JP2006299009A - Solvent-soluble polyimide resin composition and mechanical strength improving agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solvent-soluble polyimide resin composition having improved mechanical strength and a strength improving agent. <P>SOLUTION: The polyimide resin composition contains a solvent-soluble polyimide and a π-conjugated polymer. The mechanical strength improving effect is especially excellent when the π-conjugated polymer of the polyimide resin composition is one or more polymers selected from polyaniline, polypyrrole, polyfuran, polythiophene and polyacetylene. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a solvent-soluble polyimide resin composition, and more specifically, a polyimide resin composition having excellent heat resistance, solvent solubility, and moldability and improved mechanical strength, and mechanical strength of the solvent-soluble polyimide resin It relates to a strength improver for improving the strength.

  Polyimide varnishes used in the electrical / electronic materials field, the optical material field, the paint field, etc. can generally be roughly classified into a polyamic acid type which is a polyimide precursor and a solvent-soluble polyimide type. In the former, a polyamide resin varnish is applied to the surface of a material to be coated, and then heat-treated, thereby performing solvent removal and imidization reaction simultaneously to obtain a molded article of polyimide resin. Therefore, the heat treatment generally requires a high temperature of 300 ° C. or higher. On the other hand, the latter is solvent-soluble by introducing a flexible molecular chain into the molecular skeleton or by introducing a group that increases the distance of the imide ring in the molecule. Since the imidization reaction is completed, a molded product can be obtained simply by removing the solvent from the varnish, and therefore, there is an advantage that the temperature of the heat treatment can be molded at a lower temperature than the polyamic acid type. Furthermore, since the change in viscosity of the varnish during storage is small, it is very excellent in terms of molding processability.

  However, in exchange for increasing the solvent solubility of polyimide, the heat resistance and mechanical strength are slightly reduced. In particular, the decrease in mechanical strength has been a major obstacle to expanding the range of use of the solvent-soluble polyimide type. Since these are all attributable to the molecular skeleton, it is difficult to achieve both, and no effective method is known.

  For example, Patent Document 1 proposes a polyimide film containing polyetherimide with respect to a bismaleimide resin as a method for improving the mechanical strength of a polyimide resin. The polyimide resin disclosed here is a polyimide resin obtained by addition reaction of maleimide and diamine, and is not a condensation type solvent-soluble polyimide resin. For this reason, a chlorinated solvent was required as a solvent, and the mechanical strength value was not very satisfactory.

  Further, Patent Document 2 discloses that a polyaniline / polyimide composite molded body obtained by heating polyaniline / polyamic acid is excellent in mechanical strength. However, as described in paragraph [0015] of Patent Document 2, the mechanical strength of the composite molded body is almost the same as the corresponding polyimide resin, and does not improve the mechanical strength of the polyimide resin.

JP 7-316427 A JP-A-7-90179

  The present invention relates to a polyimide resin composition, and more particularly, to provide a solvent-soluble polyimide resin composition having improved mechanical strength, containing a solvent-soluble polyimide and a π-conjugated polymer, and a solvent-soluble polyimide machine It aims at providing the strength improvement agent which improves intensity | strength.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained the following knowledge in the process of developing a resin composition.
(1) The solvent-soluble polyimide and the π-conjugated polymer are highly compatible, and a uniform resin composition can be obtained without using a compatibilizer.
(2) The effect is particularly remarkable when the solvent-soluble polyimide contains a sulfone group.
(3) A polyimide resin composition containing a solvent-soluble polyimide and a π-conjugated polymer is excellent in mechanical strength (tensile strength, tensile elastic modulus).
(4) Especially when the π-conjugated polymer is polyaniline, particularly reduced polyaniline, the mechanical strength is remarkably improved.

  The present invention has been made on the basis of such knowledge, and provides the following invention.

Item 1. A polyimide resin composition comprising a solvent-soluble polyimide and a π-conjugated polymer.

Item 2 The polyimide resin composition according to Item 1, wherein the π-conjugated polymer is at least one selected from the group consisting of polyaniline, polypyrrole, polyfuran, polythiophene, and polyacetylene.

Item 3 The polyimide resin composition according to Item 2, wherein the π-conjugated polymer is polyaniline.

［式中、ｈ及びｉは、それぞれキノンジイミン型（酸化型）ポリアニリン及びフェニレンジアミン型（還元型）ポリアニリンの繰り返し単位中のモル分率を表し、０＜ｈ≦０．３、０．７≦ｉ＜１、且つｈ＋ｉ＝１である。］
で表される、還元型ポリアニリンである上記項３に記載のポリイミド樹脂組成物。 Item 4 Polyaniline has the general formula (1)

[Wherein, h and i represent mole fractions in repeating units of quinonediimine type (oxidized type) polyaniline and phenylenediamine type (reduced type) polyaniline, respectively, 0 <h ≦ 0.3, 0.7 ≦ i <1 and h + i = 1. ]
Item 4. The polyimide resin composition according to Item 3, which is a reduced polyaniline represented by:

［式中、Ｘ^１は、直接結合、−Ｏ−、−ＣＯ−、−ＳＯ_２−、又は基（ａ）

｛式中、Ｚ^１は、炭素数２〜１０の直鎖状若しくは分岐鎖状のアルキレン基、１，３−フェニレン基又は１，４−フェニレン基を表す。｝
を表す。Ｙ^１は、２価の有機基を表す。ｊは、１以上の整数を表す。］
で表される構造単位を有する溶剤可溶性ポリイミドである上記項１〜４のいずれかに記載のポリイミド樹脂組成物。 Item 5 Solvent-soluble polyimide is represented by the general formula (2)

[Wherein X ¹ represents a direct bond, —O—, —CO—, —SO ₂ —, or a group (a)

{Wherein, ^{Z 1} represents a linear or branched alkylene group, 1,3-phenylene or 1,4-phenylene group having 2 to 10 carbon atoms. }
Represents. Y ¹ represents a divalent organic group. j represents an integer of 1 or more. ]
Item 5. The polyimide resin composition according to any one of Items 1 to 4, which is a solvent-soluble polyimide having a structural unit represented by:

［式中、Ｙ^２は、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、１，３−フェニレン基、１，４−フェニレン基、又は基（ｂ）

｛式中、Ｙ^３は、−Ｏ−、−ＳＯ_２−又は−Ｃ（ＣＨ_３）_２−を表す。｝
を表す。ｋは、１以上の整数を表す。］
で表される構造単位を有する溶剤可溶性ポリイミドである上記項５に記載のポリイミド樹脂組成物。 Item 6 Solvent-soluble polyimide is represented by the general formula (3)

[Wherein Y ² represents —O—, —S—, —SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, 1,3-phenylene group, 1,4- Phenylene group or group (b)

{Wherein Y ³ represents —O—, —SO ₂ — or —C (CH ₃ ) ₂ —. }
Represents. k represents an integer of 1 or more. ]
Item 6. The polyimide resin composition according to Item 5, which is a solvent-soluble polyimide having a structural unit represented by:

Item 7 The polyimide resin composition according to any one of Items 1 to 6, wherein the solvent-soluble polyimide has an acid value of 0.1 to 30 mgKOH / g.

