JP2014118463A - Polyimide resin molded body and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide resin useful in applications such as a flexible device.SOLUTION: The problem is resolved by providing a polyimide resin molded body obtained by molding a polyimide resin, being colorless and transparent, and having the generation amount of volatile gas having the boiling point of 150°C or more generated when heated from 30°C to 340°C under nitrogen atmosphere of 0.5% or less based on the polyimide resin mass.

Description

  The present invention relates to a polyimide resin molded body used for a flexible device and the like, which is colorless and transparent and relates to a molded body with less volatile gas.

  At present, glass substrates are mainly used in the field of electronic devices such as flat panel displays and electronic paper. However, glass substrates are heavy and easily broken, so they are not necessarily ideal substrates. Therefore, studies have been actively conducted to realize a flexible device in which the substrate is replaced with glass from a polymer material. However, since many of these technologies require new production technologies and equipment, they have not been mass-produced.

In recent years, a polyimide resin has been proposed as a resin substrate for a flexible device, and it has been studied to form a thin film transistor (hereinafter referred to as TFT), a transparent electrode, a light emitting layer, etc. on a polyimide resin surface and use it as a flexible device member. . Polyimide resin moldings used in these are required to have sufficient transparency for flexible device applications and heat resistance that can withstand high-temperature processes during production.
On the other hand, flexible devices are required to have a small amount of volatile gas because they affect TFTs, transparent electrodes, light emitting layers, and the like formed on the substrate surface.

  As a method for obtaining a polyimide resin molded body, a method of forming a polyamic acid solution as shown in Patent Document 1 by a solution casting method such as a solution casting method, a thermoplastic polyimide resin as shown in Patent Document 2 A method of molding without solvent is disclosed.

JP-A-8-104750 Japanese Patent Laid-Open No. 4-331231

However, according to the study by the inventors of the present application, the method described in Patent Document 1 uses a high boiling point solvent at the time of production, so that it takes time to dry the solvent, and there is a problem in production cost. Moreover, in patent document 1, although it is not examined at all about the generation amount of the volatile gas from the obtained resin molding, according to examination of the present inventors, it manufactures by the casting method like patent document 1. It was found that the resulting polyimide resin molded body has a large amount of solvent remaining in the resin molded body, a large amount of volatile gas, and insufficient performance as a flexible device.
On the other hand, the thermoplastic polyimide resin of Patent Document 2 is colored brown, and when it is molded at a very high molding temperature, the coloration progresses. Therefore, as a flexible device application requiring colorless transparency, its performance is It was insufficient. Moreover, in patent document 2, it is not examined at all about the generation amount of the volatile gas from the obtained resin molding.
An object of the present invention is to provide a polyimide resin molded body having little influence on TFTs, transparent electrodes, light emitting layers and the like formed on a polyimide molded body such as a substrate of a flexible device.

In view of the above circumstances, the present inventors have intensively studied polyimide resins useful for applications such as flexible devices. As a result, the molded body using the polyimide resin is colorless and transparent,
And it discovered that the objective of this invention was achieved because the generation amount of specific volatile gas was 0.5% or less with respect to this polyimide resin mass, and completed this invention.

The present invention relates to the following items.
[1] A molded body obtained by molding a polyimide resin, the molded body being colorless and transparent,
In addition, the amount of volatile gas generated when heated from 30 ° C. to 340 ° C. in a nitrogen atmosphere is not more than 0.5% with respect to the mass of the polyimide resin. Polyimide resin molding.
[2] The polyimide resin molded body according to [1], wherein the total light transmittance at 400 nm at a thickness of 50 μm is 60% or more.
[3] The polyimide resin molded body according to [1] or [2], wherein the polyimide resin molded body is obtained by thermoplastic molding of the polyimide resin.
[4] The polyimide according to any one of [1] to [3], wherein a solvent content of the polyimide resin is 0.1% by mass to 12% by mass in the polyimide resin. Resin molded body.
[5] A film comprising the polyimide resin molded body according to any one of [1] to [4].

  It is possible to provide a polyimide resin molded body useful for applications such as a flexible device that does not cause deterioration in initial performance or temporal performance of a laminated device using the polyimide resin molded body.

  Hereinafter, embodiments of the present invention will be described in detail. What is described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to the following embodiment unless it exceeds the gist.

<1. Polyimide resin molding>
The polyimide resin molded body of the present invention is a molded body obtained by molding a polyimide resin, the molded body is colorless and transparent, and is generated when heated from 30 ° C. to 340 ° C. in a nitrogen atmosphere. A polyimide resin molded body characterized in that the amount of volatile gas having a boiling point of 150 ° C. or more is 0.5% or less with respect to the mass of the polyimide resin.

The polyimide resin molded body of the present invention includes a three-dimensional molded body such as a sheet having a thickness of 1 mm or more, a lens, and a light cover that cannot be molded by a general casting method.
Therefore, the polyimide resin molding obtained by the present invention is excellent in transparency and mechanical properties that cannot be achieved by the polyimide resin molding obtained by the existing casting method, and has a three-dimensionally complicated shape. In addition, when a film is produced by a general solution casting method, the arrangement of polymer chains and functional groups on the surface of the film differs depending on the presence or absence of contact with the support on the front and back of the film. Contact angle, adhesiveness, surface smoothness, etc.) may be different. However, since the polyimide resin molded body of the present invention has no or no time for contact with the support in the heated state during molding, it has a characteristic that a difference in performance hardly occurs between the front and back of the film. preferable.

The polyimide resin molding of the present invention is colorless and transparent. In this specification, being colorless and transparent means that the total light transmittance at 400 nm is 60% or more when the thickness of the polyimide resin molded body is 50 μm. The measuring method of the total light transmittance is based on JIS K7361-1.
The total light transmittance at 400 nm is preferably 70% or more, more preferably 80% or more. By being colorless and transparent, it can be suitably used in a device requiring translucency, such as a photoelectric conversion element.

  The yellowness [yellow index (YI)] of the polyimide resin molding according to the present invention when the film thickness is 50 ± 5 μm is usually −10 or more, preferably −5 or more, more preferably − 1 or more. On the other hand, it is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less. When the yellowness is in such a range, there is a tendency that light emission and light absorption are not hindered in an electronic device using the polyimide resin molding obtained in the present invention.

The polyimide resin molding of the present invention has a generation amount of a volatile gas having a boiling point of 150 ° C. or higher generated when heated from 30 ° C. to 340 ° C. in a nitrogen atmosphere, and 0.5% or less of the polyimide resin mass. It is.
Volatile gas generated from the polyimide resin molding is a solvent used in the production of the polyimide resin or precursor polyamic acid resin (such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone). Amide solvents; aprotic polar solvents such as dimethyl sulfoxide; lactone solvents such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, etc.), a solvent used for taking water out of the system during polyimide resin production ( Xylene, toluene, etc.), imidization catalyst used in polyimide resin production, or dehydrating agents (triethylamine, pyridine, acetic anhydride, acetic acid, dicyclohexylcarbodiimide, diisopropylcarbodiimide, diazabicyclooctane, etc.), when polyimide resin is powdered for That solvent (isopropyl alcohol, methanol, ethanol, etc.), low molecular weight material produced by the reaction or unreacted monomer, water and the like. When a polyimide resin molding is used for a flexible device substrate, etc., the volatile gas generated from the molding causes deterioration of the initial performance of the laminated device, degradation of performance over time, malfunction, etc. Lower layers are the cause of white turbidity, discoloration, deformation (shrinkage, expansion, waviness, foaming, etc.) and instability of adhesion, as well as corrosion of various electrical wiring / electrodes and contamination of device manufacturing equipment. preferable. In the volatile gas generated from the molded body, for example, water having a boiling point of 100 ° C. may affect the adhesive strength of each layer and the cloudiness of the layer. However, among the volatile gases generated from the molded product, it has been found that the initial performance of the laminated device and the performance over time are particularly deteriorated when the volatile gas having a boiling point of 150 ° C. or more is a specific amount or more. did. The reason why a volatile gas with a boiling point of 150 ° C or higher causes deterioration of the initial performance of the multilayer device or deterioration of the performance over time is not clear, but local alteration or penetration between layers of the multilayer device may occur. This is thought to be due to the occurrence of peeling.

When the polyimide resin molding of the present invention is heated from 30 ° C. to 340 ° C. in a nitrogen atmosphere, the amount of volatile gas having a boiling point of 150 ° C. or more is 0.5% or less with respect to the polyimide resin mass. It is preferably 0.3% or less, and preferably 0.1% or less. Moreover, there is no lower limit in particular, and the lower one is preferable, but when it is 0.0001% or more, the plasticity of the polyimide resin molded body may be improved.
Examples of the volatile gas having a boiling point of 150 ° C. or higher include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; aprotic polar solvents such as dimethyl sulfoxide; Examples include lactone solvents such as butyrolactone, γ-valerolactone, and δ-valerolactone. Among these, it is preferable to reduce the amount of N, N-dimethylacetamide generated, since the deterioration of the initial performance of the laminated device and the deterioration of performance over time can be suppressed.
The method for measuring the amount of volatile gas generated from the polyimide resin molded body of the present invention is not particularly limited as long as it is a commonly used method, and differential thermothermal weight simultaneous measurement (TG / DTA), gas chromatography , Liquid chromatography, differential thermobalance-mass spectrometer (TG-DTA / MS), infrared spectroscopy (IR), elemental analysis, nuclear magnetic resonance (NMR), mass spectrometry, or a combination of these Can be mentioned.

