JPWO2016171101A1 - Polyimide, curable resin composition, cured product - Google Patents

Abstract

The present invention relates to a polyimide obtained by reacting a tetracarboxylic acid component with a diamine component containing a diamine compound of the following formula (1), a reactive group having active hydrogen, and a reaction having an unsaturated double bond The present invention relates to a polyimide having at least one reactive group selected from a group in the molecule. In formula (1), A represents a tetravalent saturated hydrocarbon residue, and may be a linear structure or a ring structure. R1 and R2 each independently represent an alkylene group having 1 to 20 carbon atoms, and R3 and R4 each independently represent a linear alkyl group having 1 to 20 carbon atoms.

Description

The present invention is a polyimide obtained by reacting a tetracarboxylic acid component with a diamine component containing a diamine compound represented by the following general formula (1), which has a reactive group having active hydrogen, and an unsaturated double bond. The present invention relates to a polyimide having at least one reactive group selected from reactive groups having a bond in a molecule.

In recent years, with the miniaturization of electronic devices, the density of electronic components has been increasing. A material used for a printed wiring board is required to have a matching coefficient of thermal linear expansion with a semiconductor chip in order to ensure reliability, and measures are taken by increasing the resin material to a high crosslinking density. As a result, it has been pointed out that the obtained printed wiring board is inferior in toughness, and there is a demand for a flexibility imparting agent for complementing brittleness while realizing a low linear expansion coefficient.

Patent Documents 1, 2, and 3 describe polyimide siloxane solution compositions obtained from a tetracarboxylic acid component and a diamine component containing diaminopolysiloxane. Since this polyimidesiloxane solution composition gives a cured product excellent in flexibility and thermal decomposability in the air, it is preferably used as a flexibility imparting agent, but further improvement may be required from the viewpoint of outgassing. is there.

Patent Document 4 discloses a polyimide solution composition using a diamine component containing a specific alkylene diamine and / or polyoxyalkylene diamine, and Patent Document 5 discloses a thermosetting resin composition using a polyimide having a urethane bond. Things are listed. These polyimide solution compositions give a cured product excellent in flexibility without using a siloxane-based material, but have a problem that the thermal decomposition temperature is low and the heat resistance is poor.

Japanese Patent Laid-Open No. 8-253676 JP 2006-156949 A JP 2012-255107 A JP 2008-231420 A JP 2012-162736 A

The present invention provides a polyimide having flexibility and heat resistance equivalent to that of a siloxane-based material without using a siloxane-based material, a curable resin composition containing the polyimide and a curable resin, and a cured product thereof. For the purpose.

That is, the present invention relates to the following matters.

1. A polyimide obtained by reacting a tetracarboxylic acid component with a diamine component containing a diamine compound represented by the following general formula (1), from a reactive group having active hydrogen and a reactive group having an unsaturated double bond A polyimide having at least one reactive group selected in a molecule.

式（１）中、Ａは４価の飽和炭化水素残基を表し、直鎖構造であっても環構造であってもよい。Ｒ_１およびＲ_２はそれぞれ炭素数１〜２０のアルキレン基を表し、Ｒ_３およびＲ_４はそれぞれ炭素数１〜２０の直鎖状アルキル基を表す。

In formula (1), A represents a tetravalent saturated hydrocarbon residue, and may be a linear structure or a ring structure. R ₁ and R ₂ each represent an alkylene group having 1 to 20 carbon atoms, and R ₃ and R ₄ each represent a linear alkyl group having 1 to 20 carbon atoms.

2. 2. The polyimide according to 1 above, wherein the diamine compound represented by the formula (1) has 20 to 48 carbon atoms.

3. The polyimide according to 1 or 2, wherein the reactive group having active hydrogen is at least one selected from a hydroxyl group, a carboxyl group, an aldehyde group, an amino group, an imino group, and a thiol group.

4). 4. The polyimide according to any one of 1 to 3, wherein the diamine component is a diamine other than the diamine compound represented by the formula (1) and includes the diamine having the reactive group described in 1 above.

5. 5. The polyimide according to any one of 1 to 4 above, wherein the reactive group described in 1 is a carboxyl group or a hydroxyl group.

6). 5. The polyimide according to 4 above, wherein the other diamine according to 4 is an aromatic diamine represented by the following general formula (2).

式（２）中、ＸおよびＹはそれぞれ独立に直接結合、または下記一般式（３）を示し、ｒ_１はカルボキシル基または水酸基を示し、ｎ１は０以上である。

In formula (2), X and Y each independently represent a direct bond or the following general formula (3), r ₁ represents a carboxyl group or a hydroxyl group, and n 1 is 0 or more.

式中、Ｒ_５、Ｒ_６は水素、メチル基、又はハロゲン化メチル基である。

In the formula, R ₅ and R ₆ are hydrogen, a methyl group, or a halogenated methyl group.

7). The other diamine shown by said Formula (2) WHEREIN: The polyimide of said 6 whose n1 is the number of 0-2.

8). Other diamines described in 4 above are 4,4′-diamino-3,3′-dicarboxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4-diamino-2,2 ′. One selected from the group consisting of -dicarboxydiphenyl ether, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 2,2'-bis (3-amino-4-hydroxyphenyl) propane Or the polyimide of said 4 or 6 which is 2 or more types.

9. The polyimide according to any one of 1 to 8, wherein the diamine component does not contain a siloxane component.

10. 10. The method for producing a polyimide according to any one of 1 to 9 above.

11. The polyimide resin composition containing the polyimide in any one of said 1-9.

12 10. A curable resin composition comprising the polyimide according to any one of 1 to 9 and a curable resin.

13. 13. The curable resin composition as described in 12 above, comprising an epoxy resin.

14 14. The curable resin composition, wherein the epoxy resin according to 13 has two or more glycidyl groups.

15. 13. The curable resin composition according to 12, wherein the curable resin composition contains an isocyanate resin.

16. 16. The curable resin composition, wherein the isocyanate resin according to 15 has two or more isocyanate groups.

17. 13. The curable resin composition according to the above 12, wherein the curable resin composition is a composition containing a resin having an unsaturated double bond.

18. 18. The curable resin composition according to the above 17, wherein the curable resin composition contains a resin having two or more unsaturated double bonds.