Item 8 The polyimide resin composition according to any one of Items 1 to 7, which contains 1 to 50 parts by weight of a π-conjugated polymer with respect to 100 parts by weight of the solvent-soluble polyimide.

Item 9 The polyimide resin composition according to any one of Items 1 to 8, wherein the polyimide resin composition has a tensile strength of 130 MPa or more and a tensile modulus of 300 MPa or more.

Item 10 The polyimide resin composition according to any one of Items 1 to 9, wherein the resin composition has a volume resistivity of 10 ¹³ Ω · cm or more.

Item 11 A molded article obtained by molding the resin composition according to any one of Items 1 to 10.

Item 12. A strength improver for a solvent-soluble polyimide resin, wherein the strength improver is a π-conjugated polymer.

［式中、ｈ及びｉは、それぞれキノンジイミン型（酸化型）ポリアニリン及びフェニレンジアミン型（還元型）ポリアニリンの繰り返し単位中のモル分率を表し、０＜ｈ≦０．３、０．７≦ｉ＜１、且つｈ＋ｉ＝１である。］
で表される、還元型ポリアニリンである上記項１２に記載の強度向上剤。 Item 13 The strength improver is represented by the general formula (1)

[Wherein, h and i represent mole fractions in repeating units of quinonediimine type (oxidized type) polyaniline and phenylenediamine type (reduced type) polyaniline, respectively, 0 <h ≦ 0.3, 0.7 ≦ i <1 and h + i = 1. ]
Item 13. The strength improver according to Item 12, which is a reduced polyaniline represented by:

Item 15 A method for improving the mechanical strength of a solvent-soluble polyimide resin, comprising blending the mechanical strength improver of Items 11 to 14 with a solvent-soluble polyimide resin.

Item 16 A polyimide resin composition comprising a solvent-soluble polyimide resin and the mechanical strength improver according to any one of Items 11 to 14.

According to the present invention, the following excellent effects are exhibited.
(1) A solvent-soluble polyimide and a π-conjugated polymer can be made compatible without using a compatibilizer.
(2) The mechanical strength (tensile strength, tensile modulus) of the solvent-soluble polyimide resin can be improved.

  The best mode for carrying out the present invention will be described in detail below.

Solvent-soluble polyimide The solvent-soluble polyimide according to the present invention (hereinafter referred to as “the present imide”) is not particularly limited as long as it is soluble in an organic solvent, and conventionally known ones can be widely used. The polyimide resin is usually prepared by imidizing a tetracarboxylic dianhydride and a diamine component, preferably in an inert gas atmosphere.

Tetracarboxylic dianhydride component Examples of the acid component used in the present imide include aliphatic or alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, or acids thereof. As a specific example of the alicyclic tetracarboxylic dianhydride,
1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3 -Cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2,2,2 ]-Ok Down-2,3,5,6-tetracarboxylic dianhydride, and the like.

  Specific examples of the aliphatic tetracarboxylic dianhydride having an aromatic ring include 1,3,3a, 4,5,9b-hexahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] Furan-1,3-dione and the like.

  Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-diphenylsulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetra Carboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, di (3, 4-dicarboxyphenyl) dimethylsilane dianhydride, di (3,4-dicarboxyphenyl) diphenylsilane dianhydride, α, ω-alkylene (2 to 10 carbon atoms) bis (anhydrotrime) Tate), 1,3-phenylenebis (anhydrotrimellitate), 1,4-phenylenebis (anhydrotrimellitate), 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, Bis [4- (3,4-dicarboxyphenoxy) phenyl] ether dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] sulfide dianhydride, bis [4- (3,4-di Carboxyphenoxy) phenyl] sulfone dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxy Examples thereof include side dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, and the like.

  Among the above-mentioned tetracarboxylic dianhydrides, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride has the advantage of giving excellent heat resistance to solvent-soluble polyimide and compatibility with π-conjugated polymers. 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, α, ω-alkylene (having 2 to 10 carbon atoms) bis (anhydrotrimellitate) and 1-4-phenylenebis (anhydrotrimellitate) are preferred, especially 3,3 ′, 4,4′-diphenyl Sulfonetetracarboxylic dianhydride is preferred.

  Moreover, tetracarboxylic dianhydride can be used individually or in mixture of 2 or more types. When using a mixture of two or more, use 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride as one of them because of its excellent compatibility with the π-conjugated polymer. Is preferred. Although there is no restriction | limiting in particular in one or more other types, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3', 4,4 '-Diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, α, ω-alkylene (2 to 10 carbon atoms) bis (anhydrotrimellitate), 1,4-phenylene bis (anhydro trimellitate) is preferable, and α, ω-alkylene (2 to 10 carbon atoms) bis (anhydro trimellitate) is particularly preferable. When two or more are used, the ratio of each tetracarboxylic dianhydride is not particularly limited, but 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and other tetracarboxylic acids When used in combination with a dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride is preferably used in the range of 40 to 95 mol% in the total tetracarboxylic dianhydride. More preferably, the range of 50 to 95 mol%, particularly preferably 60 to 90 mol% is recommended.

Diamine Component Examples of the diamine used in the solvent-soluble polyimide according to the present invention include aliphatic diamine, alicyclic diamine, and aromatic diamine.

Aliphatic diamines include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7- Heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine,
C2-C12 alkylenediamine such as 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 2 , 5-bis (aminomethyl) bicyclo [2,2,1] heptane, 2,6-bis (aminomethyl) bicyclo [2,2,1] heptane, etc. An aliphatic diamine containing an aromatic ring having 8 to 10 carbon atoms, such as m-xylylenediamine and p-xylylenediamine.

  Examples of the alicyclic diamine include alicyclic diamines having 4 to 18 carbon atoms, preferably 6 to 13 carbon atoms. Specifically, 1,2-diaminocyclobutane, 1,3-diaminocyclobutane, 1, 2-diaminocyclopentane, 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-diaminocycloheptane, 1,3-diaminocycloheptane 1,4-diaminocycloheptane, 1,2-diaminocyclooctane, 1,3-diaminocyclooctane, 1,4-diaminocyclooctane, 1,5-diaminocyclooctane, 1,2-diaminocyclononane, , 3-Diaminocyclononane, 1,4-diaminocyclononane, 1,5-diaminocyclononane Bis (4-aminocyclohexyl) methane, bis (4-amino-2-methylcyclohexyl) methane, bis (4-amino-2,3-dimethylcyclohexyl) methane, 1,1-bis (4-aminocyclohexyl) ethane, 2,2-bis (4-aminocyclohexyl) propane and the like are exemplified.