  Although there is no special restriction | limiting in the density | concentration of the residual solvent in the polyimide resin molding of this invention, Preferably it is 12 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 1 It is not more than mass%, more preferably not more than 0.5 mass%, particularly preferably not more than 0.1 mass%. On the other hand, the lower limit is not limited and is preferably low. By adjusting the concentration of the solvent in the polyimide resin molded body within this range, the generation amount of volatile gas having a boiling point of 150 ° C. or higher when heated from 30 ° C. to 340 ° C. in a nitrogen atmosphere is reduced. When the polyimide resin molding of the present invention is used for a substrate, it is preferable because adverse effects due to a solvent that volatilizes in subsequent manufacturing processes of electronic devices and the like can be suppressed.

  The glass transition temperature (Tg) of the polyimide resin molding according to the present invention by differential scanning calorimetry (DSC method) is preferably 170 ° C. or higher, more preferably 200 ° C. or higher, more preferably 250 ° C. or higher. . It is preferable for the glass transition temperature to be in a specific range because it can be used for the subsequent high-temperature processes for manufacturing various electronic devices.

  The thermal expansion coefficient of the polyimide resin molding of the present invention is usually 70 ppm / K or less, preferably 50 ppm / K or less, more preferably 30 ppm or less, and particularly preferably 20 ppm or less in the range of 100 to 200 ° C. When the thermal expansion coefficient is in such a range, when the polyimide resin molding of the present invention is used for a substrate, there is a tendency that positional deviation, warpage, and the like can be suppressed in subsequent manufacturing processes of electronic devices and the like.

Although the ratio with respect to the polyimide resin of the polyamic acid resin or polyamic acid ester resin which is the unreacted substance contained in the polyimide resin molding which concerns on this invention is not restrict | limited, Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less. Especially preferably, it is 5 mass% or less. Moreover, there is no lower limit and the lower one is preferable.
When 30% or more of the polyamic acid resin or polyamic acid ester resin is contained in the polyimide resin, water is generated from the polyamic acid resin or polyamic acid ester resin during the manufacturing process of the electronic device using the polyimide resin molding. The progress of the process may be hindered, and the mechanical properties and transparency of the polyimide resin molded body may be changed.

The glass transition temperature (Tg) of the polyimide resin molding by differential scanning calorimetry (DSC method) is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher. When the glass transition temperature is 150 ° C. or higher, it tends to be compatible with various high-temperature processes using a polyimide resin molded body.
The thermal expansion coefficient of the polyimide resin molded body is preferably 100 ppm / K or less, more preferably 70 ppm / K or less in the range of 100 to 200 ° C. When the thermal expansion coefficient is in such a range, it tends to be compatible with a manufacturing process that requires dimensional accuracy.

The mechanical strength (tensile strength, tensile elongation, etc.) of the polyimide resin molded body obtained in the present invention depends on the molding method for melt molding and the shape of the molded body, but has the following mechanical strength. Is preferred.
The tensile strength of the polyimide resin according to the present invention is not particularly limited, but is usually 50 MPa or more, preferably 70 MPa or more, while usually 400 MPa or less, preferably 300 MPa.
a or less.
Although there is no special restriction | limiting, the tensile elasticity modulus of the polyimide resin molding which concerns on this invention is 1000 MPa or more normally, Preferably it is 1500 MPa, On the other hand, it is 20 Gpa or less normally, Preferably it is 10 Gpa or less.

  The tensile elongation of the polyimide resin molding according to the present invention is not particularly limited, but is preferably 10% GL or more, more preferably 20% GL or more, while preferably 300% GL or less, more preferably 200% GL or less. When the polyimide resin molding has such a mechanical strength, a more durable electronic device or the like tends to be obtained.

The melt viscosity of the polyimide resin molding according to the present invention is not particularly limited, but is usually 1.0 × 10 ¹ Pa · s or more, preferably 1.0 × 10 ² Pa · s or more at 330 ° C. . On the other hand, it is usually 1.0 × 10 ⁷ Pa · s or less, preferably 1.0 × 10 ⁵ Pa · s or less, more preferably 1.0 × 10 ⁴ Pa · s or less, and further preferably 5.0 × 10 ^3.
Pa · s or less, particularly preferably 3.0 × 10 ³ Pa · s or less. By being in such a range, it is preferable because secondary processing of the polyimide resin molded body is easy.
The melt viscosity of the polyimide resin obtained in the present invention can be measured by a known method, for example, the method described in JP-A-1-297427.

  The polyimide resin molding according to the present invention may contain an antioxidant in order to suppress coloring during molding, drying, and various processes using the polyimide resin molding.

  The antioxidant may be added at any stage of the polyimide resin manufacturing process and the polyimide resin molded body manufacturing process. In the process of manufacturing the polyimide resin molded body, the antioxidant is mixed with the polyimide resin powder. The method can be suitably used. When mixing antioxidant with polyimide resin powder, it is preferable at the point which can suppress both discoloration in shaping | molding of polyimide powder and coloring with time of the obtained polyimide resin molding.

The addition amount of the antioxidant is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more based on the polyimide resin. On the other hand, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less. By being in these ranges, coloring due to deterioration of the antioxidant is suppressed, aggregation and sedimentation in the liquid resin composition is suppressed, and handling properties during coating work are excellent. There exists a tendency for it to become a molding with good smoothness and color.

  Specific examples of the antioxidant include hindered phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hydroxylamine-based antioxidants.

Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide], 1,2-bis (3,5-di-tert-butyl-4-hydroxycinnamoyl) hydrazine, triethylene glycol-bis [ 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, thiodiethylenebis [3- (3,5- J-t-Buchi 4-hydroxyphenyl) propionate], 2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4 -Hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5- Di-t-butyl-4-hydroxybenzyl) -isocyanurate, 2,4, -bis [(octylthio) methyl] -o-cresol, isooctyl-3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- ( 2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2,2′-methylenebis (6-t-butyl-4-methylphenol), 4 , 4′-butylidenebis (6-t-butyl-3-methylphenol), 4,4′-thiobis (6-t-butyl-3-methylphenol), 3,9-bis [2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5- Tris [[3,5- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,1,3-tris (2 -Methyl-4-hydroxy-5-tert-butylphenyl) butane, stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [3- (3-tert-butyl-4 -Hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)], 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl-benzenepropanoic acid-2,4,8,10 -Tetraoxaspiro [5,5] undecane-3,9-diylbis (2,2-dimethyl-2,1-ethanediyl) ester, 2,4,6-tris (3 ', 5'-di-tert-butyl -4'-hydroxybenzyl) mesitylene and the like.

Among the above hindered phenolic compounds, hindered phenolic antioxidants that are highly compatible with polyimide resins are prevented from coagulating in the polyimide resin molding and bleeding out to the surface, and transparency and surface smoothness Is preferable in that a good molded product can be obtained. In particular, N, N′-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide] (trade name IRGANOX1098 manufactured by BASF), pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX 1010 manufactured by BASF), 1,2-bis (3,5-di-tert-butyl-4-hydroxycinnamoyl) hydrazine (BASF) Product name IRGANOX MD1024), bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)] (BASF product name IRGANOX 245) is a polyimide resin It is preferable in that the compatibility with the composition is excellent and coloring can be effectively suppressed.

The phosphorus-based antioxidant may be an inorganic compound or an organic compound, and is not particularly limited. Preferred phosphorus compounds include inorganic phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, and triphenyl phosphite. , Trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl- 4,4′-isopropylidene diphenyl diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (Isodecyl) Phosphi , Tris (tridecyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, phosphonic acid [ 1,1-diphenyl-4,4′-diylbistetrakis-2,4-bis (1,1-dimethylethyl) phenyl] ester, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4′- Isopropylidene diphenol alkyl phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite Sulphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, hexa ( Tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester, Sodium-bis (4-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, 1,3-bis (diphenoxyphosphoryl) Oxy) benzene, 3,9-bis (2,4-di-tert-butylphenoxy) ) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6-[(2-ethylhexyl) oxy] -12H-dibenzo [1,3,2] dioxaphosphocin, tris (2,4-di-tert-butylphenyl) phosphite, tris (mono and / or dinonylphenyl) phosphite, tris phosphite Organic phosphorus secondary such as (4-nonylphenyl), phosphorous acid (1-methylethylidene) di-4,1-phenylenetetra-c12-15-alkyl ester, diphenyl phosphite (2-ethylhexyl), etc. An antioxidant is mentioned.

Among the above-mentioned phosphorus-based antioxidants, phosphorus-based antioxidants with excellent compatibility with polyimide resins suppress aggregation and bleed-out to the surface of the polyimide resin molded body, and have excellent transparency and surface smoothness. It is preferable at the point from which a molded object is obtained. In particular, tris (2,4-di-t-butylphenyl) phosphite (trade name IRGAFOS 168 manufactured by BASF) has excellent compatibility with polyimide resin compositions, liquid polyimide resin compositions, and liquid polyamic acid resin compositions. It is preferable at the point which can suppress coloring effectively.