19. Hardened | cured material using the curable resin composition in any one of said 12-18.

When the curable resin composition containing the polyimide of the present invention is used, a cured product having high flexibility and high heat resistance equal to or higher than that of a conventional product can be obtained. Therefore, the cured product produced from the polyimide of the present invention is expected to be used as a sealing agent for printed wiring boards, overcoat materials, electronic components and semiconductor packages.

The polyimide of the present invention is a polyimide obtained by reacting a tetracarboxylic acid component with a diamine component containing a diamine compound represented by the following general formula (1), a reactive group having active hydrogen, and an unsaturated group. It is a polyimide characterized by having at least one reactive group selected from reactive groups having a double bond in the molecule. Details will be described below.

In the present invention, the diamine component includes a diamine compound represented by the following formula (1) {hereinafter sometimes referred to as a diamine compound (1)}.

式（１）中、Ａは４価の飽和炭化水素残基を表し、直鎖構造であっても環構造であってもよい。Ｒ_１およびＲ_２はアルキレン基を表し、Ｒ_３およびＲ_４は直鎖状アルキル基を表す。

In formula (1), A represents a tetravalent saturated hydrocarbon residue, and may be a linear structure or a ring structure. R ₁ and R ₂ represent an alkylene group, and R ₃ and R ₄ represent a linear alkyl group.

The total number of carbon atoms of the diamine compound (1) is preferably 20 to 48, more preferably 24 to 46, still more preferably 30 to 40, and particularly preferably 36.

R ₁ and R ₂ are alkylene groups, each having preferably 1 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, Examples include a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group, a nonadecylene group, and an eicosylene group. R ₁ and R ₂ may be the same or different from each other.

R ₃ and R ₄ are linear alkyl groups, each preferably having 1 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, Examples include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group. R ₃ and R ₄ may be the same or different from each other.

When A has a linear structure, although not particularly limited, A is preferably a residue having 1 to 4 carbon atoms,

または

Or

であることが、より好ましい。Ａが環構造の場合、特に限定はされないが、Ａは炭素数５〜７のシクロアルカンから４つの水素を除いた４個の残基であることが好ましく、

It is more preferable that When A is a ring structure, although not particularly limited, A is preferably four residues obtained by removing four hydrogens from a cycloalkane having 5 to 7 carbon atoms,

で表される４価の６員環であることがより好ましい。環構造であるＡへの基Ｒ_１〜Ｒ_４の結合位置は任意である。

The tetravalent 6-membered ring represented by The bonding position of the groups R _{1 to} R ₄ to A which is a ring structure is arbitrary.

The diamine compound (1) used in the present invention can be produced from a dimer acid obtained by dimerizing an aliphatic unsaturated carboxylic acid. In the present invention, for example, dimer diamine having 36 carbon atoms obtained from a fatty acid having 18 carbon atoms and having one or more double bonds can be used. As a commercial item, PRIAMINE 1074 (made by Croda Japan Co., Ltd.) is mentioned, for example.

As a diamine compound represented by Formula (1), the compound represented by either of following formula (1-1)-(1-3) is mentioned, for example.

The polyimide of the present invention has at least one reactive group selected from a reactive group having active hydrogen and a reactive group having an unsaturated double bond in the molecule. Active hydrogen is bonded to hydrogen bonded to O, N, and S having a large electronegativity, or to carbon having two or more groups such as CO ₂ R, CN, and COR having a large electron-withdrawing property in an organic compound. In addition to hydrogen, hydrogen in an aldehyde group is exemplified. Usually, active hydrogen has reactivity with a glycidyl group in an epoxy resin, an isocyanate group in an isothiocyanate resin, an unsaturated double bond of a resin having an unsaturated double bond, and the like. Examples of the reactive group having active hydrogen include a hydroxyl group, a carboxyl group, an aldehyde group, an amino group, an imino group, and a thiol group. Examples of the reactive group having an unsaturated double bond include a vinyl group, an allyl group, and an acryloyl group. Further, a triple bond such as a substituted or unsubstituted ethynyl group may be used in place of the unsaturated double bond. The reactive group selected from the reactive group having active hydrogen and the reactive group having an unsaturated double bond may be derived from a diamine component or a tetracarboxylic acid component. Moreover, when originating in a diamine component, the diamine compound (1) may or may not have a reactive group. In particular, the diamine component has, in addition to the diamine compound (1), a diamine having at least one reactive group in the molecule selected from a reactive group having active hydrogen and a reactive group having an unsaturated double bond (hereinafter, It is also preferable to include a “reactive group-containing diamine”.

The reactive group-containing diamine reactive group is not particularly limited, but is a carboxyl group that exhibits excellent reactivity with an epoxy resin or an isocyanate resin used as a curable resin constituting a substrate material or a sealing material. A hydroxyl group is preferred. The number of reactive groups in the reactive group-containing diamine is preferably 1 or more.

The reactive group-containing diamine is not limited to either an aromatic diamine or an aliphatic diamine as long as it has the reactive group, but an aromatic diamine represented by the following chemical formula (2) is preferable. It is.

化学式（２）中、ＸおよびＹはそれぞれ独立に直接結合、または下記式（３）における式（３−１）〜（３−８）から選ばれる基を示し、ｒ_１は反応性基を示し、ｎ１は０以上である。化学式（２）中のフェニレン環は、ハロゲン、アルキル基（好ましくは炭素数１〜約４）等で置換されていてもよい。

In chemical formula (2), X and Y each independently represent a direct bond or a group selected from formulas (3-1) to (3-8) in the following formula (3), and r ₁ represents a reactive group. , N1 is 0 or more. The phenylene ring in the chemical formula (2) may be substituted with a halogen, an alkyl group (preferably having 1 to about 4 carbon atoms), or the like.

式中、Ｒ_５、Ｒ_６は水素、メチル基、又はハロゲン化メチル基である。

In the formula, R ₅ and R ₆ are hydrogen, a methyl group, or a halogenated methyl group.

In chemical formula (2), n1 is preferably a number from 0 to 3, more preferably a number from 0 to 2, and even more preferably a number from 0 to 1.