［式中Ｙ^２は、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）−、１，３−フェニレン基、１，４−フェニレン基又は基（ｂ）を表す。］

［式中、Ｙ^３は、−Ｏ−、−ＳＯ_２−又は−Ｃ（ＣＨ_３）_２−を表す。］ As aromatic diamine, C6-C30 represented by following General formula (4), Preferably C12-C24 aromatic diamine is illustrated.

[Wherein Y ² represents —O—, —S—, —SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) —, 1,3- Represents a phenylene group, a 1,4-phenylene group or a group (b); ]

[Wherein Y ³ represents —O—, —SO ₂ — or —C (CH ₃ ) ₂ —. ]

  Specific examples of the aromatic diamine include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, and 3,4′-diaminodiphenyl sulfide. 3,3′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylketone, 3,4 ′ -Diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,2-bis (4-aminophenyl) ) Propane, 2,2-bis (3-aminophenyl) propane 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminopheno) C) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [ 4- (3-aminophenoxy) phenyl] hexafluoropropane and the like.

［式中、Ｘ^３は、−ＳＯ_２−又は−Ｃ（ＣＨ_３）_２−を表す。末端アミノ基の置換位置は、エーテル基に対して、ｍ位又はｐ位である。］
で表されるジアミンが好ましい。係る好ましいジアミンの具体例としては、２，２−ビス（４−（４−アミノフェノキシ）フェニル）プロパン、２，２−ビス（４−（３−アミノフェノキシ）フェニル）プロパン、ビス（４−（４−アミノフェノキシ）フェニル）スルホン、ビス（４−（３−アミノフェノキシ）フェニル）スルホン等が挙げられる。 Among the above diamines, the aromatic diamine represented by the general formula (4) is preferable from the viewpoint of imparting excellent heat resistance to the imide, and the general formula (5) is particularly preferable.

[Wherein X ³ represents —SO ₂ — or —C (CH ₃ ) ₂ —. The substitution position of the terminal amino group is m-position or p-position with respect to the ether group. ]
The diamine represented by these is preferable. Specific examples of such a preferred diamine include 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, bis (4- ( 4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like.

  These diamine components can be used alone or in combination of two or more. These diamine components are conventionally known or can be produced by known methods, and commercially available products are also available.

［式中、Ｘ^１は、直接結合、−Ｏ−、−ＣＯ−、−ＳＯ_２−、又は基（ａ）

｛式中、Ｚ^１は、炭素数２〜１０の直鎖状若しくは分岐鎖状のアルキレン基、１，３−フェニレン基又は１，４−フェニレン基を表す。｝
を表す。Ｙ^１は、２価の有機基を表す。ｊは、１以上の整数を表す。］
で表される構造単位を有する溶剤可溶性ポリイミドが好ましく、特に、一般式（３）

［式中、Ｙ^２は、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、１，３−フェニレン基、１，４−フェニレン基、又は基（ｂ）

｛式中、Ｙ^３は、−Ｏ−、−ＳＯ_２−又は−Ｃ（ＣＨ_３）_２−を表す。｝
を表す。ｋは、１以上の整数を表す。］
で表される溶剤可溶性ポリイミドが推奨される。 Preferred polyimide resin Among the polyimide resins, general formula (2) from the viewpoint of excellent compatibility with π-conjugated polymer and mechanical strength

[Wherein X ¹ represents a direct bond, —O—, —CO—, —SO ₂ —, or a group (a)

{Wherein, ^{Z 1} represents a linear or branched alkylene group, 1,3-phenylene or 1,4-phenylene group having 2 to 10 carbon atoms. }
Represents. Y ¹ represents a divalent organic group. j represents an integer of 1 or more. ]
A solvent-soluble polyimide having a structural unit represented by formula (3) is preferred.

[Wherein Y ² represents —O—, —S—, —SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, 1,3-phenylene group, 1,4- Phenylene group or group (b)

{Wherein Y ³ represents —O—, —SO ₂ — or —C (CH ₃ ) ₂ —. }
Represents. k represents an integer of 1 or more. ]
The solvent-soluble polyimide represented by is recommended.

Imidization Reaction The polyimide resin of the present invention can be obtained by imidizing the tetracarboxylic dianhydride component and the diamine component. The imidization reaction itself can be performed according to a known method. For example, a method of polycondensation reaction of tetracarboxylic dianhydride and diamine in an organic solvent can be mentioned. As a method of imidization reaction at that time, (1) tetracarboxylic dianhydride and diamine can be used. There are a method of distilling the produced water out of the system by heating in an organic solvent, and a method of using a compound having a dehydrating action such as acetic anhydride after the production of polyamic acid which is a polyimide precursor (2).

  Of the production methods (1) and (2), the method (1) is particularly industrially preferable. As a more specific method of (1), after dissolving the component (A) and the component (B) in an organic solvent, the mixture is heated to 100 to 250 ° C., and purified water in the reaction system is removed with an azeotropic solvent. The solvent-soluble polyimide resin of the present invention can be obtained by a method of performing a polycondensation reaction by distilling off.

  There is no particular limitation on the molar ratio in the imidization reaction between the tetracarboxylic dianhydride component and the diamine component. However, from the viewpoint of increasing the molecular weight of the polyimide resin and increasing the mechanical strength, (A) The molar ratio of the anhydride component: (B) diamine component is preferably in the range of 0.9 to 1.2: 1, particularly preferably in the range of 0.95 to 1.05. Moreover, from the point which improves the electroconductivity of a resin composition, the range whose molar ratio of (A) component: (B) component is 1.05-1.20: 1 is preferable. On the other hand, from the viewpoint of lowering the conductivity, the molar ratio of component (A): component (B) is preferably in the range of 1.00 to 1.05: 1.

  As the organic solvent used in the imidization reaction, an aprotic polar solvent is preferably used. Specifically, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl Examples include sulfoxide, 1,3-dimethyl-2-imidazolidinone, sulfolane, diglyme, triglyme, cyclohexanone, cyclopentanone, and γ-butyrolactone, and these can be used alone or as a mixed system. Of these, N-methyl-2-pyrrolidone and γ-butyrolactone are particularly preferred from the viewpoints of polymerizability and solvent solubility.