Examples of the sulfur-based antioxidant include dioctadecyl 3,3′-thiodipropionate 3,3′-thiodipropionate didodecyl, dilauryl-3,3′-thiodipropionate,
Laudylyl thiodithionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, tetrakis-methylene-3-lauryl Thiopropionate methane, distearyl-3,3′-methyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, bis [2-methyl-4- (3- n-alkylthiopropionyloxy) -5-t-butylphenyl] sulfide, β-laurylthiopropionate, 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl, bis [3- (dode Thio) propanoic acid] thiobis [2- (1,1-dimethylethyl) -5-methyl-4,1-phenylene], and the like.
Among the above-mentioned sulfur-based antioxidants, sulfur-based antioxidants with excellent compatibility with polyimide resins suppress aggregation and bleed-out to the surface of the polyimide resin molding, and have good transparency and surface smoothness. It is preferable at the point from which a molded object is obtained.

Examples of the hydroxylamine-based antioxidant include dialkylamines such as dioctadecylhydroxylamine, N, O-dialkylhydroxylamine, 1-naphthohydroxamic acid, 4,5-dibromo-N-methoxy-N-methyl-2 -Francarboxamide, 4- (hydroxyamino) quinoline N-oxide, acetohydroxamic acid, benzenesulfohydroxamic acid, benzohydroxamic acid, hydroxyurea, L-canavanine sulfate hydrate, N, N'-dimethoxy-N, N ' -Dimethyloxamide, N, N, O-triacetylhydroxylamine, N, N, O-tris (trimethylsilyl) hydroxylamine, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, O- Bis (trifluoroacetyl) Hydroxylamine, N, O-bis (trimethylsilyl) hydroxylamine, N, O-dimethylhydroxylamine hydrochloride, N- (diethylcarbamoyl) -N-methoxyformamide, N- (tert-butyl) hydroxylamine hydrochloride, N- Benzoyl-N-phenylhydroxylamine, N-carbobenzoxyhydroxylamine, N-cinnamoyl-N- (2,3-xylyl) hydroxylamine, N-hydroxyurethane, N-methoxy-N, O-bis (trimethylsilyl) carbamate N-methoxy-N-methyl-2-furancarboxamide, N-methoxy-N-methylacetamide, N-methoxydiacetamide, N-methyl-2-dimethylaminoacetohydroxamic acid, N-methyl-N, O-bis (Trimethylsilyl Vidroxylamine, N-methyl furohydroxamic acid, N-methylhydroxylamine hydrochloride, octanohydroxamic acid, salicylhydroxamic acid, sodium benzohydroxamic acid hydrate, sodium octanohydroxamic acid hydrate, N- (benzyloxy ) Tert-butyl carbamate, tert-butyl N-hydroxycarbamate, tert-butyl [bis (4-methoxyphenyl) phosphinyloxy] carbamate, 4,5-dibromo-N-methoxy-N-methyl-2 -Furancarboxamide, carboxymethoxylamine hemihydrochloride, hydroxylamine-O-sulfonic acid, L-canavanine sulfate hydrate, N, N'-dimethoxy-N, N'-dimethyloxamide, N, N, O-tri Acetylhydroxylamine, N, N, O Tris (trimethylsilyl) hydroxylamine, N, O-bis (trifluoroacetyl) hydroxylamine, N, O-bis (trimethylsilyl) hydroxylamine, N, O-dimethylhydroxylamine hydrochloride, N- (diethylcarbamoyl) -N- Methoxyformamide, N-methoxy-N, O-bis (trimethylsilyl) carbamate, N-methoxy-N-methyl-2-furancarboxamide, N-methoxy-N-methylacetamide, N-methoxydiacetamide, N-methyl-N , O-bis (trimethylsilyl) bidoxylamine, O- (2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride, O- (2-trimethylsilylethyl) hydroxylamine hydrochloride, O- (trimethylsilyl) ) Hydroxy Amine, O-4-nitrobenzylhydroxylamine hydrochloride, O-allylhydroxylamine hydrochloride, O-benzylhydroxylamine hydrochloride, O-isobutylhydroxylamine hydrochloride, O-methylhydroxylamine hydrochloride, N- (benzyloxy) ) Tert-butyl carbamate, [bis (4-methoxyphenyl) phosphinyloxy] carbamate tert-butyl and the like.
Among the hydroxylamine-based antioxidants, the hydroxylamine-based antioxidant, which has excellent compatibility with polyimide resins, suppresses aggregation and bleed-out to the surface of the polyimide resin molded body, resulting in transparency and surface smoothness. This is preferable in that a good molded body can be obtained.

The above antioxidants may be used alone or in combination of two or more, but when they are mixed, a mixture of hindered phenolic antioxidants and phosphorus antioxidants or hindered phenolic antioxidants A mixture of an agent and a sulfur-based antioxidant is preferred. N, N'-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide], especially when using a mixture of hindered phenolic antioxidants and phosphorus antioxidants (BASF
Product name IRGANOX 1098) and tris (2,4-di-t-butylphenyl) phosphite (BASF product name IRGAFOS 168), pentaerythritol tetrakis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX 1010 manufactured by BASF) and tris (2,4-di-t-butylphenyl) phosphite (trade name IRGAFOS 168 manufactured by BASF), 1,2 -Bis (3,5-di-tert-butyl-4-hydroxycinnamoyl) hydrazine (trade name IRGANOX MD1024, manufactured by BASF) and tris (2,4-di-tert-butylphenyl) phosphite (product, manufactured by BASF) Name IRGAFOS 168), bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)] (trade name IRGANOX 245, manufactured by BASF AG) and Tris (
2,4-di-tert-butylphenyl) phosphite (trade name IRGAFOS 168, manufactured by BASF)
And a mixture thereof with a polyimide resin are preferable, and coloring can be effectively suppressed. N, N'-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide], especially when using a mixture of hindered phenolic and sulfur antioxidants (Trade name IRGANOX 1098 manufactured by BASF) and dioctadecyl 3,3′-thiodipropionate (trade name IRGANOX PS 802 manufactured by BASF), pentaerythritol tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX 1010 manufactured by BASF) and dioctadecyl 3,3′-thiodipropionate (B
Mixture with ASF brand name IRGANOX PS 802), 1,2-bis (3,5-di-tert-butyl-4-hydroxycinnamoyl) hydrazine (BASF brand name IRGANOX MD1024) and 3,3 ' -Both [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene), a mixture with dioctadecyl thiodipropionate (trade name IRGANOX PS 802, manufactured by BASF) )] (BASF brand name IRGANOX 245) and 3,3'-dioctadecyl thiodipropionate (BASF brand name IRGANOX PS 802) are excellent in compatibility with polyimide resin and effective in coloring. It is preferable at the point which can be suppressed to. Moreover, the mixing ratio at the time of mixing is not specifically limited.
Further, in addition to the above antioxidants, various additives usually used in resin compositions, for example, lubricants, colorants, stabilizers, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers or mold release, as desired. You may mix | blend an agent etc. with the polyimide resin molding which concerns on this embodiment. These various fillers and additive components may be added at any stage of any process for producing a polyimide resin molded body.

<2. Polyimide resin used for polyimide resin molding of the present invention>
The polyimide resin used for the polyimide resin molding of the present invention has a structure represented by the following general formula (1).

[In the general formula (1), R ¹ represents a tetravalent organic group,
R ² represents a divalent organic group,
n represents an integer of 1 or more, and when n is 2 or more, a plurality of R ¹ and R ² present in one molecule of the structure represented by the general formula (1) may be the same or different. . ]

  n is an integer of 1 or more, and the upper limit is not particularly limited as long as the effect of the present invention is not impaired, but the weight average molecular weight of the polyimide resin represented by the general formula (1) is preferably 40000 or more, and more preferably. It is preferable from the viewpoint of toughness of the obtained polyimide resin molding that n be set to 50000 or more.

In addition, since the polyimide resin of the present invention includes a plurality of structures represented by the general formula (1), a plurality of tetravalent organic groups R ¹ and a plurality of divalent organic groups R ² are included. Here, each of the plurality of tetravalent organic groups R ¹ and the plurality of divalent organic groups R ² may have the same structure or different structures.

<For ^{R 1>}
R ¹ represents a tetravalent organic group and is not particularly limited as long as it does not impair the effects of the present invention. Specific examples of R ¹ include tetracarboxylic dianhydrides. Examples of tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides, fluorine-containing aromatic tetracarboxylic dianhydrides, and aliphatic tetracarboxylic dianhydrides.
More specifically, the following are mentioned.

(Aromatic tetracarboxylic dianhydrides)
Pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ) Methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2 , 3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxy) Phenyl) ether dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 4,4- (p- Phenylene Oxy) diphthalic dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 1,2,5,6-naphthalenedicarboxylic dianhydride, 1,4,5,8-naphthalenedicarboxylic Acid dianhydride, 2,3,6,7-naphthalenedicarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic acid Dianhydrides, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracarboxylic acid Anhydride, 2,2-bis (4-phenoxyphenyl) propanetetracarboxylic dianhydride, 4,4 '-(4,4'-isopropylidenediphenoxy) bis (phthalic anhydride), etc.

(Aromatic tetracarboxylic dianhydrides containing fluorine groups)
2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1 , 1,1,3,3,3-hexafluoropropane dianhydride, etc.

(Aliphatic tetracarboxylic dianhydride)
Ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1 , 2,4,5-Cyclohexanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, tricyclo [6.4.0.0 ^2,7 ] dodecane-1,8: 2,7-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3, 5,6-tetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, etc.