Among the reactive group-containing diamines represented by the chemical formula (2), examples of diamines having a carboxyl group as a reactive group include benzenecarboxylic acids such as 3,5-diaminobenzoic acid and 2,4-diaminobenzoic acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, 4, Carboxyphenyl compounds such as 4′-diamino-2,2 ′, 5,5′-tetracarboxybiphenyl, 3,3′-diamino-4,4′-dicarboxydiphenylmethane, 4,4′-diamino-3, 3'-dicarboxydiphenylmethane, 4,4'-diamino-2,2'-dicarboxydiphenylmethane, 2,2-bis (3-amino-4-carbo Cyphenyl) propane, 2,2-bis (4-amino-3-carboxyphenyl) propane, 2,2-bis (3-amino-4-carboxyphenyl) hexafluoropropane, 4,4′-diamino-2,2 Carboxydiphenylalkane compounds such as', 5,5'-tetracarboxybiphenyl, 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, Carboxydiphenyl ether compounds such as 4,4′-diamino-2,2′-dicarboxydiphenyl ether, 4,4′-diamino-2,2′5,5′-tetracarboxydiphenyl ether, 3,3′-diamino-4 , 4′-dicarboxydiphenylsulfone, 4,4′-diamino-3,3′-dica Carboxydiphenylsulfone compounds such as boxydiphenylsulfone, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenylsulfone, 2,2-bis [4- (4-amino-3-carboxy) Bis (carboxyphenoxyphenyl) alkane compounds such as phenoxy) phenyl] propane, bis (carboxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-carboxyphenoxy) biphenyl, 2,2-bis And bis (carboxyphenoxyphenyl) sulfone compounds such as [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone. These can be used alone or in combination of two or more.

Examples of the diamine having a hydroxyl group as a reactive group among the reactive group-containing diamine represented by the chemical formula (2) include phenols such as 3,5-diaminophenol and 2,4-diaminophenol, 3, 3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-2,2'-dihydroxybiphenyl, 4,4'-diamino- Hydroxybiphenyl compounds such as 2,2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis (3-amino-4-hydroxyphenyl) Nyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4′-diamino-2,2 Hydroxydiphenylalkane compounds such as', 5,5'-tetrahydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 4, Hydroxydiphenyl ether compounds such as 4′-diamino-2,2′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′5,5′-tetrahydroxydiphenyl ether, 3,3′-diamino-4,4 ′ -Dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxy Hydroxydiphenylsulfone compounds such as diphenylsulfone, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylsulfone, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) Bis (hydroxyphenoxyphenyl) alkane compounds such as phenyl] propane, bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 2,2-bis [4 Bis (hydroxyphenoxyphenyl) sulfone compounds such as-(4-amino-3-hydroxyphenoxy) phenyl] sulfone, bis (2-hydroxy-3-amino-5-methylphenyl) methane, 2,6-di {(2 -Hydroxy-3-amino-5-methylphenyl) methyl} -4-me Examples include tilphenol and bis {2-hydroxy-3- (2'-hydroxy-3'-amino-5'methyl) benzyl-5-methyl} methane. These can be used alone or in combination of two or more.

The reactive group-containing diamine represented by the chemical formula (2) is preferably mononuclear or binuclear, specifically 3,5-diaminobenzoic acid, 4,4′-diamino-3,3′-dicarboxyl. Diphenylmethane, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4-diamino-2,2′-dicarboxydiphenyl ether, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane And 2,2′-bis (3-amino-4-hydroxyphenyl) propane. In the present invention, 3,5-diaminobenzoic acid, 4,4'-diamino-3,3'-dicarboxydiphenylmethane, and 4,4'-diamino-3,3'-dihydroxybiphenyl are particularly preferably used.

In addition to the diamine compounds (1) and (2), the diamine component may further contain other diamines.

The other diamine is not particularly limited as long as it is a diamine other than the diamines represented by the above formulas (1) and (2), but is an aroma composed of a plurality of benzene rings represented by the following chemical formula (4). Group diamines are preferred.

化学式（４）において、ＸおよびＹはそれぞれ独立に直接結合、または前記式（３）を示し、ｎ２は１又は２である。化学式（４）中のフェニレン環は、ハロゲン、アルキル基（好ましくは炭素数１〜約４）等で置換されていてもよい。またジアミン成分が、他のジアミンとして、式（４）で表されるジアミンと式（２）で表されるジアミンを両方含有する場合、これらジアミンにおけるＸ及びＹは同一であってもよく、異なっていてもよい。

In the chemical formula (4), X and Y each independently represent a direct bond or the formula (3), and n2 is 1 or 2. The phenylene ring in the chemical formula (4) may be substituted with a halogen, an alkyl group (preferably having 1 to about 4 carbon atoms) or the like. When the diamine component contains both the diamine represented by formula (4) and the diamine represented by formula (2) as other diamines, X and Y in these diamines may be the same or different. It may be.

Examples of the aromatic diamine represented by the chemical formula (4) include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 1,4-diamino-2,5-dihalogenobenzene and the like. Diamines containing one benzene ring, bis (4-aminophenyl) ether, bis (3-aminophenyl) ether, bis (4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (4 -Aminophenyl) methane, bis (3-aminophenyl) methane, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, 2,2-bis (4-aminophenyl) propane, 2,2- Bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, o-dianisidine, o Diamines containing two benzene rings such as tolidine and tolidinesulfonic acids, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4 -Aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, α, α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, α, α'-bis (4-aminophenyl) ) Diamines containing three benzene rings such as 1,3-diisopropylbenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-amino) Phenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4 ′-(4-aminophenoxy) biphe Examples thereof include diamine compounds such as diamines containing four or more benzene rings such as nyl, 9,9-bis (4-aminophenyl) fluorene, and 5,10-bis (4-aminophenyl) anthracene. These can be used alone or in combination of two or more.

1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2 -Cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine 4,4'-methylenebiscyclohexylamine, N, N'-bis (2-aminoethyl) -1,3-propanediamine, bis (3 -Aminopropyl) ethylenediamine, 1,4-bis (3-aminopropyl) piperazine, N-methyl -2,2'-diaminodiethylamine, 3,3'-diaminodipropylamine, N, N-bis (3-aminopropyl) methylamine, bis (3-aminopropyl) ether, 1,2-bis (2- Aminoethoxy) ethane, aliphatic diamine compounds such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] -undecane, 2,2′-thiobis (ethylamine) Can be used with the above aromatic diamine.

