JP5879971B2 - Polyimide solution composition - Google Patents

Description

  The present invention relates to a polyimide solution composition obtained by reacting a tetracarboxylic acid component with a diamine component containing a diamine compound represented by the following formula (1).

  Patent Documents 1, 2, and 3 include a polyimide siloxane solution composition obtained by polymerizing and imidizing a tetracarboxylic acid component, a diaminopolysiloxane, a diamine having a polar group, and a diamine component other than the above. Is described. In order to give a cured product having both flexibility and heat resistance, this polyimidesiloxane solution composition is applied, for example, by screen printing on a flexible wiring board and then cured to form a cured insulating film of an electronic component. Is preferably used. However, it has been pointed out that siloxane-based materials cause contact failure in electronic parts due to outgassing, and there has been a demand for insulating films and protective films made of different materials.

Japanese Patent Laid-Open No. 8-253676 JP 2006-156949 A International Publication No. 2011/021628 Pamphlet

  An object of this invention is to provide the polyimide solution composition which is excellent in the softness | flexibility equivalent to a siloxane type material, and heat resistance, without using a siloxane type material.

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

1. The polyimide solution composition obtained by making the tetracarboxylic-acid component and the diamine component containing the diamine compound represented by Formula (1) react in a solvent.

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

3. 2. The polyimide solution composition according to 1 above, wherein the diamine compound represented by the formula (1) has 36 carbon atoms.

4). In the diamine compound represented by the formula (1), A is

である、上記１〜３のいずれかに記載のポリイミド溶液組成物。

The polyimide solution composition according to any one of 1 to 3 above.

5). In the diamine compound represented by the formula (1), the polyimide solution composition according to any one of the above 1 to 4, wherein R ¹ , R ² , R ³ and R ⁴ each have 4 to 15 carbon atoms.

6). Furthermore, the polyimide solution composition in any one of said 1-5 containing other diamines other than the diamine compound represented by Formula (1) as a diamine component.

7). 7. The polyimide solution composition as described in 6 above, wherein the other diamine is an aromatic diamine having a plurality of benzene rings.

8). Hardened | cured material manufactured using the polyimide solution composition in any one of said 1-7.

  When the polyimide solution composition of the present invention is used, a film excellent in mechanical properties, heat resistance and adhesiveness can be obtained, which is suitable for various uses such as an insulating film and a protective film for electronic parts. The polyimide solution composition of the present invention is prepared without using a siloxane compound. Moreover, although the film | membrane manufactured from the conventional siloxane type material is inferior to adhesiveness, the film | membrane manufactured from the polyimide solution composition of this invention has favorable adhesiveness, and is excellent in adhesiveness with a wiring board etc.

It is a figure which shows the measurement result of the tensile elasticity modulus in an Example. It is a figure which shows the measurement result of the breaking elongation in an Example. It is a figure which shows the measurement result of 5% weight reduction | decrease temperature in an Example. It is a figure which shows the measurement result of the peeling strength in an Example.

  The polyimide solution composition of the present invention can be obtained by reacting a tetracarboxylic acid component and a diamine component in a solvent. 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, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl. 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 tetravalent residue having 1 to 4 carbon atoms,

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価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 a tetravalent residue 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 following formula (1-1)-(1-3) is mentioned, for example.

  The diamine component may contain other diamines in addition to the diamine compound.

  The other diamine is not particularly limited as long as it is a diamine other than the diamine represented by the formula (1), but an aromatic diamine composed of a plurality of benzene rings represented by the following chemical formula (2) is preferable. It is.

化学式（２）において、Ｘ及びＹは、それぞれ独立に、直接結合、ＣＨ_２、Ｃ（ＣＨ_３）_２、Ｃ（ＣＦ_３）_２、Ｏ、ベンゼン環、ＳＯ_２を示し、ｎ５は１又は２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 the chemical formula (2), X and Y each independently represent a direct bond, CH ₂ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , O, a benzene ring, or SO ₂ , and n5 is 1 or 2 It is. 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.