<For ^{R 2>}
R ² is not particularly limited as long as R ² is a divalent organic group. Specific examples thereof include diisocyanate compounds; diamines such as aromatic diamine compounds, aromatic diamine compounds containing fluorine groups, and aliphatic diamine compounds. Examples of the structural unit of the compound. More specific examples include the following.

(Diisocyanate)
4,4'-Diisocyanato-3,3'-dimethylbiphenyl, 2,2-bis (4-isocyanatophenyl)
Hexafluoropropane, 4,4'-diisocyanato-3,3'-dimethyldiphenylmethane, 1,5-
Diisocyanato naphthalene, methylene diphenyl 4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, etc.

(Diamine compound)
(Aromatic diamine compound)
4,4 '-(9-fluorenylidene) dianiline, 2,7-diaminofluorene, 1,5-diaminonaphthalene, 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide, 4,4'- (Biphenyl-2,5-diylbisoxy) bisaniline, 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4 -Aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) neopentane, 4,4'-diamy -3,3'-dimethylbiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diamino-3,3'- Dihydroxybiphenyl, bis (4-amino-3-carboxyphenyl) methane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, N- (4-aminophenoxy) -4-aminobenzamine, 2 , 2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, bis (3-aminophenyl) sulfone, norbornanediamine, etc. (aromatic diamine compound containing a fluorine group)
4,4′-diamino-2- (trifluoromethyl) diphenyl ether, 5-trifluoromethyl-1,3-benzenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 4, 4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane, etc. (aliphatic diamine Compound)
1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methyl) (Cyclohexylamine) etc.

When R ² is a diamine compound, R ² is a divalent organic group represented by the general formula (2) because not only the solubility in an organic solvent is improved but also the thermoplasticity is improved. preferable. Moreover, it is preferable at the point from which the heat-resistant and tough resin molding is obtained, colorless transparency becomes high, and coloring by time-dependent deterioration can be reduced.

[In General Formula (2), Ring A ¹ and Ring A ² are each independently an alicyclic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent. Indicate
p and q each independently represent an integer of 0 or more and 10 or less.
X ¹ is a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, a carbonyl group, an aromatic group which may have a substituent,- NH-C (= O) - group shown, -NH- group, or _{-O-C z} H 2z -O- based (z is an integer of from 1 to 5). However, neither p nor q is 0.
Y ¹ and Y ² each independently represent a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, or a carbonyl group. When p or q is 2 or more, the plurality of Y ¹ , Y ² , ring A ¹ and ring A ² may be different from each other. )

The aliphatic ring of ring A ¹ and ring A ² is not particularly limited, but is a cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, norbornane ring, norbornene ring, hydrindane ring, decahydro ring The thing of 3-30 carbon atoms, such as a naphthalene ring and an adamantane ring, is mentioned. Among these, a cyclohexane ring, a cyclopentane ring, and a norbornane ring are preferable from the viewpoints of transparency, mechanical properties, and heat resistance of the polyimide resin molded body.

The aromatic rings of the ring A ¹ and the ring A ² are not particularly limited, but examples thereof include an aromatic hydrocarbon ring and an aromatic heterocyclic ring, independently.
Specific examples of the aromatic hydrocarbon group include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, a triphenylene group, a terphenylene group, a pinylene group, and a fluorene group. The aromatic hydrocarbon group for ring A ¹ and ring A ² preferably has 6 or more carbon atoms, preferably 30 or less, and more preferably 25 or less. When the carbon number is within this range, the mechanical properties and heat resistance of the polyimide resin molded product tend to be improved.
Specific examples of the aromatic heterocyclic group include a pyridylene group and a quinolylene group. The aromatic hydrocarbon group for ring A ¹ and ring A ² preferably has 2 or more carbon atoms, preferably 30 or less, and more preferably 25 or less. When the carbon number is within this range, the mechanical properties and heat resistance of the polyimide resin molded product tend to be improved.
Among the aromatic rings of ring A ¹ and ring A ² , a benzene ring, a biphenylene ring, and a terphenyl ring are preferable. Further, the aromatic ring or aliphatic ring which is ring ^{A 1} and ring ^{A 2, Y 2, Y 3} , or point of attachment to the ^{X 2} is not particularly limited.

Examples of the substituent that the aromatic ring or the aliphatic ring of ring A ¹ and ring A ² may have include a halogen atom, an alkyl group, an alkoxy group, and a hydroxyl group. Examples of the halogen atom include a fluorine atom, a bromine atom, and a chlorine atom. Examples of the alkyl group include those having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tertiary butyl group. Examples of the alkoxy group include those having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tertiary butoxy group.

  In the general formula (2), p and q are each independently an integer of 0 or more, preferably 1 or more, and on the other hand, an integer of 10 or less, preferably 5 or less.

In Formula (2), X ¹ may have a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, a carbonyl group, or a substituent. An aromatic group, —NH—C (═O) —, —NH—, or —O—C _z H _2z —O— is shown. However, z shows the integer of 1-5.
Among these, from the viewpoint of mechanical properties and heat resistance of the polyimide resin molded body, a direct bond, an oxygen atom, an alkylene group which may have a substituent, a sulfinyl group, or a sulfonyl group is preferable, and an oxygen atom In particular, an alkylene group which may have a substituent or a sulfinyl group is particularly preferable.

The alkylene group for X ¹ is not particularly limited, but is preferably an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 10 carbon atoms from the viewpoint of mechanical properties and heat resistance of the polyimide resin molded body. More preferably, it is a group. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 2,2-propanediyl group.

The aromatic group for X ¹ is not particularly limited, and examples thereof include an aromatic hydrocarbon group and an aromatic heterocyclic group. Specifically the same meanings as those mentioned ring A ^1. The aromatic hydrocarbon group for X ¹ preferably has 6 or more carbon atoms, preferably 30 or less, and preferably 25 or less from the viewpoint of mechanical properties and heat resistance of the polyimide film. Further, the aromatic heterocyclic group of X ¹ preferably has 2 or more carbon atoms, preferably 30 or less, and preferably 25 or less from the viewpoint of mechanical properties and heat resistance of the polyimide resin molded body. Among the aromatic ring of X ^1, a phenylene group, a naphthylene group and a pyridylene group, it is particularly preferred.

Examples of the substituent that the alkylene group or aromatic group of X ¹ may have include an alkyl group having 1 to 5 carbon atoms, a hydroxy group, an alkoxy group, an amino group, a carboxyl group, and an epoxy group. These substituents may be further substituted with a halogen atom such as a fluorine atom or a chlorine atom.

Y ¹ and Y ² each independently represent a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, or a carbonyl group. Among these, a direct bond or an oxygen atom is preferable. In addition, when p or q is 2 or more, there are a plurality of Y ¹ and Y ^2, but the plurality of Y ¹ and Y ² may have the same structure or may have different structures. . Here, as the alkylene group which may have a substituent, the same groups as those mentioned for X ¹ can be used.

More preferable examples of R ^{2 in} the general formula (1) include those represented by the following general formula (3) or (4).

The general formula (3) corresponds to the case where p = 2 and q = 2 in the general formula (2). In general formula (3), ring A ²² and ring A ²³ are synonymous with ring A ¹ in general formula (2), and ring A ²⁴ and ring A ²⁵ are synonymous with ring A ² in general formula (2). It is. Y ¹² and Y ¹³ are synonymous with Y ¹ in the general formula (2), and Y ¹⁴ and Y ¹⁵ are synonymous with Y ² in the general formula (2). Further, ^{X 5} has the same meaning as ^{X 1} in the general formula (2). The substituents that each may have are also synonymous.
Similarly to formula (2), ring A ²² , ring A ²³ , ring A ²⁴ and rings A ²⁵ , Y ^{12 to} Y ¹⁵ may be the same or different.

In the formula (3), the ring A ²² , the ring A ²³ , the ring A ²⁴ and the ring A ²⁵ are each independently an aromatic ring which may have a substituent. From the viewpoint of heat resistance. Among these, a phenylene group is more preferable, and a substituent that may be present is preferably a halogen atom such as a chlorine atom.
Further, from the viewpoint of mechanical properties and heat resistance of the polyimide resin molded body, Y ¹² and Y ¹³ are preferably a direct bond, an oxygen atom or a sulfur atom, and Y ¹⁴ and Y ¹⁵ may be a direct bond. preferable.

Equation (4) corresponds to the case where p = 1 and q = 1 in Equation (2). In the formula (4), the ring A ²⁶ and the ring A ²⁷ are synonymous with the ring A ¹ and the ring A ² in the formula (2), and the substituents that may be present are also synonymous. Y ¹⁶ and Y ¹⁷ are synonymous with Y ¹ and Y ² in Formula (2), and the substituents that may be present are also synonymous. Here, it is also preferable that the ring A ²⁶ and the ring A ²⁷ have the same structure, and it is also preferable that Y ¹⁶ and Y ¹⁷ have the same structure.

In formula (4), ring A ²⁶ and ring A ²⁷ each independently have an aromatic ring or substituent which may have a substituent from the viewpoint of mechanical properties and heat resistance of the polyimide resin molded article. It is preferably an aliphatic ring which may be used. Among these, an aromatic ring which may have a substituent is preferable, a phenylene group is more preferable, and a substituent which may have a halogen atom such as a chlorine atom is preferable. . Y ¹⁶ is preferably a direct bond, an oxygen atom or a sulfur atom, and Y ¹⁷ is preferably a direct bond.

