JP2014133887A - Polyimide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide resin composition which has thermal properties optimal for techniques of producing a polyimide resin molding by melting molding.SOLUTION: A resin composition contains a polyimide resin and meets the equation (I): ΔT=Tx-To≤45. In the equation (I), ΔT is the difference between Tx and To; in a temperature rising process, To is the temperature at which lowering of the storage elastic modulus initiates and equal to or higher than 150°C; E'is the storage elastic modulus at To; and Tx is the temperature at which the storage elastic modulus (E') meets the condition E'=E'/100.

Description

  The present invention relates to a thermoplastic transparent polyimide resin composition having specific thermal properties.

  Polyimide resins have excellent properties in terms of heat resistance, mechanical properties, chemical resistance, electrical properties, etc., so they are widely used in the automotive, aerospace industry, electrical, electronic, and battery fields. . However, a polyimide resin is a thermosetting resin that does not have a clear glass transition temperature even though it has excellent heat resistance. When used as a molding material, a special technique such as sintering molding must be used. In order to obtain a processed product having a complicated shape by the sintering molding method, it requires a complicated and complicated processing process such as cutting the desired shape from the polyimide block using a cutting machine such as an NC lathe, and it is expensive. There was a problem.

  Therefore, in order to improve molding processability, a thermoplastic polyimide resin that can be melt-molded at a certain temperature or higher has been developed in the same manner as general-purpose thermoplastic resins. For example, Patent Document 1 describes a thermoplastic polyimide resin having a 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid skeleton as a basic skeleton.

  Patent Document 2 describes a method of molding a polyamic acid solution by a solution casting method such as a solution casting method in order to obtain a polyimide resin film. Patent Document 3 describes a solution casting method using a polyimide resin mixed with a solvent in a solution state.

On the other hand, in order to improve the moldability of polyimide resin, etc., the relationship between the elastic modulus of polyimide resin and temperature has been studied.
For example, Patent Document 4 discloses that by controlling the chemical structure of a thermoplastic resin, the temperature dependence of the elastic modulus is reduced, the elasticity is low, the stress is low, and the cohesive strength and reliability are maintained even at high temperatures. Possible resins are described.
In Patent Document 5, since the decrease in storage elastic modulus of polyimide resin near 200 ° C. is small, the molding temperature of the molding film is close to the temperature at which it can be cooled and taken out after molding. Is obtained.

JP-A-4-331231 JP-A-8-104750 JP 2005-15629 A JP 2006-143996 A JP 2001-348437 A

  However, since the polyimide resin described in Patent Document 1 has a high glass transition temperature and crystallinity, a high temperature of 450 ° C. or higher is necessary to obtain a molten state, and there is a problem that a large process load is required. there were. Moreover, since it has a wholly aromatic skeleton, the obtained polyimide resin is colored, and there is a problem that it is not suitable for a member that requires transparency.

  In addition, the solution casting methods described in Patent Document 2 and Patent Document 3 have problems such as that only a thin-film structure can be produced and the application is limited, that it takes time to dry the solvent, and the cost for that. It was. Furthermore, according to the study by the present inventors, a polyimide suitable for a widely used solution casting method has insufficient fluidity when heated to a glass transition temperature or higher, and is not suitable for melt molding. There is a problem that there is, and this point also needs improvement.

The resin described in Example 1 of Patent Document 4 has a rapid decrease in elastic modulus at a constant temperature and may be suitable for thermoplastic molding, but the temperature at which the elastic modulus decreases is 100 ° C. or less. It cannot be applied to applications that require heat resistance. On the other hand, the polyimide resin described in Comparative Example 1 has sufficient heat resistance, but since the decrease in elastic modulus is linear and has a small inclination, it is heated to an extremely high temperature in order to obtain sufficient fluidity for thermoplastic molding. However, there is a problem that the material undergoes thermal oxidative deterioration and the color tone and physical properties of the molded product are lowered.

Patent Document 5 shows that the change in storage elastic modulus near 200 ° C. is small, but the polyimide resin described in the examples may have a lower elastic modulus than the elastic modulus change rate. It became clear by examination of this inventor. When the rate of change in elastic modulus is low, the fluidity distribution during heating becomes wide, and in order to obtain sufficient fluidity, the material must be heated to an extremely high temperature, and the material undergoes thermal oxidative degradation, resulting in a molded product. There are problems such as deterioration in color tone and physical properties. Moreover, it is expected that the transmittance is low and it is insufficient for applications requiring transparency.
As described above, a polyimide resin composition obtained by melt molding and having excellent properties such as heat resistance and transparency has not been sufficiently studied.