  The amount of the organic solvent used is preferably 100 to 500% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the tetracarboxylic dianhydride component and the diamine component. In the reaction, a part of the organic solvent can be replaced with an azeotropic solvent for the purpose of efficiently taking out water generated by the imidation reaction out of the system. Examples of the azeotropic solvent include aromatic hydrocarbons such as toluene, xylene and solvent naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclosoxane and dimethylcyclohexane. When proving these azeotropic solvents, the amount used is recommended to be in the range of about 1 to 30% by weight, preferably 5 to 20% by weight, based on the total amount of organic solvent.

  The reaction time varies depending on the type of tetracarboxylic dianhydride and the type of diamine, or the molecular weight of the polyimide resin according to the present invention, but is usually preferably 0.5 to 24 hours.

  Although there is no restriction | limiting in particular in the molecular weight of this imide, As a number average molecular weight, 5,000-200,000, Preferably, it is 8,000-100,000 at the point which is excellent in the balance of solvent solubility, mechanical strength, and heat resistance. 000, particularly preferably in the range of 10,000 to 50,000, with a weight average molecular weight of 10,000 to 300,000, preferably 15,000 to 200,000, particularly preferably 20,000 to 100,000.

  Although there is no restriction | limiting in particular as a solvent soluble polyimide resin acid value, Usually, 0.1-100 mgKOH / g, Preferably the range of 1-50 mgKOH / g is illustrated. The lower the acid value of the solvent-soluble polyimide, the higher the volume resistance value of the polyimide resin composition. Accordingly, when the insulating property is required for the polyimide resin composition, it is preferable to use a solvent-soluble polyimide having a low acid value, and when the conductivity or semi-conductivity is required, a solvent-soluble polyimide resin having a high acid value is preferable. .

π-Conjugated Polymer As the π-conjugated polymer according to the present invention, conventionally known π-conjugated polymers can be widely used. Specifically, polyacetylene, poly p-phenylene, polypyrrole, polythiophene, polyfuran, polyselenophene, polyisothianaphthene, polyphenylene sulfide, polyaniline, polyphenylene vinylene, polyethylene dioxythiophene, polythiophene vinylene, polyperiphthalene, polyanthracene, Examples include polynaphthalene, polypyrene, and polyazulene. These may have a substituent. Examples of the substituent include a halogen substituent, an alkyl group or an alkenyl group which may have a hydroxyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. And substituents such as an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms, and an alkyloxycarbonyl group. These π-conjugated polymers can be used alone or in admixture of two or more.

  By blending such a π-conjugated polymer into solvent-soluble polyimide, the tensile strength and tensile elastic modulus of the polyimide resin composition after blending can be improved. Therefore, the π-conjugated polymer according to the present invention is a mechanical strength improver of solvent-soluble polyimide resin, and improves the mechanical strength of solvent-soluble polyimide by blending π-conjugated polymer with solvent-soluble polyimide. A method is provided simultaneously.

  Specific examples of the π-conjugated polymer include π-conjugated polymer compounds having a repeating unit represented by the general formulas (6) to (11).

［式中、Ｒ^１〜Ｒ^４はそれぞれ互いに同一又は相異なって、水素原子、炭素数１〜２０の直鎖状若しくは分岐状のアルキル若しくはアルキレン基、又は炭素数１〜２０の直鎖状若しくは分岐鎖状のアルコキシ基を表す。Ｒ^１とＲ²がともに水素原子でない場合、Ｒ^１とＲ^２はは互いに結合してそれらが結合するベンゼン環とともにテトラリン環若しくはナフタレンを形成していてもよい。］
で表されるポリアニリンが挙げられる。 Specific examples of polyaniline include those represented by the general formula (6)

[Wherein, R ^{1 to} R ⁴ are the same as or different from each other, and represent a hydrogen atom, a linear or branched alkyl or alkylene group having 1 to 20 carbon atoms, or a linear or branched group having 1 to 20 carbon atoms, or A branched alkoxy group is represented. When R ¹ and R ² are not both hydrogen atoms, R ¹ and R ² may be bonded to each other to form a tetralin ring or naphthalene together with the benzene ring to which they are bonded. ]
The polyaniline represented by these is mentioned.

［式中、ｍ及びｎは、それぞれキノンジイミン型（酸化型）ポリアニリン及びフェニレンジアミン型（還元型）ポリアニリンの繰り返し単位中のモル分率を表し、０＜ｈ＜１、０＜ｎ≦１、且つｈ＋ｉ＝１である。］
で表されるキノンジイミン型（酸化型）ポリアニリン及びフェニレンジアミン型（還元型）ポリアニリンの２つの構造単位を有しているが、溶剤可溶性ポリイミドとの相溶性及び機械強度の点から還元型構造を７０モル％以上、即ち、一般式（７）において、０＜ｍ≦０．３、０．７≦ｎ＜１、且つ、ｈ＋ｉ＝１であるポリアニリンが好ましい。 Polyaniline is usually represented by the general formula (7)

[Wherein, m and n represent mole fractions in repeating units of quinonediimine type (oxidized type) polyaniline and phenylenediamine type (reduced type) polyaniline, respectively, 0 <h <1, 0 <n ≦ 1, and h + i = 1. ]
The quinonediimine type (oxidized type) polyaniline and the phenylenediamine type (reduced type) polyaniline represented by the formula (1) have a reduced type structure in view of compatibility with solvent-soluble polyimide and mechanical strength. A polyaniline that is at least mol%, that is, in the general formula (7), 0 <m ≦ 0.3, 0.7 ≦ n <1, and h + i = 1 is preferable.

［式中、Ｒ⁵及びＲ⁶は、互いに同一又は相異なって、水素原子、水酸基を有していてもよい炭素数１〜１０のアルキル基若しくはアルケニル基、炭素数１〜１０のアルコキシ基、フェニル基、又は炭素数１〜１０のアルキルオキシカルボニル基を表す。Ｒ^５とＲ^６がともに水素原子でない場合、Ｒ^５とＲ^６は互いに結合して、それらが結合するピロール環とともに、イソインドール環を形成していてもよい。Ｒ^７は、炭素数１〜４のアルキル基を表す。＊は繰り返し単位の結合位置を示す。］
で表されるポリピロールが挙げられる。 As a specific example of polypyrrole, the general formula (8)

[Wherein, R ⁵ and R ⁶ are the same as or different from each other, and each may have a hydrogen atom, a hydroxyl group, or an alkyl or alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, A phenyl group or an alkyloxycarbonyl group having 1 to 10 carbon atoms is represented. When R ⁵ and R ⁶ are not both hydrogen atoms, R ⁵ and R ⁶ may be bonded to each other to form an isoindole ring together with the pyrrole ring to which they are bonded. R ⁷ represents an alkyl group having 1 to 4 carbon atoms. * Indicates the bonding position of the repeating unit. ]
The polypyrrole represented by these is mentioned.