Specific examples of R ^{2 in} the general formula (1) include structural units of diamine compounds shown below. That is, the divalent groups derived by removing two primary amino groups from a diamine compound shown below, can be used as R ^2.
Specific examples of such diamine compounds include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-amino) Phenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) neopentane, 4,4′-diamino-3,3′-dimethylbiphenyl, 4, 4'-diamino-2,2'-dimethylbiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-di Mino-3,3′-dihydroxybiphenyl, bis (4-amino-3-carboxyphenyl) methane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, N- (4-aminophenoxy)- 4-aminobenzamine, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 4,4′-methylenebis (2-methylcyclohexylamine), 2,2-bis (4- (4-amino Phenoxy) phenyl) hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} Phenyl] hexafluoropropane, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, bis 3-aminophenyl) sulfone, etc. norbornane diamine. Among these, 4,4′-diaminodiphenyl ether, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 4 , 4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, 4,4'-diamino-2,2'-dimethylbiphenyl, N- (4-aminophenoxy) -4-aminobenzamide or 4,
Having a divalent substituent obtained by removing an amino group from 4′-methylenebis (cyclohexylamine) as R ² is preferable in that heat resistance, mechanical strength, and colorless transparency can be achieved simultaneously.

  Among the polyimide resins used in the polyimide resin molding of the present invention, 1,1′-bicyclohexane-3,3 ′ constituted by a tetracarboxylic acid residue having a bicyclohexane skeleton represented by the general formula (5) 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride is preferably used. Thus, a polyimide resin molded article constituted by a tetracarboxylic acid residue having a bicyclohexane skeleton is constituted by an aromatic ring such as biphenyl or a tetracarboxylic acid residue having a monocyclic aliphatic ring as a skeleton. Compared with the polyimide resin molded body, the effect of reducing coloring and improving solubility can be obtained. Moreover, these polyimide resin moldings are excellent in heat resistance and colorless transparency.

[In the general formula (5), R ³ represents a divalent organic group,
a represents an integer of 1 or more, and when a is 2 or more, a plurality of R ³ present in one molecule of the structure represented by the general formula (5) may be the same or different. ]

The divalent organic group of R ³ has the same meaning as R ^{2 in the} general formula (1), and the substituent that may be present is also the same.
a is an integer of 1 or more, and there is no particular upper limit as long as the effect of the present invention is not impaired, but the mass average molecular weight of the polyimide resin used for the polyimide resin molded body represented by the general formula (5) is It is preferable from the viewpoint of the strength of the polyimide film that a is preferably set to 40000 or more, more preferably 50000 or more.

  The tetracarboxylic dianhydride represented by the formula (5) includes 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-2. In addition to the anhydride, other tetracarboxylic dianhydrides may be mixed to such an extent that various physical properties such as heat resistance and colorless transparency of the polyimide resin molding according to this embodiment are not impaired. The tetracarboxylic dianhydride to be mixed may be one type or two or more types.

The weight average molecular weight (Mw) in terms of polystyrene of the polyimide resin of the present invention is usually 1.0 × 10 ³ or more, preferably 5.0 × 10 ³ or more, more preferably 1.0 × 10 ⁴ or more. On the other hand, it is usually 1.0 × 10 ⁶ or less, preferably 8.0 × 10 ⁵ or less, more preferably 5.0 × 10 ⁵ or less. This range is preferable in that solubility, solution viscosity, melt viscosity, and the like are in a range that can be easily handled by ordinary production equipment. The polystyrene-reduced weight average molecular weight of the polyimide resin can be determined by gel permeation chromatography (GPC) or the like.

The number average molecular weight (Mn) of the polyimide resin of the present invention is usually 5.0 × 10 ² or more, preferably 2.5 × 10 ³ or more, more preferably 5.0 × 10 ³ or more. On the other hand, it is usually 5.0 × 10 ⁴ or less, preferably 4.0 × 10 ⁴ or less, and more preferably 2.5 × 10 ⁴ or less. This range is preferable in that solubility, solution viscosity, melt viscosity, and the like are in a range that can be easily handled by ordinary production equipment. The number average molecular weight of the polyimide resin can be measured by the same method as the weight average molecular weight.

The molecular weight distribution (PDI, (weight average molecular weight / number average molecular weight (Mw / Mn))) of the polyimide resin of the present invention is usually 1 or more, preferably 1.1 or more, more preferably 1.2 or more. On the other hand, it is usually 3 or less, preferably 2.8 or less, more preferably 2.5 or less.
The molecular weight distribution is preferably within this range in that a highly uniform polyimide molded body can be obtained. The molecular weight distribution of the polyimide resin can be measured by the same method as the weight average molecular weight.

The melt elongation (μm) by thermomechanical analysis (TMA) of the polyimide resin of the present invention (measurement condition: measurement temperature 270 ° C., tensile load 10 g, holding time 60 minutes, sample shape 4 mm × 5 mm, thickness 45 μm) is preferably Is 1.0 × 10 ² or more, more preferably 1.0 × 10 ³ or more, and particularly preferably 1.8 × 10 ³ or more. On the other hand, it is preferably 1.0 × 10 ⁵ or less, more preferably 5.0 × 10 ⁴ or less, and particularly preferably 1.0 × 10 ⁴ or less. By being 1.0 × 10 ² or more, melt molding tends to be easy. Further, there is a tendency that such sagging during molding is suppressed by at 1.0 × 10 ⁵ or less. The thermomechanical analysis (TMA) of the polyimide resin can be measured by a known method, for example, the method described in JP-A No. 2003-155341.

Although there is no special restriction | limiting in the density | concentration of the residual solvent of the polyimide resin of this invention, 20 mass% or less is preferable, More preferably, it is 10 mass% or less. On the other hand, there is no limit on the lower limit. By adjusting the concentration of the solvent in the polyimide resin within this range, in the process of lowering the volatile gas contained in the polyimide resin molded body and obtaining the molded body described later (at the time of melting), significant foaming is seen, There tends to be no problem of combustible gas generation.
The concentration of the solvent in the polyimide resin can be measured by a known method, for example, the method described in JP-A-2006-70130.

The glass transition temperature (Tg) of the polyimide resin of the present invention by differential scanning calorimetry (DSC method) is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, more preferably 250 ° C. or higher. It exists in the tendency for the heat resistance of the polyimide resin molding of this invention to improve because a glass transition temperature is 150 degreeC or more.
The thermal expansion coefficient of the polyimide resin of the present invention is preferably 100 ppm / K or less, more preferably 70 ppm / K or less in the range of 100 to 200 ° C. When the thermal expansion coefficient is in such a range, a molded body with high dimensional accuracy tends to be manufactured.

The yellowness [yellow index (YI)] of the polyimide resin of the present invention when the film thickness is 50 ± 5 μm is usually −10 or more, preferably −5 or more, more preferably −1 or more. On the other hand, it is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less.
Although the polyimide resin of the present invention depends on a molding method for melt molding, it preferably has the following mechanical strength.
The tensile strength of the polyimide resin according to the present invention is not particularly limited, but preferably 50 MP.
a or more, more preferably 70 MPa or more, on the other hand, preferably 400 MPa or less, more preferably 300 MPa or less.
The tensile elastic modulus of the polyimide resin according to the present invention is not particularly limited, but is preferably 1000 MPa or more, particularly preferably 1500 MPa or more, and preferably 20 Gpa or less, particularly preferably 10 Gpa or less.

The melt viscosity of the polyimide resin of the present invention is not particularly limited, but is preferably 1.0 × 10 ¹ Pa · s or more, more preferably 1.0 × 10 ² Pa · s or more at 330 ° C. On the other hand, preferably 1.0 × 10 ⁷ Pa · s or less, more preferably 1.0 × 10 ^5.
Pa · s or less, more preferably 1.0 × 10 ⁴ Pa · s or less, further preferably 5.0 × 10 ³ Pa · s or less, and particularly preferably 3.0 × 10 ³ Pa · s or less. Polyimide having a melt viscosity of 1.0 × 10 ¹ Pa · s or higher is preferable in that it has high toughness and is suitable for use as a molded product. Further, a polyimide having a melt viscosity of 1.0 × 10 ⁷ Pa · s or less is preferable in that it has good fluidity and is suitable for thermoplastic molding.
The melt viscosity of the polyimide resin obtained in the present invention can be measured by a known method, for example, the method described in JP-A-1-297427.

The polyimide resin of the present invention is not particularly limited, but may contain components other than polyimide such as unreacted substances and other additives generated when the polyimide resin is obtained. Content of the polyimide contained in the polyimide resin of this invention is 50 mass% or more normally, Preferably it is 80 mass% or more, on the other hand, there is no restriction | limiting in an upper limit. By adjusting the concentration of the polyimide resin within this range, foaming and coloring at the time of melting can be suppressed, and good workability tends to be achieved.
The ratio of the unreacted polyamic acid resin or polyamic acid ester resin to the polyimide resin in the polyimide resin is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass. The following is preferable. When 30% or more of the polyamic acid resin or the polyamic acid ester resin is contained in the polyimide resin, the polyimide resin and the polyamic acid resin or the polyamic acid ester resin may be phase-separated to cause white turbidity in the polyimide resin. . Moreover, when the polyimide resin phase-separated inhomogeneously is used for melt molding, the molded body may also be non-uniform, and irregularities or cloudiness may occur in the molded body.