Among the diamine components, the diamine compound (1) is preferably contained in an amount of 40 to 99 mol%, more preferably 50 to 95 mol%, still more preferably 60 to 95 mol%, particularly 65 to 95 mol%. It is preferable that When the content of the diamine compound (1) is less than 40 mol%, the obtained cured product is inferior in flexibility, and when it exceeds 99 mol%, there is a risk that poor curing occurs when the cured product is used. is there.

Among the diamine components, the reactive group-containing diamine is preferably contained in an amount of 1 to 60 mol%, more preferably 5 to 50 mol%, still more preferably 5 to 40 mol%, and particularly preferably 5 to 35 mol%. When the content of the reactive group-containing diamine exceeds 60 mol%, the resulting cured product is inferior in flexibility, and when it is less than 1 mol%, there is a risk that poor curing will occur when a cured product is obtained. is there. When the diamine component contains the diamine compound (2), the proportion of the diamine compound (2) in the diamine component is also preferably 1 to 60 mol%, more preferably 5 to 50 mol%, still more preferably 5 to 40 mol. %, Particularly preferably 5 to 35 mol%.

  Among the diamine components, diamines other than the diamine compound (1) and the reactive group-containing diamine may be added as long as the physical properties of the resulting cured film are not significantly impaired.

Examples of the tetracarboxylic acid component include aromatic tetracarboxylic acids or their acid dianhydrides and esterified products of lower alcohols, alicyclic tetracarboxylic acids or their acid dianhydrides and lower alcohols. Preferable examples are esterified products.
Aromatic tetracarboxylic acids include biphenyltetracarboxylic acid, naphthalenetetracarboxylic acid, pyromellitic acid, and tetracarboxylic acid having a structure in which the benzene rings of two o-benzenedicarboxylic acid groups are bonded together by a linking group. Can be mentioned. As this linking group, —O—, —CO—, —SO ₂ —, an alkylene group (preferably having 1 to 3 carbon atoms, etc.), a halogenated alkylene group (preferably having 1 to 3 carbon atoms, etc.), a phenylene group or A group formed by combining these under conditions where oxygen atoms do not continue to each other is mentioned.
Examples of the biphenyltetracarboxylic acid include 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid. Carboxylic acid is mentioned.
Examples of the naphthalenetetracarboxylic acid include 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 4,5,8-naphthalenetetracarboxylic acid.
Examples of the tetracarboxylic acid having a structure in which the benzene rings of the two o-benzenedicarboxylic acid groups are bonded with a linking group include 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, 3, 3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2-bis (3,4-benzenedicarboxylic acid) hexafluoropropane, 1,4 -Bis (3,4-benzenedicarboxylic acid) benzene, 2,2-bis [4- (3,4-phenoxydicarboxylic acid) phenyl] propane, 1,1-bis (2,3-dicarboxyphenyl) ethane, Aromatic tetracarboxylic acids such as 4,4 ′-(4,4′-isopropylidenebisphenoxy) diphthalic acid may be mentioned.
As the alicyclic tetracarboxylic acid, a substituted or unsubstituted cycloalkyl group (preferably having 4 to 7 carbon atoms), a polyalicyclic type in which a plurality of alicyclic rings are composed of two or more common carbon atoms ( Preferably, 4 hydrogen atoms in a bridged ring type (preferably having 7 to 12 carbon atoms) in which the ring-forming carbon atoms further form a ring by a chemical bond are substituted with carboxylic acid groups. Specifically, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetra Carboxylic acid, 3-methyl-4-cyclohexene-1,2,4,5-tetracarboxylic acid, 5- (1,2-dicarboxyethyl) -3-methyl-3-cyclohexene-1,2-dica Boronic acid, [1,1′-bi (cyclohexane)]-3,3 ′, 4,4′-tetracarboxylic acid, [1,1′-bi (cyclohexane)]-2,3,3 ′, 4 ′ Tetracarboxylic acid, [1,1′-bi (cyclohexane)]-2,2 ′, 3,3′-tetracarboxylic acid, 4,4′-methylenebis (cyclohexane-1,2-dicarboxylic acid), 4, 4 ′-(propane-2,2-diyl) bis (cyclohexane-1,2-dicarboxylic acid), 4,4′-oxybis (cyclohexane-1,2-dicarboxylic acid), 4,4′-thiobis (cyclohexane-) 1,2-dicarboxylic acid), 4,4′-sulfonylbis (cyclohexane-1,2-dicarboxylic acid), 4,4 ′-(dimethylsilanediyl) bis (cyclohexane-1,2-dicarboxylic acid), 4, 4 '-(tetrafluoropropane-2,2-dii ) Bis (cyclohexane-1,2-dicarboxylic acid), octahydropentalene-1,3,4,6-tetracarboxylic acid, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid Acid, 6- (carboxymethyl) bicyclo [2.2.1] heptane-2,3,5-tricarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclo [4.2.2.02,5] decane-3,4,7,8-tetracarboxylic acid , Tricyclo [4.2.2.02,5] dec-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxatricyclo [4.2.1.02,5] nonane-3 , 4,7,8-tetracarboxylic acid, decahydro-1,4: 5,8-dimethanonaphth Talen-2,3,6,7-tetracarboxylic acid and the like can be preferably mentioned. These can be used alone or in combination of two or more.

The tetracarboxylic acid component is not particularly limited, but biphenyltetracarboxylic acid, tetracarboxylic acid having a structure in which benzene rings of two o-benzenedicarboxylic acid groups are bonded to each other by a linking group, and alkylcyclohexane Preferred examples include alkyl tetracarboxylic acids (especially those having two carboxylic acid groups in each of the cycloalkyl group and the alkyl group in the alkylcycloalkyl group), especially 2,3,3 ′, 4′-biphenyl. Tetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic acid, 5- (1,2-dicarboxyethyl)- Uses amorphous tetracarboxylic acid components such as 3-methyl-3-cyclohexene-1,2-dicarboxylic acid Rukoto is preferable. In the present invention, 2,3,3 ', 4'-biphenyltetracarboxylic acid is particularly preferably used because of excellent heat resistance.