［式中、Ｒ^７及びＲ^８は、互いに同一又は相異なって、水素原子、水酸基を有していてもよい炭素数１〜１０のアルキル基若しくはアルケニル基、炭素数１〜１０のアルコキシ基、フェニル基、又は炭素数１〜１０のアルキルオキシカルボニル基を表す。Ｒ^７及びＲ^８が水素原子でない場合、Ｒ⁷とＲ⁸は互いに結合して、それらが結合するフラン環とともに、イソベンゾフラン環を形成していてもよい。＊は繰り返し単位の結合位置を示す。］
で表されるポリフランが挙げられる。 As a specific example of polyfuran, general formula (9)

[Wherein, R ⁷ and R ⁸ are the same as or different from each other, and may have a hydrogen atom, a hydroxyl group having 1 to 10 carbon atoms or an alkenyl group, an alkoxy group having 1 to 10 carbon atoms, A phenyl group or an alkyloxycarbonyl group having 1 to 10 carbon atoms is represented. When R ⁷ and R ⁸ are not a hydrogen atom, R ⁷ and R ⁸ may be bonded to each other to form an isobenzofuran ring together with the furan ring to which they are bonded. * Indicates the bonding position of the repeating unit. ]
The polyfuran represented by these is mentioned.

［式中、Ｒ^９及びＲ^１０は、互いに同一又は相異なって、水素原子、水酸基を有していてもよい炭素数１〜１０のアルキル基若しくはアルケニル基、炭素数１〜１０のアルコキシ基、フェニル基、又は炭素数１〜１０のアルキルオキシカルボニル基を表す。Ｒ^９及びＲ^１０が水素原子でない場合、Ｒ^９とＲ^１０は互いに結合して、それらが結合するフラン環とともに、イソベンゾチオフェン環を形成していてもよい。＊は繰り返し単位の結合位置を示す。］
で表されるポリチオフェン及びその誘導体が挙げられる。 Specific examples of polythiophene include those represented by the general formula (10)

[Wherein, R ⁹ and R ¹⁰ are the same as or different from each other, and may have a hydrogen atom, a hydroxyl group having 1 to 10 carbon atoms or an alkenyl group, an alkoxy group having 1 to 10 carbon atoms, A phenyl group or an alkyloxycarbonyl group having 1 to 10 carbon atoms is represented. When R ⁹ and R ¹⁰ are not a hydrogen atom, R ⁹ and R ¹⁰ may be bonded to each other to form an isobenzothiophene ring together with the furan ring to which they are bonded. * Indicates the bonding position of the repeating unit. ]
The polythiophene represented by these, and its derivative (s) are mentioned.

［式中、Ｒ¹¹及びＲ¹²は、互いに同一又は相異なって、水素原子、ハロゲン原子、水酸基を有していてもよい炭素数１〜１０のアルキル基若しくはアルケニル基、炭素数１〜１０のアルコキシ基、フェニル基、又は炭素数１〜１０のアルキルオキシカルボニル基を表す。＊は繰り返し単位の結合位置を示す。］
で表されるポリアセチレン及びその誘導体が挙げられる。 Specific examples of the polyacetylene include those represented by the general formula (11)

[Wherein, R ¹¹ and R ¹² are the same as or different from each other, and each may have a hydrogen atom, a halogen atom, or a hydroxyl group, an alkyl group or an alkenyl group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms] An alkoxy group, a phenyl group, or an alkyloxycarbonyl group having 1 to 10 carbon atoms is represented. * Indicates the bonding position of the repeating unit. ]
The polyacetylene represented by these, and its derivative (s) are mentioned.

  In the present invention, these π-conjugated polymers may be in an undoped state or a doped state, and can be appropriately selected depending on the purpose of use of the polyimide resin composition. For example, when used in applications requiring conductivity, it is preferable to use a π-conjugated polymer in a doped state, and in applications requiring insulation, it is preferable to use it in an undoped state. There is no restriction | limiting in particular as a dopant, A conventionally well-known dopant can be used. Specific examples of the dopant include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, borohydrofluoric acid, phosphorous hydrofluoric acid, and perchloric acid, and organic substances such as aliphatic carboxylic acids and aromatic carboxylic acids. Carboxylic acid, methanesulfonic acid. Examples include organic sulfonic acids such as toluenesulfonic acid, organic compounds having a phenolic hydroxyl group, and the like.

  Among these π-conjugated polymers, polyaniline, polypyrrole, polyfuran, polythiophene, and polyacetylene are preferable from the viewpoint of excellent compatibility with solvent-soluble polyimide, heat resistance, and improved mechanical strength of solvent-soluble polyimide resin. Among these, polyaniline, particularly reduced polyaniline is preferable.

  In addition, among the π-conjugated polymers, a polyimide resin composition after blending by blending any blending amount of 1 to 50 parts by weight of the π-conjugated polymer with respect to 100 parts by weight of the solvent-soluble polyimide. What has the property which improves the tensile strength of a thing 30% or more with respect to the thing before a mixing | blending, Preferably it is 40% is desirable.

Polyimide resin composition As long as the polyimide resin composition of the present invention contains a solvent-soluble polyimide resin and a π-conjugated polymer, the content ratio is not particularly limited, and can be selected from an arbitrary range. Usually, the range of 1 to 100 parts by weight, preferably 1 to 50 resin parts, particularly preferably 5 to 30 parts by weight is exemplified with respect to 100 parts by weight of the solvent-soluble polyimide.

  There is no restriction | limiting in particular as a method of obtaining the resin composition containing a solvent soluble polyimide resin and (pi) conjugated polymer, It can mix by arbitrary methods. For example, a method in which a polyimide resin and a π-conjugated polymer are mixed in an organic solvent is exemplified. More specifically, the polyimide reaction product after the imidization reaction is completed and the π-conjugated polymer are dissolved as they are or in a solvent. Or the method of distilling an organic solvent after mixing with what was disperse | distributed is illustrated. Or the method of distilling a solvent off after mixing the isolated solvent soluble polyimide and (pi) conjugated polymer from the imidation reaction product in the organic solvent is illustrated. As the organic solvent, an aprotic polar solvent is preferably used. Specifically, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, 1,3- Examples thereof include dimethyl-2-imidazolidinone, sulfolane, diglyme, triglyme, cyclohexanone, cyclopentanone, and γ-butyrolactone, and these can be used alone or as a mixed system. Of these, N-methyl-2-pyrrolidone and γ-butyrolactone are particularly preferred from the viewpoints of polymerizability and solvent solubility.

  The mixing temperature and time vary depending on the types of polyimide resin and π-conjugated polymer and the content ratio thereof, but the temperature is usually 0 to 150 ° C., preferably 0 to 100 ° C., and the time is 0.5 to 24 hours. Illustrated.

