JP2809624B2 - Method for producing polyimide resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Objects of the Invention] (Industrial application field) The present invention relates to a method for producing a novel polyimide resin having good heat resistance and adhesiveness superior to conventional polyimide resins. (Prior Art) A polyimide resin is widely known as a resin having excellent heat resistance, electrical insulation, and mechanical properties. For this reason, in recent years, polyimide resins have been used in the field of the semiconductor industry, and demands for new performance improvements have been increasing. For example, when a polyimide resin is used as an alignment film of a liquid crystal display element, the polyimide film is required to have high light transmittance. In addition, when a polyimide resin is used as an interlayer insulating film of an IC or the like, it is required to have high adhesion to a substrate. However, when a conventional polyimide resin is produced by subjecting a polyamic acid, which is a precursor thereof, to a cyclization reaction by heat treatment, it is colored yellow-brown, and thus has a problem in that light transmittance is reduced. Also, when a conventional polyimide resin is adhered to the substrate, the adhesion to the substrate is poor,
There is a problem that moisture invades from between the substrate and the polyimide resin, and greatly reduces the reliability of the liquid crystal display element, IC, or LSI. (Problems to be Solved by the Invention) The present invention has been made in order to solve the above problems, and a method for easily producing a polyimide resin having low light transmittance and excellent adhesion to a substrate. The purpose is to provide. [Structure of the Invention] (Means and Actions for Solving the Invention) The method for producing a polyimide resin according to the present invention comprises a 2,2-
Bis (hydroxyaminophenyl) hexafluoropropane (I) and a diamino compound represented by the general formula H ₂ N—Z—NH ₂ . Is reacted in an organic solvent with a tetracarboxylic dianhydride represented by the general formula And m repeating units represented by And a polyamic acid having a 0.5 g / dl concentration N-methyl-2-pyrrolidone solution having an intrinsic viscosity of 0.15 dl / g or more at 30 ° C. (where Ar is Represents a tetravalent organic group selected from: _{CH 2 2, CH 2 3 CH} 2 4, CH 2 6, CH 2 7, CH 2 8, CH 2 9, CH 2
_{10, CH 2 3 O-CH} 2 -CH 2 -OCH 2 3, Represents a divalent organic group selected from: m and n are 0.01 ≦ m /
(Representing a number satisfying (m + n) ≦ 1.0), followed by a cyclization reaction. Hereinafter, the present invention will be described in more detail. The polyimide resin obtained by the present invention comprises 2,2-bis (hydroxyaminophenyl) hexafluoropropane (I) and, if necessary, a diamino compound represented by the general formula (II) and a diamino compound represented by the general formula (III) It is produced through a step of synthesizing a polyamic acid by a polycondensation reaction with tetracarboxylic dianhydride and a step of cyclizing the obtained polyamic acid. In the method of the present invention, examples of 2,2-bis (hydroxyaminophenyl) hexafluoropropane (I) include 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane and 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane, 2-
(3-hydroxy-4-aminophenyl) -2- (4-
(Hydroxy-3-aminophenyl) hexafluoropropane and the like. One or more of these compounds are used. In the present invention, examples of the diamino compound represented by the general formula (II) include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 4,4 '-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'
-Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane,
4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl Ketone, 2,2'-bis (p-aminophenyl) propane,
2'-bis (p-aminophenyl) hexafluoropropane, 1,3-bis (m-aminophenoxybenzene), 1,3
-Bis (p-aminophenoxybenzene), 1,4-bis (p-aminophenoxybenzene), 4-methyl-2,4
-Bis (p-aminophenyl) -1-pentene, 4-methyl-2,4-bis (p-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-p-aminobenzyl) Benzene, iminodi-p-phenylenediamine,
1,5-diaminonaphthalene, 2,6-diaminonaphthalene,
4-methyl-2,4-bis (p-aminophenylpentane), 5 (or 6) -amino-1- (p-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) Phosphine oxide, 4,4'-diaminoazobenzene, 4,4'-diaminodiphenylurea, 4,4'-
Bis (p-aminophenoxy) biphenyl, 2,2-bis [p- (p'-aminophenoxy) phenyl] propane, 2,2-bis [p- (m-aminophenoxy) phenyl] propane, 4,4 ' -Bis (p-aminophenoxy)
Benzophenone, 4,4'-bis (p-aminophenoxy) diphenylsulfone, 4,4'-bis [p- (α, α