In addition, in the polyimide of the present invention, a reactive group selected from a reactive group having an active hydrogen such as a hydroxyl group, a carboxyl group, an aldehyde group, an amino group, an imino group, and a thiol group, and a reactive group having an unsaturated double bond In order to have at least one in the molecule, a reactive group-containing tetracarboxylic acid component may be included.

The ratio of the tetracarboxylic acid component and the diamine component used in the present invention is approximately equimolar, preferably 0.8 to 1.2, more preferably 0.9 to tetracarboxylic acid component per 1 mol of diamine component. The ratio is about 1.1 mol.

式中Ｒ_７、Ｒ_８は直鎖状アルキル基であり、例えば、メチル基、エチル基、プロピル基、ブチル基等を挙げることができる。Ｒ_７およびＲ_８は互いに同一であっても異なっていてもよい。Ｒ_９，Ｒ_１０は非反応性のものとしては水素、メチル基やエチル基等の直鎖状アルキル基およびそのハロゲン化物、フェニル基、アラルキル基などが挙げられ、反応性のものとしては水酸基、カルボキシル基、アミノ基、エポキシ基、チオール基などが挙げられる。Ｒ_９およびＲ_１０は互いに同一であっても異なっていてもよい。The diamine component used in the present invention preferably contains no siloxane component. The siloxane component is a component (compound) having a structure represented by the following general formula (5) and having a repeating unit number n3 of 2 or more. “Non-containing siloxane component” preferably means that the number of moles of the compound having a siloxane component in the diamine component is 0 mol%. Normally, the tetracarboxylic acid component does not contain a siloxane component.

In the formula, R ₇ and R ₈ are linear alkyl groups, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. R ₇ and R ₈ may be the same or different from each other. R ₉ and R ₁₀ are non-reactive such as hydrogen, linear alkyl groups such as methyl and ethyl groups, and their halides, phenyl groups, aralkyl groups, etc., and reactive groups are hydroxyl groups, Examples thereof include a carboxyl group, an amino group, an epoxy group, and a thiol group. R ₉ and R ₁₀ may be the same as or different from each other.

Moreover, it is preferable that the diamine component used in this invention does not contain an aliphatic ether component. The aliphatic ether component is a component (compound) having an R—O—R bond (R is an alkyl group having 2 or more carbon atoms). The phrase “not containing an aliphatic ether component” preferably means that the number of moles of the compound having an R—O—R bond in the diamine component is 0 mol%.

The polyimide of the present invention can also be expressed as the following polyimide.
It has a structural unit represented by the following general formula (1 ′), and has at least one reactive group selected from a reactive group having active hydrogen and a reactive group having an unsaturated double bond in the molecule. Polyimide.

（式中、Ｂ^１は４価のテトラカルボン酸残基であり、Ａ、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は一般式（１）と同じである。）

(In the formula, B ¹ is a tetravalent tetracarboxylic acid residue, and A, R ₁ , R ₂ , R ₃ and R ₄ are the same as those in the general formula (1).)

Here, in the formula (1 ′), a group represented by —N—R ₁ —A (—R ₃ ) (— R ₄ ) —R ₂ —N— is a diamine represented by the above general formula (1). It is a residue of the compound, and all the explanations of the general formula (1) apply to this group. Examples of the tetracarboxylic acid residue represented by B ¹ include the residues of the tetracarboxylic acid component, and all the descriptions of the tetracarboxylic acid component apply to the tetracarboxylic acid that gives the tetracarboxylic acid residue. . The explanation of the reactive group having active hydrogen, the reactive group having an unsaturated double bond, and the reactive group selected from these is as described above. Moreover, the ratio of the preferable mole number of the structural unit represented by Formula (1 ') in all the structural units of the polyimide of this invention is preferable of the diamine compound represented by the said Formula (1) in the diamine component mentioned above. This is the same as the mole ratio.
The reactive group may be bonded to any of B ¹ , R ₁ , R ₂ , R ₃ and R ₄ represented by the general formula (1 ′), or the general formula in the polyimide of the present invention. It may be bonded to a structural unit other than (1 ′), for example, B ² or D in the following formula (6).

（式中、Ｂ^２はテトラカルボン酸残基であり、Ｂ^１と同一であっても異なっていてもよい。Ｄは、上記−Ｒ_１−Ａ（−Ｒ_３）（−Ｒ_４）−Ｒ_２−以外の構造を有するジアミン残基である。）

(In the formula, B ² is a tetracarboxylic acid residue and may be the same as or different from B ^1. D is the above-mentioned —R ₁ —A (—R ₃ ) (— R ₄ ) —R. _It is a diamine residue having a structure other than _2- .

  When -D- in the above formula (6) has a reactive group, a preferred example of the structure of -D- is a structure represented by the following general formula (2 ').

（Ｘ、Ｙ、ｒ_１、ｎ１は、上記一般式（２）と同じである）

(X, Y, r ₁ and n1 are the same as those in the general formula (2)).

Examples of tetracarboxylic acid residues represented by B ² include residues of the tetracarboxylic acid component, and all the descriptions of the tetracarboxylic acid component are all described in terms of the tetracarboxylic acid resulting in the tetracarboxylic acid residue. apply. Moreover, when D in the said Formula (6) has a reactive group, the ratio of the preferable mole number of the structural unit of the formula (6) which has this reactive group in all the structural units of the polyimide of this invention is the diamine mentioned above. It is the same as the preferable ratio of the reactive group containing diamine in a component. When the polyimide of the present invention has a structural unit represented by the formula (1 ′) and a structural unit represented by the formula (6), both the structural units may be bonded in a block shape, or randomly. May be bonded to.