  In the polyimide resin composition of the present invention, known silica, alumina, mica and other fillers, carbon powder, pigments, dyes, polymerization inhibitors, thickeners, thixotropic agents, precipitation preventions, as long as the effects of the present invention are not impaired. An agent, an antioxidant, a dispersant, a pH adjuster, a surfactant, various organic solvents, various resins and the like can be added.

  The method for obtaining the resin composition or the molded product thereof from the resin varnish is not particularly limited, and a conventionally known method can be used. For example, the resin varnish of the present invention is applied to the surface of the substrate and then dried. Examples include a method of distilling off the solvent to form a film, a film or a sheet, a method of injecting the resin varnish of the present invention into a mold, and then distilling off the solvent to obtain a molded body. .

  More specifically, as a method of forming a film, a film or a sheet, the resin varnish of the present invention is based on a known method such as a spin coating method, a dip method, a spray method or a casting method depending on the viscosity or the like. The method of drying after apply | coating to the material surface is illustrated.

  Any substrate can be used depending on the use of the final product. For example, non-conductive substances, for example, textile products such as cloth, synthetic resin films, and glass can be used.

  As a method for drying the applied varnish, a normal heating and drying furnace can be used. An inert gas (nitrogen, argon) or the like can be used as the atmosphere of the drying furnace. Although it can select suitably as a drying temperature with the boiling point of a solvent, Usually, 50-300 degreeC, More preferably, it is 80-200 degreeC, Most preferably, the temperature range of 100-200 degreeC is illustrated. Although drying time can be suitably selected with thickness, a density | concentration, and the kind of solvent, about 0.05-500 minutes are illustrated. If necessary, drying may be performed under reduced pressure.

  After drying, a product having the resin composition of the present invention as a film can be obtained as it is, and it can also be obtained as a film by separating the resin composition from the substrate.

  In addition, when a molded body is obtained using a mold, a predetermined amount of resin varnish is injected into the mold (especially, a rotating mold is preferred) and then dried at the same temperature and time as the molding conditions for films and the like. Thus, a molded body can be obtained.

The specific resistance value of the polyimide resin composition of the present invention and the resin molded product obtained by molding the polyimide resin composition varies depending on the dope state of the π-conjugated polymer, but is usually 25 ° C., 60% RH, applied voltage The surface specific resistance value under the condition of 500 V is in the range of 10 ⁵ to 10 ¹⁴ Ω, and the volume specific resistance value is in the range of 10 ⁶ to 10 ¹⁴ Ω · cm. In particular, in applications that require insulation, it is preferable to use an undoped π-conjugated polymer. In this case, the resulting polyimide resin composition is usually 1 × 10 ¹³ Ω · cm or more in terms of volume resistance. .

  The mechanical strength varies depending on the type of polyimide resin, the type of π-conjugated polymer, and the content ratio thereof, but usually has a tensile strength in the range of 130 to 400 MPa, preferably 150 to 300 MPa, and a tensile modulus of 3000. It is -6000MPa, Preferably it is the range of 3500-5000MPa. For example, the solvent-soluble polyimide resin represented by the general formula (3) alone usually has a tensile strength in the range of 80 to 110 MPa, 100 parts by weight of the polyimide represented by the general formula (3), and a π-conjugated polymer In the polyimide resin composition of the present invention containing the above, an improvement in mechanical strength of 20% or more is usually observed relative to that before blending.

  The resin molded body thus obtained is excellent in heat resistance and mechanical strength, so it can be used in applications such as electrical / electronic fields, optical materials, paints, and more specifically, printed wiring boards, flexible printed wiring boards. Base films such as copper-clad laminates, adhesives, or substrate materials such as cover films and cover coats, solid capacitors, antistatic films, electromagnetic shielding materials, adhesives, paints, wiring materials, display materials, overcurrent protection It can be used in elements and semiconductor elements.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited at all by an Example. In addition, the symbol of the compound in an Example and a comparative example, and the measurement of each characteristic are as follows. Moreover, unless otherwise indicated in each Example and a comparative example, a part represents a weight part.

(A) Acid value After about 2 g of a polyimide resin solution, which is a reaction product after completion of the imidation reaction, was accurately weighed and diluted with 60 ml of tetrahydrofuran, the acid value was measured according to JIS K0070-1966, and the polyimide resin pure content Converted into

(B) Molecular weight A sample for molecular weight measurement was prepared by diluting about 1 g of a polyimide resin solution, which is a reaction product after the imidation reaction, with 30 ml of dimethylformamide. For this measurement sample, the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polyethylene oxide were determined by gel permeation chromatography (GPC) using dimethylformamide as the mobile phase.

(C) Mechanical strength: Tensile strength and tensile modulus A solution of a polyimide resin and a π-conjugated polymer was applied on a polytetrafluoroethylene (PTFE) sheet, and dried at 150 ° C. for 1 hour. A resin film having a thickness of about 50 μm was obtained. A 10 mm × 80 mm sample piece was cut out from the obtained resin film to prepare a measurement sample. This measurement sample was measured according to JIS K7127, using an Instron universal testing machine manufactured by Instron, at a distance between chucks of 50 mm, a tensile speed of 10 mm / min, and a test temperature of 25 ° C.

(D) Volume resistivity value A solution of a polyimide resin and a π-conjugated polymer is applied on a polytetrafluoroethylene (PTFE) sheet, dried at 150 ° C. for 1 hour, and a resin having a thickness of about 50 μm. A film was obtained. From the obtained resin film, a sample piece of 8 cm × 8 cm was cut out to prepare a measurement sample. For this measurement sample, the volume specific resistance value is measured under the conditions of an applied voltage of 500 V and 25 ° C. × 60% RH using a vibration capacity type electrometer TR8401 manufactured by ADVANTEST, an insulation resistance measurement power supply TR300C, and an insulation resistance meter TR43C. did.

Synthesis Example 1 (Synthesis example of solvent-soluble polyimide A)
Mixed solvent 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (hereinafter abbreviated as “DSDA”) 48.9 g of NMP 360 g and xylene 40 g, 2,2-bis [4- (p- Aminophenoxy) phenyl] propane (hereinafter abbreviated as “BAPP”) 56.0 g was dissolved at room temperature and then refluxed at 180 ° C. for 3 hours to carry out an imidization reaction (reaction product water: about 4.9 g). The polyimide resin (solvent soluble polyimide A) in the obtained polyimide resin solution had an acid value of 3.9 mg KOH / g weight average molecular weight (Mw) of 96,800 and a number average molecular weight (Mn) of 39,800. .