  Examples of the aromatic diamine represented by the chemical formula (2) include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 1,4-diamino-2,5-dihalogenobenzene, and the like. Diamines containing one benzene, 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-to Diamines containing two benzenes such as gin and tolidine sulfonic acids, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-amino) Phenyl) benzene, 1,4-bis (3-aminophenyl) benzene, α, α′-bis (4-aminophenyl) -1,4-diisopropylbenzene, α, α′-bis (4-aminophenyl)- Diamines containing three benzenes such as 1,3-diisopropylbenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4 ′-(4-aminophenoxy) biphenyl, 9,9 Examples include diamine compounds such as diamines containing 4 or more benzenes such as -bis (4-aminophenyl) fluorene and 5,10-bis (4-aminophenyl) anthracene.

  In addition, aliphatic diamine compounds such as hexamethylene diamine and diaminododecane can be used together with the diamine. In addition, a diamine compound having a polar group such as a hydroxyl group, an amide group, a carboxylic acid group, or a sulfonic acid group in the molecule may be used in order to provide reactivity with other resins and crosslinking materials.

  Among the diamine components, the diamine compound (1) is preferably contained in an amount of 5 to 100 mol%, more preferably 5 to 95 mol%, still more preferably 15 to 90 mol%.

  Examples of the tetracarboxylic acid component include 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid. Carboxylic acid, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Acid, 2,2-bis (3,4-benzenedicarboxylic acid) hexafluoropropane, pyromellitic acid, 1,4-bis (3,4-benzenedicarboxylic acid) benzene, 2,2-bis [4- (3 , 4-phenoxydicarboxylic acid) phenyl] propane, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalene Aromatic tetracarboxylic acids such as tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,1-bis (2,3-dicarboxyphenyl) ethane, or their acid dianhydrides or lower Alcohol esterified products and fats such as cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3-methyl-4-cyclohexene-1,2,4,5-tetracarboxylic acid Preferable examples include cyclic tetracarboxylic acids, or acid dianhydrides and esterified products of lower alcohols. The tetracarboxylic acid component is preferably a tetracarboxylic dianhydride that can be easily reacted with a diamine. In the present invention, it is particularly preferable to use 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride.

  The ratio of the tetracarboxylic acid component and the diamine component used in the present invention is approximately equimolar, preferably 0.95 to 1.2, more preferably 1.0 to tetracarboxylic acid component per 1 mol of the diamine component. The ratio is about 1.1 mol.

  The solvent used in the reaction is not 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, but an organic polar solvent having excellent solubility. Is preferred. Examples of the organic polar solvent include nitrogen-containing solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, N- Ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, etc .; solvents containing sulfur atoms such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, hexamethylsulfuramide, etc. Phenolic solvents such as cresol, phenol and xylenol; diglyme solvents such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme) and tetraglyme; oxygen atoms in the molecule Solvent, such as acetone, methanol, ethanol, ethylene glycol, dioxane, isophorone, tetrahydrofuran; lactone solvents such .gamma.-butyrolactone, .gamma.-valerolactone; can be cited other pyridine, tetramethylurea and the like. Moreover, you may use together other organic solvents, such as aromatic hydrocarbon type solvents, such as benzene, toluene, and xylene, solvent naphtha, and benzonitrile, as needed.

  The polyimide solution composition of this invention can be manufactured by making a tetracarboxylic-acid component, a diamine compound (1), and another diamine compound react as needed 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. Further, a tetracarboxylic acid component and a diamine component are reacted in a solvent at a temperature of about 100 ° C. or less 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 as 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.

  In the present invention, it is suitable that the polyimide solution is dissolved in a solvent at a solid content concentration of at least 3% by mass, preferably 5 to 60% by mass, more preferably 20 to 40% by mass. As for the viscosity of the polyimide solution 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: N-methyl-2-pyrrolidone, measurement temperature: 30 ° C.), which is a measure of the molecular weight of polyimide, is preferably 0.15 or more, more preferably 0.16 to 2.

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

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

  In order to obtain a curable solution composition, a curable component employed in a normal curable resin composition such as an epoxy resin, a polyvalent isocyanate, a phenol resin, or a guanamine resin can be suitably used.

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

  That is, in the polyimide solution 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.