The polyimide of the present invention and the polyimide resin composition containing the polyimide can be produced by reacting a tetracarboxylic acid component and the diamine compound (1) in a solvent. Here, “reacting” means that a tetracarboxylic acid component and a diamine component react to form an imide ring while forming a polyimide skeleton, that is, polymerization / imidization. Therefore, conventionally known polymerization and imidization methods can be suitably used. For example, the tetracarboxylic acid component and the diamine component can be heated at a temperature of about 100 to 250 ° C. in a solvent to be polymerized and imidized in one step. In addition, a tetracarboxylic acid component and a diamine component are reacted in a solvent at a temperature of less than about 100 ° C. to obtain a polyimide precursor (polyamic acid), and then heated to about 100 to 250 ° C. for imidization or dehydration. It can also be imidized by a chemical imidizing agent such as acetic anhydride / pyridine system or dicyclohexylcarbodiimide which is a cyclizing reagent. In the imidization reaction, an azeotropic agent such as toluene or xylene may be added and reacted to remove the generated water from the system.

The solvent used in the reaction is not particularly limited as long as it provides a solvent environment for obtaining a polyimide by suitably reacting (polymerizing / imidizing) a tetracarboxylic acid component and a diamine component. N, N-dimethylformamide Amide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyllactone, γ-valerolactone, δ-valerolactone , Γ-caprolactone, ε-caprolactone, cyclic ester solvents such as α-methyl-γ-butyllactone, carbonate solvents such as ethylene carbonate and propylene carbonate, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetra Glyco and other glyco Le solvents, m- cresol, p- cresol, 3-chlorophenol, phenol solvents such as 4-chlorophenol, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide or the like is employed. Furthermore, other common organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, tetrahydrofuran Dimethoxyethane, diethoxyethane, dibutyl ether, ethanol, methanol and the like can also be used. These may be mixed and used as long as they provide a solvent environment for obtaining polyimide. If necessary, an aromatic hydrocarbon solvent such as benzene, toluene or xylene may be used in combination.

In the present invention, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-, which is aprotic and has a boiling point of 150 to 220 ° C. Ethyl-2-pyrrolidone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyl lactone and the like can be preferably used. In particular, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether are preferable because of their low hygroscopicity and excellent drying characteristics.

In the present invention, it is preferable that the polyimide resin composition is dissolved in a solvent at least 3 wt%, preferably 5 to 60 wt%, more preferably 20 to 50 wt% as a solid content concentration. As for the viscosity of the polyimide resin composition, the solution viscosity at 25 ° C. (E-type rotational viscosity) is preferably 0.1 to 1000 Pa · s, more preferably 0.1 to 300 Pa · s. When the viscosity is within this range, it is easy to handle and excellent in workability. The logarithmic viscosity (measurement concentration: 0.5 g / 100 ml, solvent: triglyme or N-methyl-2-pyrrolidone, measurement temperature: 30 ° C.), which is a measure of the molecular weight of polyimide, is preferably 0.15 or more. Preferably it is 0.16-2.

In this invention, when mentioning the density | concentration or viscosity of a polyimide resin composition, the thing which does not contain a filler and another additive is meant.

The polyimide resin composition of the present invention comprises the polyimide obtained as described above and a solvent as essential components, and various components can be suitably added depending on the application. Therefore, regardless of the definition of the concentration or viscosity of the polyimide resin composition, it is also within the scope of the present invention that the polyimide resin composition contains a filler and other additives.

In order to obtain a curable resin composition, an ordinary curable resin composition such as an epoxy resin, a cyanate resin, an isocyanate resin, a phenol resin, a guanamine resin, a benzoxazine resin, or a resin having an unsaturated double bond is used. A conventionally known curable resin to be employed can be suitably used. Examples of the epoxy resin include those having two or more glycidyl groups. Examples of the cyanate resin include those having two or more cyanate groups. Examples of the isocyanate resin include those having two or more isocyanate groups. Examples of the benzoxazine resin include those having two or more benzoxazine rings. Examples of the resin having an unsaturated double bond include those having two or more carbon-carbon unsaturated double bonds.

Moreover, you may use together conventionally well-known hardening | curing agents, such as an acid anhydride employ | adopted for a normal curable resin composition, an amine, and a thiol, with the said curable resin composition.

As a catalyst for accelerating the reaction of the curable resin composition, a conventionally known curing accelerator employed in a normal curable resin composition can be suitably used.

Moreover, a photoinitiator can be added to the curable resin composition of this invention, and it can also be used as a photocurable resin composition. As a photoinitiator, the conventionally well-known photoinitiator employ | adopted as a normal photocurable resin composition can be used conveniently.

  The curable resin composition of the present invention preferably contains 30% by weight or more of the polyimide of the present invention, more preferably 35% by weight or more, and particularly preferably 40% by weight or more. This is preferable because the effect of obtaining a product can be further enhanced. The curable resin composition of the present invention may be cured by any method of thermal curing, photocuring (curing by irradiation with ultraviolet rays or the like), radiation curing, or electron beam curing.

Furthermore, organic or inorganic fillers, pigments, antifoaming agents and the like can be suitably used.

That is, in the polyimide resin composition of the present invention, conventionally known curing components, fillers, additives and the like as described in Patent Document 1 and Patent Document 2, for example, can be suitably used depending on the application.

In addition, the polyimide resin composition of the present invention can be used by impregnating a woven fabric or a non-woven fabric made of glass, carbon, or organic fiber depending on the application.

The polyimide film produced using the polyimide resin composition of the present invention is excellent in mechanical properties such as tensile elastic modulus, breaking strength, breaking elongation, and heat resistance, printed wiring board, overcoat material, electronic component and semiconductor package. It is suitable for being used as a sealant for facing. That is, there is no problem in mechanical properties and heat resistance as in the case of using a conventional polyimide siloxane solution composition. In fact, when the curable resin composition containing the polyimide of the present invention is used, the elastic modulus in the tensile test is 1.5 GPa or less, the elongation at break is 15% or more, and the 5% weight loss temperature in air is 330. A cured product having a high heat resistance equal to or higher than that of a conventional product and having high heat resistance equal to or higher than that of a conventional product can be obtained. And since the siloxane compound is not contained in the polyimide of this invention, even if it uses for a printed wiring board, an overcoat material, an electronic component, and the sealing agent for semiconductor packages, there is no fear of causing the contact failure by outgas.

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples.

[Measurement method of solid content]
The sample polyimide resin composition was heat-treated at 200 ° C., and the weight was recorded every 30 minutes. When the amount of weight loss before and after 30 minutes is less than 0.5% by weight of the sample weight before the heat treatment, the measurement is finished. From the sample weight before the heat treatment (w1) and the sample weight after the heat treatment (w2) The solid content concentration was calculated by the following formula.