Synthesis Example 2 (Synthesis example of solvent-soluble polyimide B)
In a mixed solvent of 360 g of NMP and 40 g of xylene, 48.9 g of DSDA and 59.0 g of 2,2-bis [4- (p-aminophenoxy) phenyl] sulfone (hereinafter abbreviated as “BAPS”) are dissolved at room temperature, and then 180 g. The mixture was refluxed at 3 ° C. for 3 hours to carry out an imidization reaction (reaction product water: about 4.9 g). The polyimide resin (solvent soluble polyimide B) in the obtained polyimide resin solution had an acid value of 4.8 mgKOH / g weight average molecular weight (Mw) of 67,600 and a number average molecular weight (Mn) of 33,200. .

Synthesis Example 3 (Synthesis example of solvent-soluble polyimide C)
In a mixed solvent of 360 g of NMP and 40 g of xylene, 39.1 g of DSDA, 11.2 g of TMEG [DSDA / TMEG = 80/20 (molar ratio)], 2,2-bis [4- (p-aminophenoxy) phenyl] sulfone (hereinafter, “ This is abbreviated as “BAPS.”) 59.0 parts by weight was dissolved at room temperature and then refluxed at 180 ° C. for 3 hours to carry out an imidation reaction (about 4.9 parts of reaction product water). The polyimide resin (solvent soluble polyimide C) in the obtained polyimide resin solution had an acid value of 3.8 mgKOH / g weight average molecular weight (Mw) of 82,400 and a number average molecular weight (Mn) of 37,000. .

Synthesis Example 4 (Synthesis example of polyaniline B)
60 parts of black powder of polyaniline (polyaniline A) (reduction type content ratio 48 mol%) is added to a mixed solution of 100 parts of hydrazine, 160 parts of methanol, and 200 parts of water to form a slurry state. Stirring was performed for a time to obtain an off-white powder. The obtained off-white powder was filtered off and vacuum dried at room temperature to prepare polyaniline (polyaniline B) having a high content of reduced structure. When the ratio of phenylenediamine type (reduced type) / quinone diimine type (oxidized type) in the polyaniline was calculated from FT-IR spectrum analysis, the content ratio of reduced type was 84 mol%.

Example 1
10 parts by weight of polyaniline B (reduction type content ratio 84 mol%) prepared in Synthesis Example 4 is added to 450 parts by weight of polyimide resin solution (90 parts by weight of polyimide resin) containing solvent-soluble polyimide A prepared in Synthesis Example 1. And mixed at 25 ° C. for 1 hour. The obtained resin varnish (resin concentration: about 22% by weight) was uniform and did not precipitate or separate insoluble matters. This resin varnish was formed on a polytetrafluoroethylene (hereinafter abbreviated as “PTFE”) sheet by using a doctor blade to form a coating of about 250 μm and dried under reduced pressure at 150 ° C. for 1 hour. A film of a polyimide resin composition having a thickness of about 50 μm was prepared. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 160 MPa, and the tensile elastic modulus was 5000 Mpa.

Example 2
10 parts by weight of polyaniline B (reduction type content ratio 84 mol%) prepared in Synthesis Example 4 is added to 450 parts by weight of polyimide resin solution (90 parts by weight of polyimide resin) containing solvent-soluble polyimide B prepared in Synthesis Example 2. And mixed at 25 ° C. for 1 hour. The obtained resin varnish (resin concentration: about 22% by weight) was uniform and did not precipitate or separate insoluble matters. The resin varnish was formed on a PTFE sheet using a doctor blade to form a coating film having a thickness of about 250 μm, and dried under reduced pressure at 150 ° C. for 1 hour, thereby forming a polyimide resin composition film having a thickness of about 50 μm. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 155 MPa, and the tensile elastic modulus was 4900 MPa.

Example 3
10 parts by weight of polyaniline B (reduction type content ratio 84 mol%) prepared in Synthesis Example 4 is added to 450 parts by weight of a polyimide resin solution (90 parts by weight of polyimide resin) containing solvent-soluble polyimide C prepared in Synthesis Example 3. And mixed at 25 ° C. for 1 hour. The obtained resin varnish (resin concentration: about 22% by weight) was uniform and did not precipitate or separate insoluble matters. The resin varnish was formed on a PTFE sheet using a doctor blade to form a coating film having a thickness of about 250 μm, and dried under reduced pressure at 150 ° C. for 1 hour, thereby forming a polyimide resin composition film having a thickness of about 50 μm. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 135 MPa, and the tensile elastic modulus was 4500 MPa.

Example 4
A resin varnish and a polyimide resin composition film were prepared in the same manner as in Example 1 except that polyaniline A (reduced-type content ratio 47 mol%) was used instead of polyaniline B (reduced-type content ratio 84 mol%). . The resin varnish was uniform and no insoluble matter was deposited or separated. Moreover, the volume resistance value of the obtained film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 120 MPa, and the tensile elastic modulus was 3500 MPa.

Example 5
Polyaniline B prepared in Synthesis Example 4 (reduced-type content ratio 84 mol%) 50 weights to a polyimide solution obtained by adding 100 parts by weight of NMP to 250 parts by weight of a solvent-soluble polyimide A-containing polyimide resin solution (polyimide resin 50 parts by weight). Part was added and mixed at 40 ° C. for 1 hour. The obtained resin varnish (resin concentration: about 25% by weight) was uniform and no precipitation of insoluble matter was observed. A polyimide resin composition film was prepared from this resin varnish by the same method as in Example 1. The volume resistance value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 160 MPa, and the tensile elastic modulus was 5000 Mpa.

Example 6
Polyaniline B (reduced-type content ratio 84 mol%) prepared in Synthesis Example 4 is added to a polyimide solution obtained by adding 150 parts by weight of NMP to 150 parts by weight of a polyimide resin solution containing polyimide A (30 parts by weight of polyimide resin). Part was added and mixed at 40 ° C. for 1 hour. The obtained resin varnish (resin concentration: about 18% by weight) was uniform, and precipitation of insoluble matters was not observed. A polyimide resin composition film was prepared from this resin varnish by the same method as in Example 1. The volume resistance value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 115 MPa, and the tensile elastic modulus was 3300 MPa.

Comparative Example 1
A polyimide resin solution containing the solvent-soluble polyimide A prepared in Synthesis Example 1 is formed on a PTFE sheet by using a doctor blade to form a coating film of about 250 μm and dried under reduced pressure at 150 ° C. for 1 hour. A 50 μm resin film was prepared. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 95 MPa, and the tensile elastic modulus was 2500 MPa.

Comparative Example 2
A polyimide resin solution containing the solvent-soluble imide B prepared in Synthesis Example 2 is formed on a PTFE sheet by using a doctor blade to form a coating film of about 250 μm and dried under reduced pressure at 150 ° C. for 1 hour. A 50 μm resin film was prepared. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 105 MPa, and the tensile elastic modulus was 2800 Mpa.