Moreover, in order to control the fluidity | liquidity at the time of the polyimide resin melting of the below-mentioned process, the additive may be added to the polyimide resin which concerns on this invention. For example, a coupling agent such as a silane coupling agent or a titanium coupling agent can be added to the polyimide resin according to the present invention.
Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ -Aminoethyltrimethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, and γ- Examples include aminobutyl tributoxysilane.

  Examples of the titanium coupling agent include γ-aminopropyltriethoxytitanium, γ-aminopropyltrimethoxytitanium, γ-aminopropyltripropoxytitanium, γ-aminopropyltributoxytitanium, γ-aminoethyltriethoxytitanium, γ -Aminoethyltrimethoxytitanium, gamma-aminoethyltripropoxytitanium, gamma-aminoethyltributoxytitanium, gamma-aminobutyltriethoxytitanium, gamma-aminobutyltrimethoxytitanium, gamma-aminobutyltripropoxytitanium, and gamma- Examples include aminobutyl tributoxy titanium.

The polyimide resin according to the present invention may contain one type of coupling agent or may contain two or more types of coupling agents. The amount of the coupling agent contained in the polyimide resin according to the present invention is preferably 0.1% by mass or more and 3% by mass or less with respect to the polyimide resin from the viewpoint of improving the physical properties of the obtained film.
In addition, if necessary, for example, an inorganic filler or an organic filler such as powder, granule, plate, or fiber can be blended within a range that does not impair the object of the invention.

Examples of inorganic fillers include oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice or pumice balloon; hydroxides such as aluminum hydroxide, magnesium hydroxide or basic magnesium carbonate; calcium carbonate, Carbonates such as magnesium carbonate, dolomite or dosonite; sulfates and sulfites such as calcium sulfate, barium sulfate, ammonium sulfate or calcium sulfite; talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate, Silicates such as montmorillonite or bentonite; carbons such as carbon fiber, carbon black, graphite or carbon hollow sphere; molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate or boron Powder-like, granular, plate-like, or fibrous inorganic fillers such as fibers; Powder-like, granular, fibrous, or whisker-like metal fillers such as metal elements, metal compounds, and alloys; silicon carbide, silicon nitride, Examples thereof include powder fillers such as zirconia, aluminum nitride, titanium carbide, and potassium titanate, granular, fibrous, or whisker-like ceramic fillers.

On the other hand, examples of the organic filler include shell fibers such as fir shells, carbon nanotubes, fullerenes, wood flour, cotton, jute, paper strips, cellophane pieces, aromatic polyamide fibers, cellulose fibers, nylon fibers, polyester fibers, Examples thereof include polypropylene fiber, thermosetting resin powder, and rubber.
As a filler, what was processed into flat form, such as a nonwoven fabric, may be used, and a plurality of materials may be mixed and used. Furthermore, if desired, various additives commonly used for resins, such as lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers or release agents, You may mix | blend with the polyimide resin which concerns on invention. These various fillers and additive components may be added at any stage of any process for producing the polyimide resin.

<3. Manufacturing method of polyimide resin>
There is no special restriction | limiting in the manufacturing method of the polyimide resin of this invention. As an example of a method for producing a polyimide resin, a method for producing a polyamic acid resin or a polyamic acid ester resin, which is a polyimide resin precursor, and converting the obtained precursor into a polyimide resin will be described.

  The reaction for obtaining a polyamic acid from tetracarboxylic dianhydride and a diamine compound can be carried out under conventionally known conditions. There are no particular limitations on the order of addition or addition method of the tetracarboxylic dianhydride and the diamine compound. For example, a polyamic acid resin can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and stirring at an appropriate temperature.

The amount of the diamine compound is usually 0.8 mol or more, preferably 1 mol or more with respect to 1 mol of tetracarboxylic dianhydride. On the other hand, it is 1.2 mol or less normally, Preferably it is 1.1 mol or less. By making the quantity of a diamine compound into such a range, it exists in the tendency for the yield of the polyamic acid resin obtained to improve.
The concentration of the tetracarboxylic dianhydride and the diamine compound in the solvent can be appropriately set according to the reaction conditions and the viscosity of the polyamic acid resin solution. For example, the total weight of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more with respect to the total amount of the solution, while usually 70%. It is not more than mass%, preferably not more than 30 mass%. By setting the amount of the reaction substrate in such a range, a polyamic acid resin tends to be obtained at a low cost and in a high yield.

  The reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and is usually 100 ° C. or lower, preferably 80 ° C. or lower. The reaction time is not particularly limited, but is usually 1 hour or more, preferably 2 hours or more, while it is usually 100 hours or less, preferably 24 hours or less. By performing the reaction under such conditions, a polyamic acid resin tends to be obtained at a low cost and in a high yield. The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere.

Solvents used in this reaction include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene and mesitylene; carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and fluorobenzene. Halogenated hydrocarbon solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; ether solvents such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; N, N-dimethylformamide, N Amide solvents such as N, dimethylacetamide and N-methyl-2-pyrrolidone; aprotic polar solvents such as dimethyl sulfoxide; pyridine, picoline, lutidine, quinoline and i Heterocyclic solvents such as quinoline; phenol solvents such as phenol and cresol; lactone solvents such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone, etc., but are not particularly limited. . As the solvent, one kind of substance can be used, or two or more kinds of substances can be mixed and used.

  The polyamic acid resin or polyamic acid ester resin obtained by reacting the tetracarboxylic dianhydride with the diamine compound is mainly selected from the following general formulas (6), (7) and (8) Contains at least one unit.

In the general formulas (6), (7) and (8), R ¹⁰ , R ¹⁴ and R ¹⁸ are each independently synonymous with R ¹ in the general formula (1) and may have a substituent. Is also synonymous.
R ¹¹ , R ¹⁵ and R ¹⁹ are each independently synonymous with R ² in the general formula (1), and the substituents which may be present are also synonymous.
R ¹² , R ¹³ , R ¹⁶ , R ¹⁷ , R ²⁰ and R ²¹ represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms which may have a substituent. Although there is no special restriction | limiting as an alkyl group, Usually, it is a C1-C14 alkyl group, A C1-C10 alkyl group is preferable, a methyl group, an ethyl group, n-propyl group, isopropyl group, n- A butyl group or an isobutyl group is more preferable, and a methyl group or an ethyl group is still more preferable. Examples of the substituent that the alkyl group may have include a halogen atom.

In the polyamic acid resin or polyamic acid ester resin obtained in the present embodiment, the abundance ratio of the general formulas (6) to (8) is not particularly limited. The polyimide resin according to the present embodiment is obtained by converting the polyamic acid resin or the polyamic acid ester resin thus obtained into a polyimide resin by a method described later.

  The polyimide resin according to the present invention can be obtained by imidizing the polyamic acid resin or polyamic acid ester resin thus obtained by the method described later.

<Imidization>
The polyamic acid resin or polyamic acid ester resin described above is subjected to dehydration cyclization or dealcoholization cyclization (hereinafter collectively referred to as imidization) in the presence of a solvent to produce a polyimide resin. This method is preferable in that a polyimide resin having high fluidity upon melting can be obtained.

  The imidization can be performed using any conventionally known method, and examples thereof include thermal imidization by thermal cyclization and chemical imidization by chemical cyclization. These imidization reactions may be used alone or in combination.

(Heat imidization)
Below, the method of the heat imidation in a solution is demonstrated.
A polyimide resin solution can be obtained by heating a polyamic acid resin or a polyamic acid ester resin in the presence of a solvent.
Examples of the solvent used when imidizing the polyamic acid resin or the polyamic acid ester resin include the solvents used in the reaction for obtaining the polyamic acid resin or the polyamic acid ester resin. Among them, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are highly soluble in polyamic acid resin, polyamic acid ester resin and polyimide resin, and have a boiling point. This is preferable because the imidization reaction proceeds efficiently.

In this case, water (or alcohol) generated by the imidization reaction inhibits the ring closure reaction, and thus is preferably discharged out of the reaction system. For example, a method may be used in which water is discharged out of the system by mixing an azeotropic solvent such as toluene or xylene and azeotroping with water.
The concentration of the polyamic acid resin or polyamic acid ester resin in the imidization reaction solution is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and usually 80% by mass or less. Preferably it is 60 mass% or less, More preferably, it is 40 mass% or less. 5 mass% or more is preferable in terms of high production efficiency, and 80 mass% or less is preferable in that the solution viscosity is easy to handle with ordinary manufacturing equipment.

  The imidation reaction temperature is not particularly limited, but is usually 50 ° C or higher, preferably 80 ° C or higher, more preferably 120 ° C or higher, and usually 300 ° C or lower, preferably 280 ° C or lower, more preferably 250 ° C or lower. . It is preferable in that the imidization reaction proceeds efficiently when it is 50 ° C. or higher, and it is preferable in that the side reaction other than the imidization reaction is suppressed when it is 300 ° C. or lower. The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere.

Moreover, tertiary amines etc. can also be added as a catalyst which accelerates | stimulates imidation. Specifically, trimethylamine, triethylamine, tripropylamine, tributylamine, tritanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N- Methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, isoquinoline, and the like can be used as a catalyst. The amount of the catalyst used is preferably from 0.1 to 100 mol%, more preferably from 1 to 10 mol%, based on the carboxyl group or ester group. When the amount of the catalyst used is in such a range, the reaction can be performed at a low cost and with a high yield.