In view of the above, an object of the present invention is to provide a thermoplastic polyimide composition having thermal properties optimal for a technique for obtaining a polyimide resin molded body by melt molding. Moreover, it aims at providing the polyimide resin composition which is excellent also in characteristics, such as heat resistance and transparency.
As a result of intensive studies, the present inventors have found that a polyimide resin composition having a polyimide resin having specific thermal properties is suitable for melt molding, and have reached the present invention.
That is, the gist of the present invention is as follows.

[1] A resin composition containing a polyimide resin, wherein the temperature at which the storage elastic modulus begins to decrease during the temperature rising process is To, the storage elastic modulus at _{To is E'To} , and the storage elastic modulus ( _E'Tx ) is A polyimide characterized in that a difference ΔT between Tx and To is expressed by the following formula (I) and To is 150 ° C. or higher, where Tx is a temperature when E ′ _Tx = E ′ _To / 100 Resin composition.
ΔT = Tx-To ≦ 45 (I)
[2] The polyimide resin composition according to [1], wherein a total light transmittance at 400 nm at a thickness of 50 μm of the polyimide resin composition is 60% or more.
[3] A film comprising the polyimide resin composition according to [1] or [2].

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to obtain the thermoplastic polyimide resin composition which has the thermal property optimal for the method of obtaining a polyimide resin molding by melt molding. Specifically, since the polyimide resin composition of the present invention exhibits high fluidity under mild heating conditions at the time of melting, the processability at the time of melt molding is improved.
Since the polyimide resin composition of the present invention can be molded at a low temperature as compared with an existing wholly aromatic skeleton thermoplastic polyimide resin or the like, the process load can be further reduced. Thus, it becomes possible by using the polyimide resin composition of this invention to manufacture the molded object using the highly practical polyimide resin composition.
Moreover, according to this invention, the polyimide resin composition which is excellent also in characteristics, such as heat resistance and transparency, can be obtained. According to the present invention, since the fluidity of the polyimide resin composition is rapidly improved by heating, excessive temperature and prolonged heating can be avoided, physical non-uniformity such as voids, irregularities, foaming, coloring, A molded body of a polyimide resin composition with little optical property non-uniformity such as white turbidity can be obtained.

It is a figure which shows the relationship between the storage elastic modulus and temperature rising temperature of the polyimide resin composition of this invention.

  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.

The present invention is a polyimide resin composition, wherein, in the temperature rising process, the temperature at which the storage elastic modulus begins to decrease is To, the storage elastic modulus at _To is E ' _To , and the storage elastic modulus (E' _Tx ) is E ' _{Assuming that} the temperature when _Tx = _E′To / 100 is Tx, the difference ΔT between Tx and To is expressed by the following formula (I), and To is 150 ° C.
It is the polyimide resin composition characterized by the above.
ΔT = Tx-To ≦ 45 (I)

Here, To, Tx, E ′ _To and E ′ _Tx will be described with reference to FIG. FIG. 1 is a graph showing changes in temperature rise and storage elastic modulus of a polyimide resin composition, where the Y axis shows the storage elastic modulus of the polyimide resin composition, and the X axis shows the temperature rise of the polyimide resin composition. ing. In the present invention, the point at which the rate of change changes (leaves) from the straight line before the decrease in storage elastic modulus from the start of temperature rise, that is, the point of inflection, is the temperature at which the decrease in storage elastic modulus begins, To the storage modulus of the polyimide resin composition and E _{'the to} when the. The storage elastic modulus E ′ _Tx is E ′ _Tx = E ′ _To / 100, and the temperature at this time is Tx.