-Dimethyl-p'-aminobenzyl) phenoxy] benzophenone, 4,4'-bis [p- (α, α-dimethyl-
[p'-aminobenzyl) phenoxy] diphenyl sulfone, bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethyldisiloxane, and bis (p-aminophenyl) tetramethyldisiloxane Can be mentioned. The hydrogen atom of the aromatic nucleus of these aromatic diamines is substituted with at least one substituent selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group and a phenyl group. It may be a compound. Examples of the diamino compound represented by the general formula (II) include, in addition to the above-mentioned aromatic diamines, dimethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, 1,2 -Bis (3'-aminopropoxy) ethane, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, 1,3
-Diaminocyclohexane, 4,4'-diaminodicyclohexylisopropane, 1,4-xylylenediamine, 2,6
-Diaminopyridine, 2,4-diamino-S-triazine, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyl Examples include disiloxane and bis (γ-aminopropyl) tetraphenyldisiloxane. The diamino compound represented by the general formula (II) may not necessarily be used, and if necessary, one or more compounds selected from the above groups may be used. In the method of the present invention, examples of the tetracarboxylic dianhydride represented by the general formula (III) include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, , 3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3 ', 4'-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride Object, screw (3,
4-dicarboxyphenyl) tetramethyldisiloxane dianhydride, 1-4-5-8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, butanetetracarboxylic acid And dianhydrides. Note that these compounds are compounds in which a hydrogen atom is substituted with at least one substituent selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group. You may. As the compound represented by the general formula (III), one or more compounds selected from the above groups are used. The polyamic acid which is a precursor of the polyimide resin obtained by the present invention comprises 2,2-bis (hydroxyaminophenyl) hexafluoropropane (I) and, if necessary, a diamino compound (II), and tetracarboxylic dianhydride ( II
It can be synthesized by subjecting I) to a polycondensation reaction in an organic solvent. At this time, as the organic solvent used, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, γ-butyrolactone, sulfolane, N, N, N ', N'-tetramethylurea, hexamethylphosphamide and the like can be mentioned. In this reaction, 2,2-bis (hydroxyaminophenyl) hexafluoropropane (I) and a diamino compound (I
The ratio with (I) is determined according to the ratio of the repeating unit in the target polyimide resin. The total amount of 2,2-bis (hydroxyaminophenyl) hexafluoropropane (I) and diamino compound (II) and the ratio of tetracarboxylic dianhydride (III) were 0.9 to 1.1: 1 in molar ratio. And the ratio of The reaction conditions are as follows: reaction temperature -20 to 150 ° C, reaction time 1
It ranges from 0 minutes to 20 hours. Under the above conditions, a polyamic acid having m repeating units represented by the general formula (IV) and n repeating units represented by the general formula (V) is produced. The generated polyamic acid may be used as a solution in the next step. Alternatively, the resulting polyamic acid solution may be poured into a poor solvent such as water, methanol, ethanol, acetone, or methyl ethyl ketone to precipitate a polymer, which may be washed and dried to recover a solid, which may be used in the next step. In the method of the present invention, the molecular weight of the polyamic acid to be synthesized is not particularly limited, but it is preferable that the molecular weight is such that a film capable of maintaining sufficient physical strength when applied to a substrate can be formed. From this viewpoint, the intrinsic viscosity of the 0.5 g / dl polyamic acid / N-methyl-2-pyrrolidone solution at 30 ° C. is desirably 0.15 dl / g or more. Further, by cyclizing the polyamic acid synthesized as described above, the polyimide resin of the first invention of the present application can be produced. This cyclization is performed by heat treatment or chemical treatment. In the method by heat treatment,
By coating the polyamic acid solution on a suitable substrate such as glass and stainless steel, and heating the polyamic acid film or film obtained by removing the solvent to 100 to 400 ° C.,
A cyclization reaction is caused to produce a polyimide resin. Also,
In the method by the chemical treatment, the polyamic acid solution is subjected to -20 in the presence of acetic anhydride, triethylamine, pyridine, sodium acetate, zinc acetate, manganese acetate, cobalt acetate or the like.