(Chemical imidization)
The case where chemical imidation is used as the imidation method will be described below.
A polyimide resin solution can be obtained by chemically imidizing a polyamic acid resin or a polyamic acid ester resin in the presence of a solvent.
Examples of the solvent used when imidizing the polyamic acid resin or the polyamic acid ester resin include the solvent for the heating imidization.

  The concentration of the polyamic acid resin or polyamic acid ester resin in the imidization reaction solution is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 20% by mass or more, and preferably It is 80 mass% or less, More preferably, it is 60 mass% or less, Most preferably, it is 40 mass% or less. 5% by mass or more is preferable in terms of high production efficiency, and 80% or less is preferable in that the solution viscosity is easy to handle with ordinary production equipment. The imidation reaction temperature is not particularly limited, but is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, particularly preferably 120 ° C. or higher, more preferably 300 ° C. or lower, more preferably 280 ° C. or lower, particularly preferably 250. It is below ℃. It is preferable in that the imidization reaction proceeds efficiently when it is 50 ° C. or higher, and it is preferable in that the side reaction other than the imidization reaction is suppressed when it is 300 ° C. or lower. The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere.

Further, a tertiary amine or the like can be added as a catalyst for promoting imidization in the same manner as in the heating imidization.
N, N-2-substituted carbodiimide such as N, N-dicyclohexylcarbodiimide or N, N-diphenylcarbodiimide; acid anhydride such as acetic anhydride or trifluoroacetic anhydride; chloride such as thionyl chloride or tosyl chloride Acetyl chloride, acetyl bromide, propionyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, isobutyryl fluoride Ride, n-butyryl chloride, n-butyryl bromide, n-butyryl iodide, n-butyryl fluoride, mono-, di-, tri-chloroacetyl chloride, mono-, di-, tri- Lomoacetyl chloride, mono-, di-, tri-iodoacetyl chloride, mono-, di-, tri-fluoroacetyl chloride, chloroacetic anhydride, phenylphosphonic dichloride, thionyl chloride, thionyl bromide, thionyl iodide or thionyl fluoride Halide compounds such as rides; phosphorus compounds such as phosphorus trichloride, triphenyl phosphite, or cyanide diethyl phosphate can be added. The amount of these dehydrating condensing agents to be used is usually 0.5 mol, preferably 1 mol or more, and usually 20 mol or less, preferably 10 mol or less, relative to 1 mol of the polyamic acid resin or polyamic acid ester resin skeleton. These can be used alone or in combination of two or more.
Further, the polyamic acid resin or polyamic acid ester resin used in the present invention, the polyimide resin obtained by the present invention and the polyimide resin may be end-capped as necessary. By end-capping, the polyamic acid resin or polyamic acid ester resin and polyimide resin terminal polymerizability are lowered, and this is preferable in that the viscosity of the polyimide resin solution or the melt viscosity of the polyimide resin is stabilized.

The terminal sealing method is not limited, and any conventionally known method may be used. You may seal in any step which prepares a polyamic acid resin, a polyamic acid ester resin, and a polyimide resin. A preferable method includes a method using a terminal blocking agent. For example, when sealing with a terminal blocking agent, as the terminal blocking agent, any conventionally known blocking agent may be used. For example, the terminal blocking agent used when sealing a terminal amino group is used. As acid anhydrides such as phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride or (2-methyl-2-propenyl) succinic anhydride; And organic acid chlorides such as benzoic acid chloride. In addition, examples of the terminal blocking agent for sealing the terminal acid anhydride group include amine compounds such as 3-aminophenylacetylene, aniline, and cyclohexylamine.

<Composition of polyimide resin solution>
The concentration of the polyimide resin in the polyimide resin solution obtained by imidation of the polyamic acid or polyamic acid ester according to the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, On the other hand, it is preferably 80% by mass or less, more preferably 50% by mass or less. By adjusting the concentration of the polyimide resin in the solution within this range, an extreme increase in viscosity during the reaction can be suppressed, and good workability can be achieved in the subsequent solidification process.

The viscosity of the polyimide resin solution obtained by imidation of polyamic acid or polyamic acid ester according to the present invention is not particularly limited, but is preferably 10 mPa · s or more, more preferably 1.0 × 10 ² mPa · s or more. On the other hand, it is preferably 5.0 × 10 ⁴ mPa · s or less, more preferably 2.0 × 10 ⁴ mPa · s or less. By adjusting the viscosity of the polyimide resin solution within the above range, it is preferable in that the solvent can be easily removed from the polyimide resin solution described later.

The viscosity of the polyimide resin solution is measured at 25 ° C. using an E-type viscometer. The viscosity can be measured by a known method, for example, according to the method described in International Publication No. 99/60622.
Thus, the polyimide resin preferable for melt molding can be prepared by adjusting the substance composition ratio in the polyimide resin solution.

  In the polyimide resin solution obtained by imidation of polyamic acid or polyamic acid ester according to the present invention, the ratio of the unreacted polyamic acid resin or polyamic acid ester resin to the polyimide resin is not particularly limited, but is preferably 30% by mass. Hereinafter, it is further preferably 20% by mass or less, particularly preferably 10% by mass or less, and there is no particular lower limit, and a lower value is preferable. When more than 30% by mass of the polyamic acid resin or polyamic acid ester resin is contained in the polyimide resin solution, white turbidity may occur due to phase separation of the polyimide resin and the polyamic acid resin or polyamic acid ester resin. Moreover, when the polyimide resin obtained from the polyimide resin solution which phase-separated nonuniformly is used for melt molding, a molded object also becomes non-uniform | heterogenous and an unevenness | corrugation, white turbidity, etc. may arise in a molded object.

The ratio of the polyamic acid resin or the polyamic acid ester resin to the polyimide resin in the polyimide resin solution is represented by the following formula.
Ratio of polyamic acid resin or polyamic acid ester resin in polyimide resin solution to polyimide resin = (substance amount of polyamic acid resin or polyamic acid ester resin in polyimide resin solution) / (polyamic acid resin or polyamic acid in polyimide resin solution) Substance amount of ester resin + substance amount of polyimide resin in polyimide resin solution) × 100
The substance amount of the polyamic acid resin or polyamic acid ester resin in the polyimide resin solution is the weight of the polyamic acid resin or polyamic acid ester resin component contained in the polyimide resin solution, represented by the general formulas (6), (7) and ( It is obtained by dividing by the average molecular weight of each repeating unit represented by 8).

  The substance amount of the polyimide resin in the polyimide resin solution is obtained by dividing the weight of the polyamic acid resin or polyamic acid ester resin component contained in the polyimide resin solution by the molecular weight of the repeating unit represented by the general formula (1). It is done. Various methods for measuring the amount of polyamic acid resin or polyamic acid ester resin in polyimide resin solution are known, including nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR method), and imide ring closure. Quantitative determination of water content, method of neutralization titration of carboxylic acid contained in polyamic acid (see JP 2009-269958 A), measurement of luminescence intensity or absorption intensity by labeling specific functional groups (See Japanese Patent No. 4529760).

[Step of removing polyimide from polyimide resin solution to obtain polyimide resin]
The process of obtaining the polyimide resin from the polyimide resin solution is not particularly limited as long as the organic solvent or water contained in the polyimide resin solution can be removed. For example, the polyimide resin solution has a low solubility of the polyimide resin. A method for removing a solvent such as an organic solvent and water by precipitating a polyimide resin by adding a solution therein, separating the deposited polyimide resin according to the present invention, and heating and / or depressurizing the polyimide resin solution. Can be mentioned.

  The solvent for precipitating the polyimide resin can be appropriately selected depending on the type of the polyimide resin, but ethers such as diethyl ether or diisopropyl ether; ketones such as acetone, methyl ethyl ketone, isobutyl ketone or methyl isobutyl ketone; methanol, ethanol or isopropyl alcohol And alcohol. Of these, alcohols such as isopropyl alcohol are preferable in that precipitates can be obtained efficiently, the boiling point is low, and drying is easy.

  The temperature at which the polyimide resin is deposited can be suitably selected as appropriate, but is usually 5 ° C. or higher, preferably 10 ° C. or higher, and usually 80 ° C. or lower, preferably 60 ° C. or lower, more preferably 50 ° C. or lower. It is. The time at which the polyimide resin is deposited is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 3 hours or shorter, preferably 2 hours or shorter.

The pressure at the time of polyimide resin deposition may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere.
Examples of the method for separating the polyimide resin during precipitation from the solvent include filtration, centrifugation, and sedimentation. Especially, filtration is preferable at the point which can collect | recover polyimide resins efficiently. It is preferable to remove the solvent remaining in the polyimide resin with respect to the solvent and the separated polyimide resin. The method for removing the solvent is not particularly limited as long as the solvent is removed, and specifically, hot air heating, vacuum drying, infrared heating, microwave heating, heating by contact using a hot plate or a hot roll, etc. The processing method is mentioned. Among these, vacuum drying is preferable because the polyimide resin can be efficiently dried in a short time.

A suitable temperature can be appropriately used for removing the solvent, but it is usually 40 ° C. or higher, preferably 60 ° C. or higher, and usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. is there. The time for removing the solvent is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 4 hours or shorter, preferably 3 hours or shorter, more preferably 2 hours or shorter.
The pressure at the time of removing the solvent is not particularly limited, but is usually 0.01 MPa or more, and usually less than atmospheric pressure, preferably 0.09 MPa or less, more preferably 0.08 MPa or less when drying under reduced pressure.