<Storage modulus>
The storage elastic modulus is a component stored in the object among the energy generated by external force and strain. The decrease in the storage elastic modulus above the inflection point is the softening of the polyimide resin composition via the glass transition. Represents. When the temperature difference ΔT ≦ 45 ° C. when E ′ _Tx = E ′ _To / 100, the fluidity is excellent at a low temperature and particularly suitable for molding. The reason for this is not clear, but it is presumed that fluidity suddenly develops above the glass transition temperature of the polyimide resin, resulting in melt properties suitable for thermoplastic molding.
When ΔT is in the above range, when the temperature is raised for hot-melt molding of the polyimide resin composition, an excessive amount of heat is not required until the required melt viscosity is reached, and the process load is reduced and heating is being performed. Of the polyimide resin composition tends to hardly progress. In addition, non-uniform distribution of viscosity is unlikely to occur, and molding defects due to poor melting tend to be suppressed.
ΔT is more preferably 40 ° C. or less, further preferably 35 ° C. or less, further preferably 30 ° C. or less, further preferably 25 ° C. or less, and particularly preferably 20 ° C. or less.
On the other hand, the lower limit value of ΔT is not particularly limited and is preferably as low as possible, but is particularly preferably 1 ° C. or higher. When ΔT is greater than 1 ° C., the viscosity does not decrease rapidly and the molding conditions tend to be easily controlled.
The storage elastic modulus of the polyimide resin obtained in the present invention can be measured using a dynamic viscoelasticity measuring device (DMS).

In the temperature rising process, the temperature To at which the storage elastic modulus of the polyimide resin composition starts to decrease is 150 ° C. or higher. Preferably it is 200 degreeC or more, More preferably, it is 250 degreeC or more. Moreover, there is no upper limit in particular and it can select suitably according to a use.
When To is 150 ° C. or higher, it is preferable in that the heat resistance of the molded body obtained using the polyimide resin composition of the present invention can be improved.

  A method for obtaining a polyimide resin composition in which the difference ΔT between Tx and To is represented by the formula (I) and To is 150 ° C. or higher is not particularly limited. For example, there is a method in which an imidization reaction is performed in the presence of a solvent and a polyimide resin composition is obtained using a synthesized polyimide resin. Moreover, the method of sealing the terminal reactive group of a polyimide resin is also mentioned. Polyimide resins obtained by these methods are likely to exhibit fluidity because their melt viscosity rapidly decreases upon heating, and are represented by the formula (I), and To tends to be 150 ° C. or higher.

<Polyimide resin composition>
The polyimide resin composition of the present invention contains at least a polyimide resin. Components other than the polyimide resin are not particularly limited, and may include, for example, a polyamic acid resin that is an unreacted product at the time of polyimide resin generation, a polyimide resin composition of a polyamic acid ester resin, a solvent used for polyimide resin generation, and the like. . In addition, it has inorganic fillers, organic fillers, metal fillers, lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers, release agents, etc. Also good.

  The ratio of the polyimide resin in the polyimide resin composition is not particularly limited, but is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. On the other hand, there is no limit on the upper limit. By adjusting the concentration of the polyimide resin composition 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 polyamic acid resin or polyamic acid ester resin to the polyimide resin composition in the polyimide resin composition is not particularly limited, but is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. . When the ratio of the polyamic acid resin or the polyamic acid ester resin in the polyimide resin composition is within an appropriate range, the polyimide resin and the polyamic acid resin or the polyamic acid ester resin do not phase separate, and the polyimide resin composition is cloudy. Tend not to occur. By using a polyimide resin composition that is not phase-separated for melt molding, the components in the molded body also become uniform, and there is a tendency that irregularities and cloudiness do not occur in the molded body.

The concentration of the solvent (residual solvent) used for producing the polyimide resin in the polyimide resin composition of the present invention is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, more preferably 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 lower. By adjusting the concentration of the residual solvent in the polyimide resin composition within this range, it is preferable that remarkable foaming is not observed at the time of melting described later, or that a combustible gas is not generated. The concentration of the residual solvent in the polyimide resin composition can be measured according to the description in JP-A-2006-70130.

The polyimide resin in the polyimide resin composition preferably has a terminal amino group sealing rate of 70% or more. By being in this range, thermal stability, transparency, color tone and the like tend to be good. This is because the chemical stability is enhanced by sealing the terminal amino group. From the viewpoint of further improving these effects, it is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. Further, the upper limit of the terminal amino group sealing rate is usually 100%. As will be described later, the terminal amino group sealing rate is the ratio of the raw acid dianhydride and the diamine compound used, the amount and type of the terminal blocking agent used in the terminal blocking reaction step, and the catalyst used in the chemical amination step. It can be controlled by the type of dehydrating agent and the amount of these used. Further, the terminal amino group sealing rate can be determined by ¹ H-NMR measurement. In the present invention, “sealing the terminal amino group” means that the hydrogen atom bonded to the terminal primary amino group is replaced by the terminal blocking agent described later.