Solid content concentration (%) = [w2 / w1] × 100

[Measurement method of solution viscosity]
Using a 25 mL volumetric flask, the polyimide resin composition was diluted to approximately 0.5 g / dL, and the logarithmic viscosity (η _inh ) was measured using a No. 100 Canon Fenceke viscometer. A 10 mL sample was used for the measurement.

[Mechanical properties of polyimide]
[Mechanical properties]
The prepared polyimide resin composition is coated on a glass substrate, heated on a hot plate at 60 ° C. to 100 ° C., then heated in a hot air oven at 120 ° C. for 30 minutes, and subsequently at 200 ° C. for 60 minutes as a final treatment. It heated and produced the polyimide film whose thickness is about 25 micrometers-40 micrometers. The obtained polyimide film was cut into a width of 4 mm and a gauge distance of 20 mm to obtain a test piece. About this test piece, using a tensile tester (manufactured by Shimadzu Corp .; Ez-test), under conditions of a temperature of 25 ° C., a humidity of 50% RH, a crosshead speed of 5 mm / min, and a distance between chucks of 50 mm, The breaking strength and elongation at break were measured according to ASTM D638.

[Pyrolysis temperature]
The prepared polyimide resin composition is coated on a glass substrate, heated on a hot plate at 60 ° C. to 100 ° C., then heated in a hot air oven at 120 ° C. for 30 minutes, and subsequently at 200 ° C. for 60 minutes as a final treatment. It heated and produced the polyimide film whose thickness is about 25 micrometers-40 micrometers. About the obtained polyimide film, 5% weight reduction | decrease temperature (the product made from BRUKERaxs; TG-DTA2000SA) was measured using TG-DTA. The measurement was performed at a temperature rising rate of 5 ° C./min in a nitrogen atmosphere.

[Method for producing cured film]
The curable resin composition 1.5 to 1.6 g was placed on a Teflon (registered trademark) sheet-attached glass substrate and heated on a hot plate at 100 to 120 ° C. for 20 to 30 minutes to volatilize most of the solvent. . Thereafter, using a polyimide film having a thickness of 50 μm as a spacer, the resin composition was sandwiched between the glass substrate and another glass substrate, and heated in an oven at 150 ° C. for 2 hours. Furthermore, one glass substrate was removed and the cured | curing material film was created by heating again in 150 degreeC oven for 2 hours.

[Mechanical properties of curable resin composition]
The cured product film obtained above was cut into a dumbbell shape having a gauge distance of 20 mm and a width of 4 mm to obtain a test piece. This test piece is compliant with ASTM D638 using a tensile tester (manufactured by Shimadzu Corporation; Ez-test) under the conditions of a temperature of 25 ° C., a humidity of 50% RH, a crosshead speed of 5 mm / min, and a distance between chucks of 30 mm. Then, the tensile elastic modulus, breaking strength, and breaking elongation were measured.

[Thermal decomposition temperature of curable resin composition]
About the hardened | cured material film obtained above, 5% weight reduction | decrease temperature was measured using TG-DTA (The product made from BRUKERaxs; TG-DTA2000SA). The measurement was performed in an air atmosphere at a heating rate of 5 ° C./min.

The raw materials used are as follows.
<Acid anhydride>
a-BPDA: 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (molecular weight 294.22, manufactured by Ube Industries, Ltd.)
ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (molecular weight 310.21, reagent)
BPADA: 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic anhydride (molecular weight 520.49, reagent)
B-4400: 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (molecular weight 264.23, manufactured by DIC Corporation)
<Diamine>
PRIAMINE 1074: Aliphatic diamine (amine equivalent 273.7, manufactured by CRODA JAPAN CO., LTD.)
D400: Jeffamine D400 (molecular weight 444.4, manufactured by Mitsui Chemicals Fine Co., Ltd.)
<Reactive group-containing diamine>
MBAA: 4,4′-diamino-3,3′-dicarboxydiphenylmethane (molecular weight 286.3, manufactured by Wakayama Seika Kogyo Co., Ltd.)
MCDPE: 4,4′-diamino-2,2′-dicarboxydiphenyl ether (molecular weight 288.3, manufactured by Wakayama Seika Kogyo Co., Ltd.)
BAPDA: 2,2′-bis (3-amino-4-hydroxyphenyl) propane (molecular weight 258.3, manufactured by Wakayama Seika Kogyo Co., Ltd.)
HFHIP: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (molecular weight 366.3, manufactured by Wakayama Seika Kogyo Co., Ltd.)
DABA: 3,5-diaminobenzoic acid (molecular weight 152.15, manufactured by Nippon Pure Chemicals Co., Ltd.)
HAB: 4,4′-diamino-3,3′-dihydroxybiphenyl (molecular weight 216.24, manufactured by Wakayama Seika Kogyo Co., Ltd.)
<Solvent>
TG: Triglyme NMP: N-methyl-2-pyrrolidone cyclohexanone <curable resin>
828EL: Liquid bisphenol A type epoxy resin jER828EL (epoxy equivalent 185, manufactured by Japan Epoxy Resin Co., Ltd.)
<Curing agent>
THPA: Tetrahydrophthalic anhydride (molecular weight 152.2, manufactured by Shin Nippon Chemical Co., Ltd.)
<Curing accelerator>
DBU: 1,8-diazabicyclo [5.4.0] undecene-7 (molecular weight 152, manufactured by San Apro Co., Ltd.)

[Synthesis of polyimide]
<Example 1>
In a glass separable flask with a capacity of 300 ml, 35.4 g (0.067 mol) of PRIAMINE 1074 as a diamine, 21.9 g (0.074 mol) of a-BPDA as an acid anhydride, and a part of TG (total of TG) as a solvent 60.0 g) and stirred at 100 ° C. until the salt was completely dissolved. Then, it heated up to 180 degreeC and stirred for 1 hour and heat-polymerized. Subsequently, the solution was cooled to 100 ° C., 2.76 g (0.010 mol) of reactive group-containing diamine MBAA and the remaining solvent TG were added, stirred until completely dissolved, and then heated to 180 ° C. The mixture was stirred for 6 hours and subjected to heat polymerization. All of this reaction was performed under a nitrogen atmosphere. The resulting polyimide resin composition was a solution having a polymer solid content concentration of 61.1% by weight and η _inh 0.22. The obtained polyimide was measured for mechanical properties and thermal decomposition temperature. The results are shown in Table 1. In Table 1, the content (mol%) of the diamine compound (1) and the content (mol%) of the reactive group-containing diamine indicate the ratio in the diamine component.