  When the amount of the solvent is small, the solvent such as an organic solvent or water may be removed by heating and / or reducing the pressure of the obtained polyimide resin solution without performing the operation of extracting the polyimide resin.

<4. Method for obtaining a polyimide resin molding>
The method for obtaining the polyimide resin molded body of the present invention will be described below.
The polyimide resin molding of the present invention is obtained by melting and molding the polyimide resin described above to obtain a polyimide resin molding. First, the process of melting the polyimide resin of the present invention will be described.
The melting temperature is not particularly limited as long as it is equal to or higher than the melting point of the polyimide resin of the present invention.

  Further, if desired, inorganic fillers, organic fillers, metal fillers, lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, as long as the object of the present invention is not impaired. A flame retardant, a plasticizer, a mold release agent, etc. can be mix | blended. The above-described polyimide resin may be a thermoplastic resin, and may be prepared by mixing the above filler and various additive components used as desired and kneading in a kneader, or may be prepared in advance with a thermoplastic resin and a desired one. Depending on the conditions, the additive component used may be quantitatively supplied to the extruder and kneaded, and the filler may be prepared by side-feeding and kneading the filler in the melted portion.

  Furthermore, you may laminate with the polyimide resin of this invention which softened what processed the filler into flat form, such as a nonwoven fabric. The kneading machine is not particularly limited as long as it can knead the polyimide resin, the filler, and the additive. For example, a screw extruder such as a single-screw extruder or a multi-screw extruder, an elastic extruder, a hydro extruder, or the like. Non-screw extruders such as dynamic extruders, ram-type continuous extruders, roll-type extruders, and gear-type extruders can be exemplified.

Next, the process of shaping the polyimide resin melt will be described. The above polyimide resin can be produced by various methods such as injection molding, extrusion molding, hollow molding, compression molding, lamination molding, roll processing, stretching, stamping, hot pressing, or T-die method. By a molding method, it is molded into a desired molded product. In particular, since a film-like polyimide resin molded body molded by an extrusion molding method, a lamination molding method, a stretching method or the like is colorless and transparent, it can be suitably used as a transparent heat-resistant film for various electronic devices. Further, by using an injection molding method or the like, various molded products such as lenses and light guide plates can be manufactured. The reaction temperature at that time is not particularly limited, but is usually not lower than the glass transition temperature, and is usually not higher than the decomposition temperature.
When molding is performed without using a mold, such as extrusion molding, roll processing method, stretching processing method, etc., the atmosphere may be in the air or in an inert atmosphere, and the pressure may be any of normal pressure, pressurized pressure, or reduced pressure. .

<5. Applications of polyimide resin moldings>
The polyimide resin molding of the present invention can be made into a colorless and transparent polyimide resin molding of various shapes by the above-mentioned various molding methods. As a result, not only film applications, which are typical uses of polyimide resins, but also a wide range of applications are possible. For example, flexible solar cell member, display member, IC packaging tray, IC manufacturing tray, IC socket, wafer carrier, connector, socket, hard disk carrier, liquid crystal display carrier, crystal oscillator manufacturing tray, copier separation claw , Heat insulating bearings for photocopiers, gears for photocopiers, thrust washers, transmission rings, piston rings, oil seal rings, bearing retainers, pump gears, conveyor chains, slide bushes for stretch machines, heat-resistant insulation tape, heat-resistant adhesive tape, high-density magnetic It can be used for manufacturing a recording base, a speaker cone, a speaker diaphragm, a film for a condenser or a flexible printed circuit board, and the like. Further, for example, it is also used for manufacturing a structural member reinforced with glass fiber or carbon fiber, a small coil bobbin, or a molded product of a terminal insulating tube.

  Further, it can be used for the production of laminated materials such as insulating spacers, magnetic head spacers or transformer spacers. Moreover, it can be used for manufacture of enamel coating materials such as electric wire / cable insulation coating materials, low-temperature storage tanks, space insulation materials, and integrated circuits. Furthermore, it can also be used for the production of heat-resistant yarns, woven fabrics or nonwoven fabrics.

  Examples The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Measurement of volatile gas species and amount]
150 ° C. when a polyimide resin molding is heated from 30 ° C. to 340 ° C. at a heating rate of 10 ° C./min in a He atmosphere using a differential thermal-thermogravimetric measuring device (TG / DTA6300 manufactured by SII) The weight loss from 1 to 340 ° C. was defined as the residual solvent content. The generated gas was introduced into a mass spectrometer (5973N manufactured by Agilent Technologies) to identify the generated gas species.
[Measurement of total light transmittance]
It was measured according to the test method for total light transmittance of JIS K 7361-1. The total light transmittance at 400 nm was measured using a spectrophotometer UV-2500PC manufactured by Shimadzu Corporation. The higher the transmittance, the better the transparency of the film. The measured film thickness is shown in Table 1.

<Synthesis example>
(First Step: Synthesis of 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride (H-BPDA))
150 g of 1,1′-biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation) was dissolved in a solution obtained by dissolving 83.3 g of sodium hydroxide in 593 g of water. An aqueous solution of 1,1′-biphenyl-3,3 ′, 4,4′-tetracarboxylic acid tetrasodium salt was prepared, and this salt was nuclear hydrogenated at 10 MPaG and 120 ° C. using a ruthenium / carbon catalyst. Subsequently, 429 g of a 49% sulfuric acid aqueous solution was dropped, and the precipitated solid was filtered to obtain 157 g of dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid (H-BTC) (yield 81%).

  To a 300 ml three-necked flask equipped with a thermometer, a stirrer, and a Dimroth condenser, 33.7 g (0.98 mol) of the obtained H-BTC and 90 g of acetic anhydride were added under nitrogen. The mixture was heated with stirring and reacted at reflux temperature (130 ° C. to 140 ° C.) for 3 hours. After the reaction, the reaction solution was cooled to 10 ° C., and the solid was filtered to obtain white crystals. The obtained crystals were washed with toluene and dried with a vacuum drier to obtain 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4, 23.5 g (yield 78%) of a 4′-dianhydride (H-BPDA) -containing composition was obtained.

(Second process: Preparation of polyamic acid resin solution)
Add 41.39 g (0.135 mol) of H-BPDA obtained in the first step to 206 g of N, N-dimethylacetamide and 4,4′-diaminodiphenyl ether (manufactured by Wakayama Seika Co., Ltd.), and heat at 80 ° C. for 6 hours. Stirring was performed to obtain the desired polyamic acid resin solution.

(Third step: a step of imidizing a polyamic acid ester resin in the presence of a solvent to obtain a polyimide resin)
To the four-necked flask equipped with a dry nitrogen gas introduction tube, a cooler, a Dean-Stark aggregator filled with toluene, and a stirrer, the total amount of the polyamic acid ester resin solution obtained in the synthesis example was added, and 41.2 g of toluene was added. . Next, the inside of the three-necked flask was set to a nitrogen atmosphere, the internal temperature was heated to 190 ° C., and water generated accompanying imidization was removed azeotropically with toluene. When heating, refluxing and stirring were continued for 13 hours, generation of water was not observed. Next, 3.24 g of phthalic anhydride was added as a terminal blocking agent, followed by heating, refluxing and stirring for 4 hours to obtain a polyimide resin solution. The obtained polyimide resin solution was dropped into 3000 ml of isopropyl alcohol, and the precipitated polyimide resin was collected by filtration to obtain a white powder of polyimide resin. The amount of residual solvent contained in the obtained polyimide resin powder was 1.5% by mass.

<Example 1>
1.3 grams of the resulting polyimide resin powder was extruded from an orifice with an inner diameter of 1 mm and a length of 10 mm using a Shimadzu elevated flow tester (Shimadzu Corporation, CFT-500A) at 310 ° C. and a load of 40 kg to obtain a thermoplastic polyimide resin. A rod-shaped thermoplastic molded article was obtained. The measurement result of the volatile gas generated from the obtained polyimide resin molding is shown in the table below. Moreover, 0.2 g of polyimide resin solid obtained at 350 ° C. is sandwiched between two polyimide films (Kapton manufactured by Toray DuPont), and polyimide is heated at 300 ° C. for about 3 minutes with a heating press (small heating press 180E manufactured by Imoto Seisakusho). The resin was melted by heating. Then, after heating and compressing at 300 ° C. for about 1 minute at a pressure of 10 MPa, cooling was performed to obtain a polyimide resin molded body. The results of measuring the total light transmittance of the obtained polyimide resin molding are shown in the table below.

<Comparative Example 1>
The same tests as in Examples were performed on a transparent polyimide film (product name: Neoprim L-3430) manufactured by Mitsubishi Gas Chemical Company, Inc. The results are shown in Table 1.

Claims (5)

  A molded body obtained by molding a polyimide resin, the molded body being colorless and transparent, and having a boiling point of 150 ° C. or more generated when heated from 30 ° C. to 340 ° C. in a nitrogen atmosphere. The amount of generation is 0.5% or less with respect to the polyimide resin mass.   2. The polyimide resin molded body according to claim 1, wherein the total light transmittance at 400 nm in a thickness of 50 μm is 60% or more.   The polyimide resin molded body according to claim 1 or 2, wherein the polyimide resin molded body is obtained by thermoplastic molding of the polyimide resin.   The solvent content of the said polyimide resin is 0.1 to 12 mass% in this polyimide resin, The polyimide resin molded object of any one of Claims 1-3 characterized by the above-mentioned.   The film containing the polyimide resin molding of any one of Claims 1-4.