A cyclization reaction is caused by reacting in a temperature range of ~ 150 ° C for 1 minute to 10 hours to produce a polyimide resin. Such a polyimide resin has 2,2
Since a hydroxyl group and a fluorine atom derived from 2-bis (hydroxyaminophenyl) hexafluoropropane are introduced, adhesion to a substrate can be improved. In addition, 2,2-bis (hydroxyaminophenyl) hexafluoropropane has a lower degree of coloring than other aromatic diamines and a lower degree of coloring even in a solution state. Excellent light transmittance. Further, it is considered that the presence of the fluorine atom also improves the light transmittance of the polyimide resin. Note that the relationship between the total numbers m and n of the respective repeating units is 0.01 ≦
The reason why m / (m + n) ≦ 1.0 is that when this value is less than 0.01, the hydroxyl groups and fluorine atoms introduced into the polymer skeleton are small, so that the adhesion to the substrate cannot be improved. A more preferable range of the value of m / (m + n) is 0.1 to 0.9. This is because if the value is less than 0.1, the adhesion to the substrate tends to decrease, while if it exceeds 0.9, the heat resistance of the obtained polyimide resin tends to decrease. (Example) Hereinafter, an example of the present invention will be described. Example 1 In a reaction flask equipped with a stir bar, a thermometer, and a dropping funnel, 14.71 parts by weight of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 50 parts by weight of N, N-dimethylacetamide were placed. It was charged, sufficiently stirred, and cooled to 0 ° C. The suspension was kept at 0 ° C. and 4.67 parts by weight of p-phenylenediamine, 0.75 parts by weight of bis (γ-aminopropyl) tetramethyldisiloxane and 2,2-bis (4-hydroxy-3-
Aminophenyl) hexafluoropropane 1.13 parts by weight with N,
A solution dissolved in 70 parts by weight of N-dimethylacetamide,
The solution was gradually dropped from the dropping funnel. 0-10 ° C after dropping
For 6 hours to synthesize a polyamic acid. A part of this reaction solution was dropped into a poor solvent to precipitate a polyamic acid, and washed and dried to recover the polyamic acid as a solid.The polyamic acid / N-methyl-2-pyrrolidone solution having a concentration of 0.5 g / dl was obtained. Was measured at 30 ° C. to find that the intrinsic viscosity was 1.09 dl / g. Next, the reaction solution was uniformly coated on a glass substrate at a rotation speed of 2000 rpm using a spinner,
After drying for a minute to remove the solvent, it was peeled off from the substrate. This film was heated at 250 ° C. for 1.5 hours to cause a cyclization reaction,
A 1.4 μm-thick polyimide film was obtained. The elemental analysis values of this polyimide almost agreed with the calculated values as shown in Table 1. FIG. 1 shows the infrared absorption spectrum of this polyimide. As is clear from FIG. ^1, there is strong characteristic absorption of the imide group at 1780 cm ⁻¹ , indicating that the obtained polymer is a polyimide resin. Next, in the same manner as above, a solution of polyamic acid is uniformly applied on a glass substrate to a thickness of 1 μm, and then heat-treated to form a polyimide film, and adhered according to the method specified in JIS K-5400, 6.14. An acidity test (cross-cut peeling) was performed.
As a result, 50 grids were formed, but did not peel at all. Further, the light transmittance of a polyimide film having a thickness of 1 μm formed in the same manner as described above at a wavelength of 450 nm was measured and found to be 85%. Example 2 In a reaction flask equipped with a stirring rod, a thermometer, and a dropping funnel, 8.727 parts by weight of pyromellitic dianhydride, 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride 12.885
Parts by weight and 70 parts by weight of N, N-dimethylacetamide were charged, sufficiently stirred, and cooled to 10 ° C. Add this suspension to 10
C. and 29.301 parts by weight of 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane was added to N, N-
A solution dissolved in 70 parts by weight of dimethylacetamide was gradually dropped from a dropping funnel. After completion of the dropwise addition, stirring was continued at 15 ° C. for 7 hours to synthesize a polyamic acid. The intrinsic viscosity of the polyamic acid measured in the same manner as in Example 1 was 0.88 dl / g. Next, the above reaction solution was uniformly applied on a glass substrate at a rotation speed of 2000 rpm using a spinner,
For 30 minutes at 150 ° C to remove the solvent, and then at 300 ° C
For 2 hours to cause a cyclization reaction, and a film thickness of 1.7 μm
Was obtained. When the adhesion of this polyimide film to a glass substrate was examined in the same manner as in Example 1, no fifty grids were peeled off. Example 3 In a reaction flask equipped with a stirring rod, a thermometer, and a dropping funnel, 17.450 parts by weight of pyromellitic dianhydride and 90 parts by weight of N-methyl-2-pyrrolidone were charged, and sufficiently stirred to 10 ° C. Cool. Keep the suspension at 10 ° C,
14.949 parts by weight of bis- (4-hydroxy-3-aminophenyl) hexafluoropropane and 11.692 parts by weight of 1,4-bis (p-aminophenoxy) benzene were added to N-methyl-2.