  The polyimide film produced using the polyimide solution composition of the present invention is excellent in mechanical properties such as tensile elastic modulus, breaking strength and breaking elongation, heat resistance and adhesiveness, and is suitable for use in electronic parts. That is, there is no problem in mechanical properties and heat resistance as in the case of using a conventional polyimide siloxane solution. And since the film using the polyimide solution of this invention has favorable adhesiveness, when it uses for an electronic component, it is excellent also in adhesiveness with a board | substrate etc.

  Hereinafter, the present invention will be described in more detail based on specific examples. In addition, this invention is not limited to the following examples.

The raw materials used are as follows.
<Acid anhydride>
а-BPDA: 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (molecular weight 294.22, manufactured by Ube Industries, Ltd.)
<Diamine>
PRIAMINE 1074: Dimer diamine (amine equivalent 250-300 g / mol, manufactured by Claude Japan Co., Ltd.)
KF-8010: siloxane diamine (amine equivalent of 400 to 500 g / mol, manufactured by Shin-Etsu Chemical Co., Ltd.)
Jeffamine D400: polyoxypropylenediamine, molecular weight 434.78, manufactured by Mitsui Chemicals Fine Co., Ltd.)
BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] propane (molecular weight 410.52, manufactured by Wakayama Seika Kogyo Co., Ltd.)
<Solvent>
NMP: N-methyl-2-pyrrolidone

  Evaluation methods and the like in Examples and Comparative Examples are as follows.

[Measurement method of solid content]
The sample solution composition was heat-treated while being heated in the order of 120 ° C. for 10 minutes and then 250 ° C. for 60 minutes. From the sample weight (w1) before the heat treatment and the weight (w2) after the heat treatment, the solid content concentration was calculated by the following formula.

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

[Measurement method of solution viscosity]
The solution viscosity at 10 rpm at 25 ° C. was measured using an E-type rotational viscometer.

[Mechanical properties]
The prepared polyimide solution was coated on a glass substrate, heated in a hot air oven at 80 ° C. for 30 minutes, and then heated at 200 ° C. for 60 minutes to be cured to prepare a polyimide film having a thickness of approximately 60 μm. The obtained polyimide film was cut into a width of 10 mm and a length of 100 mm to obtain a test piece. About this test piece, using a tensile tester (Orientec; Tensilon UCT-5T) under conditions of a temperature of 25 ° C., a humidity of 50% RH, a crosshead speed of 50 mm / min, and a distance between chucks of 50 mm. The breaking strength and elongation at break were measured.

[Pyrolysis temperature]
The prepared polyimide solution was applied onto a glass substrate and cured by heating in a hot air oven at 80 ° C. for 30 minutes and then at 200 ° C. for 60 minutes to prepare a polyimide film having a thickness of approximately 60 μm. About the obtained polyimide film, 5% weight reduction temperature was measured using TG-DTA. The measurement was performed at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere.

[Peel strength (adhesion test)]
The prepared polyimide solution was applied to a polyimide film (Upilex 25S) and dried in a hot air oven at 80 ° C. for 30 minutes to obtain a dry film of a polyimide solution having a coating thickness of about 20 μm. Thereafter, the dried film is covered with a rolled copper foil (mirror surface) and heated and pressed at a temperature of 200 ° C., a pressing pressure of 30 kgf / cm for 30 minutes using a press machine, and a polyimide film / dried film of prepared polyimide solution / copper. An adhesive film laminated in the order of foil was obtained. A 180 ° peel test was carried out by pulling the copper foil side of the adhesive film.

<Example 1>
In a glass flask having a volume of 500 ml, 27.37 g of PRIAMINE 1074 (amine equivalent 274 g / mol) and 30.79 g of BAPP as a diamine and a part of NMP as a solvent were added and stirred at 50 ° C. for 30 minutes to dissolve the diamine. . Thereafter, 36.78 g of acid anhydride а-BPDA and the remaining solvent NMP were charged (total of NMP was 284.81 g, monomer molar ratio was а-BPDA: PRIAMINE 1074: BAPP = 10: 4: 6). In a nitrogen atmosphere, the mixture was heated and stirred at 50 ° C. for 1 hour, then heated to 180 ° C. and subjected to heat polymerization for 15 hours. The obtained polyimide solution was a solution having a polymer solid content concentration of 25 to 26% by weight and ηinh 0.63. The imidization rate was substantially 100%. Using this polyimide solution, a polyimide film was prepared and measured for mechanical properties, thermal decomposition temperature and peel strength by the above-described methods. The results are shown in Table 1.

