or different for each repeating unit, and is selected from the group consisting of an unsubstituted or substituted aliphatic diamine residue having 2 to 56 carbon atoms, an alicyclic diamine residue, and an aromatic diamine residue. A dimer diamine residue derived from at least one diamine residue and a polymerized fatty acid having 20 to 48 carbon atoms;
(The weight ratio of the diamine residue to the dimer diamine residue is 0: 100 to 90:10, and the ratio of the imide bond exceeds 50%)
A polyimide resin having a repeating unit represented by and having a functional group at the end of the molecular chain.   The polyimide resin according to claim 4, wherein the functional group at the molecular chain terminal is a functional group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and an amino group. (I) General formula (2):

(Where
R ¹ is an unsubstituted or substituted aliphatic tetracarboxylic acid residue having 0 to 66 carbon atoms, an alicyclic tetracarboxylic acid residue, or an aromatic tetracarboxylic acid residue.
One or more tetracarboxylic dianhydrides represented by
(II) General formula (3):

(Where
R ² is at least one diamine residue selected from the group consisting of an unsubstituted or substituted aliphatic diamine residue having 2 to 56 carbon atoms, an alicyclic diamine residue, and an aromatic diamine residue. ) One or more aliphatic, alicyclic, and / or aromatic diamines, and (III) one or more dimer diamines derived from polymerized fatty acids having 20 to 48 carbon atoms. A first step of obtaining a polyamic acid by reacting a cyclic and / or aromatic diamine and a dimer diamine in a weight ratio of 0: 100 to 90:10; and imidating the polyamic acid. Including two steps;
In order to introduce a functional group at the terminal, in the first step or the second step, a compound containing one carboxyl group and one acid anhydride group, a compound containing one carboxyl group and one amino group, a carboxyl group Adding at least one compound selected from the group consisting of a compound containing two and one amino group, a compound containing one phenolic hydroxyl group and one amino group, and a compound containing two secondary amino groups A process for producing a polyimide resin characterized by the above. (I) General formula (2):

(Where
R ¹ is an unsubstituted or substituted aliphatic tetracarboxylic acid residue having 0 to 66 carbon atoms, an alicyclic tetracarboxylic acid residue, or an aromatic tetracarboxylic acid residue.
One or more tetracarboxylic dianhydrides represented by
(II) General formula (3):

(Where
R ² is at least one diamine residue selected from the group consisting of an unsubstituted or substituted aliphatic diamine residue having 2 to 56 carbon atoms, an alicyclic diamine residue, and an aromatic diamine residue. ) One or more aliphatic, alicyclic, and / or aromatic diamines, and (III) one or more dimer diamines derived from polymerized fatty acids having 20 to 48 carbon atoms. In the first step of obtaining a polyamic acid by reacting a cyclic and / or aromatic diamine with the dimer diamine in a weight ratio of 0: 100 to 90:10, a functional group is introduced at the terminal. A first step in which the equivalent ratio of tetracarboxylic dianhydride to diamine is 0.5 or more and less than 1.0; and a second step of imidizing the polyamic acid;
The manufacturing method of the polyimide resin characterized by including.   A polyimide resin produced by the production method according to claim 6.   The epoxy resin adhesive characterized by including the epoxy resin composition as described in any one of Claims 1-5.   The epoxy resin coating agent characterized by including the epoxy resin composition as described in any one of Claims 1-5.   An article to which the epoxy resin adhesive according to claim 9 or the epoxy resin coating agent according to claim 10 is applied.