-A solution dissolved in 90 parts by weight of pyrrolidone was gradually dropped from a dropping funnel. After completion of the dropwise addition, stirring was continued at 15 ° C. for 7 hours to synthesize a polyamic acid. The intrinsic viscosity of the polyamic acid measured in the same manner as in Example 1 was 0.98 dl / g. Next, the adhesion of the polyimide film obtained from the polyamic acid to the glass substrate was examined in exactly the same manner as in Example 2. As a result, 50 grids did not peel off at all. Example 4 In a reaction flask equipped with a stir bar, a thermometer, and a dropping funnel, 11.739 parts by weight of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 8.731 parts by weight of pyromellitic dianhydride and N, N-dimethylacetamide 100 parts by weight,
Stir well and cool to 10 ° C. The suspension was kept at 10 ° C., and 7.328 parts by weight of 2,2-bis (4-hydroxy-3-aminophenyl) hexafluoropropane and 20.06 parts by weight of 2,2-bis (p-aminophenyl) hexafluoropropane Was dissolved in 100 parts by weight of N, N-dimethylacetamide, and the solution was gradually dropped from a dropping funnel. After dropping,
Stirring was continued at 15 ° C. for 7 hours to synthesize a polyamic acid. The intrinsic viscosity of this polyamic acid measured in the same manner as in Example 1 was 1.13 dl / g. Next, the adhesion of the polyimide film obtained from the polyamic acid to the glass substrate was examined in exactly the same manner as in Example 2. As a result, 50 grids did not peel off at all. Comparative Example In a reaction flask equipped with a stirring rod, a thermometer, and a dropping funnel, 8.728 parts by weight of pyromellitic dianhydride, 3,3 ′, 4,
4'-benzophenonetetracarboxylic dianhydride 12.884
Parts by weight and 80 parts by weight of N, N-dimethylacetamide were charged, sufficiently stirred, and cooled to 10 ° C. Add this suspension to 10
° C, 4,4'-diaminodiphenyl ether 16.01
A solution in which 6 parts by weight of N, N-dimethylacetamide was dissolved in 70 parts by weight was gradually dropped from a dropping funnel. After completion of the dropwise addition, stirring was continued at 15 ° C. for 7 hours to synthesize a polyamic acid. The intrinsic viscosity of this polyamic acid measured in the same manner as in Example 1 was 1.73 dl / g. Next, the adhesion of the polyimide film obtained from the polyamic acid to the glass substrate was examined in exactly the same manner as in Example 2, and 50 grids were completely peeled off. The light transmittance of a 1 μm-thick polyimide film measured at a wavelength of 450 nm was 53%. As described above, the conventional polyimide film not using 2,2-bis (hydroxyaminophenyl) hexafluoropropane as a raw material is inferior in both adhesion to a substrate and light transmittance. [Effects of the Invention] As described in detail above, according to the present invention, it is possible to provide a method for easily producing a polyimide resin having excellent adhesion to a substrate and excellent transparency.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing an infrared absorption spectrum of a polyimide resin in Example 1 of the present invention.

Claims (1)

(57) [Claims] 1. 2,2-bis (hydroxyaminophenyl) hexafluoropropane (I) and a diamino compound represented by the general formula H ₂ N—Z—NH ₂ ... (II); formula Is reacted in an organic solvent with a tetracarboxylic dianhydride represented by the general formula And m repeating units represented by And a polyamic acid having a 0.5 g / dl concentration N-methyl-2-pyrrolidone solution having an intrinsic viscosity of 0.15 dl / g or more at 30 ° C. (where Ar is Represents a tetravalent organic group selected from: _{CH 2 2, CH 2 3 CH} 2 4, CH 2 6, CH 2 7, CH 2 8, CH 2 9, CH 2
_{10, CH 2 3 O-CH} 2 -CH 2 -OCH 2 3, Represents a divalent organic group selected from: m and n are 0.01 ≦ m /
(Representing a number that satisfies (m + n) ≦ 1.0), followed by a cyclization reaction. 2. The method for producing a polyimide resin according to claim 1, wherein the cyclization reaction is performed by heat treatment or chemical treatment.