<Examples 2 to 11 and Comparative Example 1>
In Examples 2 to 11 and Comparative Example 1, each polyimide resin composition was synthesized according to Example 1 with the composition shown in Table 1. For the polyimides obtained in Examples 2 to 11, mechanical properties and thermal decomposition temperature were measured. The results are shown in Table 1.

[Creation of curable resin composition]
<Example 12>
15.2 g of the polyimide solution synthesized in Example 1 as a curing agent, 0.621 g of 828EL as a curable resin, 0.0052 g of DBU as a curing accelerator, and 8.97 g of TG as a solvent are placed in a 30 mL capacity sample tube. The mixture was mixed until completely uniform to obtain an epoxy resin composition. Using the obtained epoxy resin composition, a cured product film was prepared and measured for mechanical properties and thermal decomposition temperature. The results are shown in Table 2. In Table 2, the weight ratio of the composition to the composition represents the weight ratio of the curing agent to the weight of the obtained cured film.

[Method for producing cured film]
The curable resin composition 1.5 to 1.6 g was placed on a Teflon (registered trademark) sheet-attached glass substrate and heated on a hot plate at 100 to 120 ° C. for 20 to 30 minutes to volatilize most of the solvent. . Thereafter, using a polyimide film having a thickness of 50 μm as a spacer, the resin composition was sandwiched between the glass substrate and another glass substrate, and heated in an oven at 150 ° C. for 2 hours. Furthermore, one glass substrate was removed and the cured | curing material film was created by heating again in 150 degreeC oven for 2 hours.

[Mechanical properties]
The cured product film obtained above was cut into a dumbbell shape having a gauge distance of 20 mm and a width of 4 mm to obtain a test piece. This test piece is compliant with ASTM D638 using a tensile tester (manufactured by Shimadzu Corporation; Ez-test) under the conditions of a temperature of 25 ° C., a humidity of 50% RH, a crosshead speed of 5 mm / min, and a distance between chucks of 30 mm. Then, the tensile elastic modulus, breaking strength, and breaking elongation were measured.

<Examples 13-25, Comparative Examples 2-3>
In Examples 13 to 25 and Comparative Examples 2 to 3, according to Example 12, each epoxy resin composition was obtained with the composition shown in Table 2. Using the obtained epoxy resin composition, a cured product film was prepared and measured for mechanical properties and thermal decomposition temperature. The results are shown in Table 2.

The cured product obtained from the curable resin composition using the polyimide of the present invention as a curing agent was confirmed to have improved flexibility and heat resistance. In addition, since no siloxane-based material is used, contact failure due to outgassing is not caused. Therefore, the polyimide of the present invention has an effect of effectively improving characteristics such as flexibility and heat resistance of a thermosetting resin composition used in the electric and electronic fields.

Claims (19)

A polyimide obtained by reacting a tetracarboxylic acid component with a diamine component containing a diamine compound represented by the following general formula (1),
A polyimide having in the molecule at least one reactive group selected from a reactive group having active hydrogen and a reactive group having an unsaturated double bond.

In formula (1), A represents a tetravalent saturated hydrocarbon residue, and may be a linear structure or a ring structure. R ₁ and R ₂ each independently represent an alkylene group having 1 to 20 carbon atoms, and R ₃ and R ₄ each independently represent a linear alkyl group having 1 to 20 carbon atoms. The polyimide of Claim 1 whose carbon number of the diamine compound represented by the said Formula (1) is 20-48. The polyimide according to claim 1 or 2, wherein the reactive group having active hydrogen is at least one selected from a hydroxyl group, a carboxyl group, an aldehyde group, an amino group, an imino group, and a thiol group. The polyimide according to any one of claims 1 to 3, wherein the diamine component includes a diamine other than the diamine compound represented by the formula (1) and having the reactive group. The polyimide according to any one of claims 1 to 4, wherein the reactive group is a carboxyl group or a hydroxyl group. The polyimide according to claim 4, wherein the other diamine is an aromatic diamine represented by the following general formula (2).

In the formula, X and Y each independently represent a direct bond or a group represented by any one of formulas (3-1) to (3-8) in the following general formula (3), and r ₁ represents a carboxyl group or Represents a hydroxyl group, and n1 is a number of 0 or more.

In the formula, R ₅ and R ₆ are hydrogen, a methyl group, or a halogenated methyl group. The other diamine shown by said Formula (2) WHEREIN: The polyimide of Claim 6 whose n1 is the number of 0-2. The other diamine is 4,4′-diamino-3,3′-dicarboxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4-diamino-2,2′-dicarboxydiphenyl ether , 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and one or more selected from the group consisting of 2,2′-bis (3-amino-4-hydroxyphenyl) propane The polyimide according to claim 4 or 6, wherein The polyimide according to any one of claims 1 to 8, wherein the diamine component does not contain a siloxane component. The manufacturing method of the polyimide of any one of Claim 1 to 9. The polyimide resin composition containing the polyimide of any one of Claim 1 to 9. A curable resin composition comprising the polyimide according to any one of claims 1 to 9 and a curable resin. The curable resin composition of Claim 12 containing an epoxy resin as curable resin. The curable resin composition according to claim 13, wherein the epoxy resin has two or more glycidyl groups. The curable resin composition of Claim 12 containing isocyanate resin as curable resin. The curable resin composition according to claim 15, wherein the isocyanate resin has two or more isocyanate groups. The curable resin composition of Claim 12 containing resin which has an unsaturated double bond as curable resin. The curable resin composition according to claim 17, wherein the resin having an unsaturated double bond has two or more unsaturated double bonds. Hardened | cured material using the curable resin composition of any one of Claims 12-18.