<Example 2>
48.17 g of PRIAMINE 1074 and 9.03 g of BAPP, 32.36 g of acid anhydride and 32.36 g of NMP, and 268.69 g of solvent (the molar ratio of monomers is а-BPDA: PRIAMINE 1074: BAPP = 10: 8: Except for 2), a polyimide film was prepared in the same manner as in Example 1 and measured for mechanical properties, thermal decomposition temperature, and peel strength. The results are shown in Table 1.

<Example 3>
38.32 g of PRIAMINE 1074 and 12.32 g of BAPP, 29.42 g of acid anhydride and 240.16 g of NMP as a solvent (the molar ratio of monomers is а-BPDA: PRIAMINE 1074: BAPP = 10: 7: Except for 3), a polyimide film was produced in the same manner as in Example 1 and measured for mechanical properties, thermal decomposition temperature, and peel strength. The results are shown in Table 1.

<Example 4>
36.13 g of PRIAMINE 1074 and 22.58 g of BAPP, 35.60 g of acid anhydride and 282.92 g of NMP (molar ratio of the monomer is а-BPDA: Priamin 1074: BAPP = 10: 55. 5: 4.5) A polyimide film was prepared in the same manner as in Example 1 except that the mechanical properties, thermal decomposition temperature, and peel strength were measured. The results are shown in Table 1.

<Example 5>
14.23 g of PRIAMINE 1074 and 42.69 g of diamine, 38.25 g of acid anhydride, 38.25 g of NMP, and 285.52 g of NMP (molar ratio of monomers is а-BPDA: PRIAMINE 1074: BAPP = 10: 2: Except for 8), a polyimide film was prepared in the same manner as in Example 1 and measured for mechanical properties, thermal decomposition temperature, and peel strength. The results are shown in Table 1.

<Comparative Example 1>
Except that the diamine was BAPP 53.37 g, the acid anhydride was а-BPDA 38.25 g, and the solvent was NMP 274.85 g (monomer molar ratio was а-BPDA: BAPP = 10: 10). A polyimide film was prepared in the same manner as in Example 1 and measured for mechanical properties, thermal decomposition temperature, and peel strength. The results are shown in Table 1.

<Comparative Example 2>
The diamine is siloxane diamine (KF-8010) 21.91 g and BAPP 38.42 g, the acid anhydride is а-BPDA 35.31 g, the solvent is NMP 286.92 g (the molar ratio of the monomers is а-BPDA: KF-8010: A polyimide film was prepared in the same manner as in Example 1 except that BAPP = 10: 2.2: 7.8), and mechanical properties, thermal decomposition temperature, and peel strength were measured. The results are shown in Table 1.

<Comparative Example 3>
The diamine is siloxane diamine (KF-8010) 39.84 g and BAPP 29.56 g, the acid anhydride is а-BPDA 35.31 g, the solvent is NMP 365.11 g (the molar ratio of the monomers is а-BPDA: KF-8010: A polyimide film was prepared in the same manner as in Example 1 except that BAPP = 10: 4: 6), and mechanical properties, thermal decomposition temperature, and peel strength were measured. The results are shown in Table 1.

<Comparative example 4>
68.72 g of siloxane diamine (KF-8010) and BAPP
15.27 g, acid anhydride 35.31 g, and solvent NMP 357.91 g (monomer molar ratio: а-BPDA: KF-8010: BAPP = 10: 6.9: 3.1) Except for the above, a polyimide film was prepared in the same manner as in Example 1, and the mechanical properties, thermal decomposition temperature, and peel strength were measured. The results are shown in Table 1.