Comparative Example 3
A polyimide resin solution containing the solvent-soluble imide C prepared in Synthesis Example 3 is formed on a PTFE sheet by using a doctor blade to form a coating film of about 250 μm and dried under reduced pressure at 150 ° C. for 1 hour. A 50 μm resin film was prepared. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 80 MPa, and the tensile elastic modulus was 2700 MPa.

Comparative Example 4
20 parts by weight of polyaniline B prepared in Synthesis Example 4 was dissolved in 80 parts by weight of NMP to prepare a polyaniline resin solution. The polyaniline resin solution was formed on a PTFE sheet by using a doctor blade to form a coating film having a thickness of about 250 μm and dried under reduced pressure at 150 ° C. for 1 hour to prepare a resin film having a thickness of about 50 μm. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 100 MPa, and the tensile elastic modulus was 2800 Mpa.

Comparative Example 5
20 parts by weight of polyaniline A was dissolved in 80 parts by weight of NMP to prepare a polyaniline resin solution. The polyaniline resin solution was formed on a PTFE sheet by using a doctor blade to form a coating film having a thickness of about 250 μm and dried under reduced pressure at 150 ° C. for 1 hour to prepare a resin film having a thickness of about 50 μm. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 90 MPa, and the tensile elastic modulus was 2700 MPa.

Example 6
To 450 parts by weight of a polyimide resin solution containing 90% by weight of a polyimide soluble in solvent A prepared in Synthesis Example 1, ethyl 3-methyl-4-pyrrolecarboxylate and butyl 3-methyl-4-pyrrolecarboxylate 100 parts by weight of a 10% by weight copolymer NMP solution was added and mixed at 25 ° C. for 1 hour. The obtained resin varnish (resin concentration: about 18% by weight) was uniform, and precipitation of insoluble matters was not observed. A coating film having a thickness of about 250 μm was formed on the PTFE sheet using a doctor blade, and the resin varnish was dried under reduced pressure at 150 ° C. for 1 hour, thereby forming a resin film having a thickness of about 50 μm. The volume resistance value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 140 MPa, and the tensile modulus was 4600 MPa.

Comparative Example 6
Using a doctor blade, an about 250 μm solution of NMP 10 wt% solution of a copolymer of ethyl 3-methyl-4-pyrrolecarboxylate and butyl 3-methyl-4-pyrrolecarboxylate used in Example 6 was applied. A film was formed and dried under reduced pressure at 150 ° C. for 1 hour to prepare a resin film having a thickness of about 50 μm. The volume resistivity value of this film was 1 × 10 ¹³ Ω · cm or more, the tensile strength was 70 MPa, and the tensile modulus was 2400 MPa.

According to the present invention, a solvent-soluble polyimide resin composition having improved mechanical strength can be obtained. This polyimide resin composition is highly useful industrially as a material for electric and electronic parts by utilizing this excellent property. More specifically, this polyimide resin composition is a base for printed wiring boards, copper-clad laminates and the like. It can be used for applications such as film materials, adhesives, cover films, substrate materials such as cover coats, solid capacitors, antistatic films, electromagnetic wave shields, paints, wiring materials, display materials, overcurrent protection devices, and semiconductor elements. .

Applicant New Japan Rika Co., Ltd.

Claims (16)

  A polyimide resin composition comprising a solvent-soluble polyimide and a π-conjugated polymer.   The polyimide resin composition according to claim 1, wherein the π-conjugated polymer is at least one selected from the group consisting of polyaniline, polypyrrole, polyfuran, polythiophene, and polyacetylene.   The polyimide resin composition according to claim 2, wherein the π-conjugated polymer is polyaniline. Polyaniline has the general formula (1)

[Wherein, h and i represent mole fractions in repeating units of quinonediimine type (oxidized type) polyaniline and phenylenediamine type (reduced type) polyaniline, respectively, 0 <h ≦ 0.3, 0.7 ≦ i <1 and h + i = 1. ]
The polyimide resin composition according to claim 3, which is a reduced polyaniline having a repeating unit represented by: Solvent-soluble polyimide is represented by the general formula (2)

[Wherein X ¹ represents a direct bond, —O—, —CO—, —SO ₂ —, or a group (a)

{Wherein, ^{Z 1} represents a linear or branched alkylene group, 1,3-phenylene or 1,4-phenylene group having 2 to 10 carbon atoms. }
Represents. Y ¹ represents a divalent organic group. j represents an integer of 1 or more. ]
The polyimide resin composition according to claim 1, which is a solvent-soluble polyimide having a structural unit represented by: Solvent-soluble polyimide is represented by the general formula (3)

[Wherein Y ² represents —O—, —S—, —SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ) ₂ —, 1,3-phenylene group, 1,4- Phenylene group or group (b)

{Wherein Y ³ represents —O—, —SO ₂ — or —C (CH ₃ ) ₂ —. }
Represents. k represents an integer of 1 or more. ]
The polyimide resin composition according to claim 5, which is a solvent-soluble polyimide having a structural unit represented by:   The polyimide resin composition according to any one of claims 1 to 6, wherein the solvent-soluble polyimide has an acid value of 0.1 to 30 mgKOH / g.   The polyimide resin composition according to claim 1, comprising 1 to 50 parts by weight of a π-conjugated polymer with respect to 100 parts by weight of the solvent-soluble polyimide.   The polyimide resin composition according to any one of claims 1 to 8, wherein the polyimide resin composition has a tensile strength of 130 MPa or more and a tensile modulus of 3000 MPa or more. The polyimide resin composition according to claim 1, wherein the polyimide resin composition has a volume resistivity of 10 ¹³ Ω · cm or more.   The molded object obtained by shape | molding the resin composition in any one of Claims 1-10.   A mechanical strength improver for a solvent-soluble polyimide resin, wherein the mechanical strength improver is a π-covalent polymer. The mechanical strength improver is represented by the general formula (1)

[Wherein, h and i represent mole fractions in repeating units of quinonediimine type (oxidized type) polyaniline and phenylenediamine type (reduced type) polyaniline, respectively, 0 <h ≦ 0.3, 0.7 ≦ i <1 and h + i = 1. ]
The mechanical strength improver according to claim 12, which is a reduced polyaniline represented by:   It is a mechanical strength improver, and by blending 1 to 50 parts by weight of the mechanical strength improver with respect to 100 parts by weight of the solvent-soluble polyimide, the tensile strength of the solvent-soluble polyimide resin composition after blending is determined before blending. The mechanical strength improver according to claim 12, which has a property of improving by 30% or more.   A method for improving the mechanical strength of a solvent-soluble polyimide resin, comprising blending the mechanical strength improver according to claim 11 to the solvent-soluble polyimide resin. A polyimide resin composition comprising a solvent-soluble polyimide resin and the mechanical strength improver according to claim 11.