<Comparative Example 5>
10.43 g of Jeffamine D400 and 39.41 g of BAPP, 35.31 g of acid anhydride, and 355.45 g of NMP as solvent (molar ratio of monomers, а-BPDA: Jeffamine D400: BAPP = 10: A polyimide film was prepared in the same manner as in Example 1 except that it was set to 2: 8), and mechanical properties, thermal decomposition temperature, and peel strength were measured. The results are shown in Table 1.

<Comparative Example 6>
21.74 g of diamine Jeffamine D400 and 30.79 g of BAPP, 36.78 g of acid anhydride and 367.92 g of NMP (molar ratio of monomers is а-BPDA: Jeffamine D400: BAPP = 10: Except for 4: 6), a polyimide film was prepared in the same manner as in Example 1 and measured for mechanical properties, thermal decomposition temperature, and peel strength. The results are shown in Table 1.

<Comparative Example 7>
Diamine: Jeffamine D400 28.70 g and BAPP 22.58 g, acid anhydride: а-BPDA 35.60 g, solvent: NMP 260.62 g (molar ratio of monomers: а-BPDA: Jeffamine D400: BAPP = 10: 5.5: 4.5) A polyimide film was prepared in the same manner as in Example 1 except that the thermal decomposition temperature and peel strength were measured. The results are shown in Table 1. The mechanical properties could not be measured because the coating film was very brittle and could not be peeled from the glass substrate as a film capable of measuring mechanical strength.

  The measurement results of the tensile modulus, elongation at break, 5% weight loss temperature and peel strength in the above Examples and Comparative Examples are shown in FIGS.

  FIG. 1 and FIG. 2 show the relationship between the content of diamine compounds other than BAPP and the tensile modulus and elongation at break, respectively. The higher the content of PRIAMINE 1074, which is the diamine compound (1) in the present invention, or KF-8010, which is the siloxane diamine, the tensile modulus decreased and the elongation at break increased, so that the flexibility increased. It was shown that. On the other hand, it was shown that when none of PRIANIME 1074 and siloxane diamine was used and only BAPP was contained or when Jeffamine D400, which is a polyoxypropylene diamine, was contained, the tensile modulus was high and flexibility was not imparted.

  FIG. 3 shows the relationship between the content of diamine compounds other than BAPP and the 5% weight loss temperature. Even when the content of PRIAMINE 1074 or KF-8010 was increased, the change in the 5% weight loss temperature was small, indicating that the heat resistance did not decrease. On the other hand, it was shown that when the content of Jeffamine D400 is increased, the heat resistance is greatly reduced.

  FIG. 4 shows the relationship between the content of diamine compounds other than BAPP and peel strength. It has been shown that when PRIAMINE 1074 or Jeffamine D400 is contained, the peel strength is large, and the adhesiveness is higher than when KAM-8010 is contained.

  Therefore, it was shown that the polyimide film manufactured using the polyimide solution composition containing PRIAMINE 1074 has flexibility and heat resistance, and also has adhesiveness.

Claims (8)

The nitrogen-containing solvent, the polyimide solution composition polyimide is dissolved including a repeating unit represented by the following formula (I).

In the formula ( I ), 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. The polyimide solution composition according to claim 1, wherein the total number of carbon atoms of A, R ¹ , R ² , R ³ and R ⁴ is 20 to 48. The polyimide solution composition according to claim 1, wherein the total number of carbon atoms of A, R ¹ , R ² , R ³ and R ⁴ is 36. Oite the formula (I), A is,

The polyimide solution composition according to any one of claims 1 to 3, wherein Oite the formula ^(I), R ^1, the number of carbon atoms of R 2, ^{R 3} and ^{R 4} are 4 to 15, respectively, the polyimide solution composition according to any one of claims 1-4. Said polyimide further includes other repeating unit other than the repeating unit represented by formula (I), polyimide solution composition according to any one of claims 1 to 5. The said other repeating unit is a repeating unit represented by following formula (II), The polyimide solution composition of Claim 6 characterized by the above-mentioned.

In formula (II), B represents a divalent aromatic hydrocarbon residue having a plurality of benzene rings. Hardened | cured material manufactured using the polyimide solution composition of any one of Claims 1-7.

Images