  The polyimide resin composition of the present invention is preferably transparent and less colored. In the present specification, being colorless or transparent means that the transmittance of light at 400 nm is usually 60% or more, preferably 70% or more, and particularly preferably 80% or more when the thickness of the polyimide resin composition is 50 μm. Say something. The polyimide resin composition obtained in the present invention having a high light transmittance is suitably used in a device that requires translucency, such as a photoelectric conversion element. In this specification, the total light transmittance in a light beam of 400 nm according to JIS K 7361-1 is used as the transmittance.

  The yellowness (yellow index (YI)) of the polyimide resin composition of the present invention when the film thickness is 50 ± 5 μm is usually −10 or more, preferably −5 or more, more preferably −1. That's it. 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 composition 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 composition of the present invention is not particularly limited, but is usually 50 MPa or more, preferably 70 MPa or more, and is usually 400 MPa or less, preferably 300 MPa or less.
The tensile modulus of the polyimide resin composition of the present invention is not particularly limited, but is usually 1000 MPa or more, preferably 1500 MPa, and is usually 20 Gpa or less, preferably 10 Gpa or less.
The tensile elongation of the polyimide resin composition of 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 composition has such mechanical strength, a more durable molded body can be obtained.

The polyimide resin composition of the present invention preferably has the following melt properties.
The melt viscosity of the polyimide resin composition 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, it is preferably 1.0 × 10 ⁷ Pa · s or less, more preferably 5.0 × 10 ⁵ Pa · s or less, and even more preferably 1.0 × 10 ⁵ Pa · s or less. 1.0x1
A polyimide resin composition having a melt viscosity of 0 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 molding. The melt viscosity can be controlled by the molecular weight, molecular composition, etc. Usually, the melt viscosity increases as the molecular weight increases. The melt viscosity of the polyimide resin composition obtained in the present invention can be measured by the method of JP-A-1-297427.

The polystyrene-reduced mass average molecular weight (Mw) of the polyimide resin composition of the present invention is preferably 1.0 × 10 ³ or more, more preferably 5.0 × 10 ³ or more, more preferably 1.0 × 10 ⁴ or more. Particularly preferably, it is 5.0 × 10 ⁴ or more. On the other hand, it is preferably 1.0 × 10 ⁶ or less, more preferably 8.0 × 10 ⁵ or less, more preferably 5.0 × 10 ⁵ or less, and particularly preferably 2.0 × 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 equivalent mass average molecular weight of the polyimide resin composition according to the present invention can be determined by gel permeation chromatography (GPC).

The number average molecular weight (Mn) of the polyimide resin composition of the present invention is preferably 5.0 × 10 ² or more, more preferably 2.5 × 10 ³ or more, more preferably 5.0 × 10 ³ or more, and particularly preferably 2 0.0 × 10 ⁴ or more. On the other hand, it is preferably 5.0 × 10 ⁵ or less, more preferably 4.0 × 10 ⁵ or less, more preferably 2.5 × 10 ⁵ or less, and particularly preferably 8.0 × 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 composition according to the present invention can be measured by the same method as the mass average molecular weight.

The molecular weight distribution (PDI, (mass average molecular weight / number average molecular weight (Mw / Mn))) of the polyimide resin composition 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.
It is preferable that the molecular weight distribution is in this range in that a highly uniform solution and molded body can be obtained.

The glass transition temperature (Tg) by the differential scanning calorimetry (DSC method) of the polyimide resin composition of this invention is 150 degreeC or more normally, Preferably it is 200 degreeC or more, More preferably, it is 250 degreeC or more. When the glass transition temperature is 150 ° C. or higher, the heat resistance of the molded body of the polyimide resin composition obtained in the present invention tends to be improved.
Moreover, it is preferable that it is 100 ppm / K or less in the range of 100-200 degreeC, and, as for the thermal expansion coefficient of a polyimide resin composition, it is more preferable that it is 70 ppm / K or less. When the thermal expansion coefficient is in such a range, a molded body with high dimensional accuracy tends to be manufactured.

<Polyimide resin in polyimide resin composition>
The polyimide resin in the polyimide resin composition 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 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 a structural unit of tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides containing fluorine groups, and aliphatic tetracarboxylic dianhydrides. More specifically, the following are mentioned.

(Aromatic tetracarboxylic dianhydride)
Examples of the aromatic tetracarboxylic dianhydride include tetramellitic dianhydride, tetramellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, etc. Carboxylic 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, 1,1′-biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 2,2-bis (3,4) -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′ , 3,3'-Benzophenone Lacarboxylic dianhydride, 4,4-oxydiphthalic dianhydride, 4,4- (p-phenylenedioxy) diphthalic dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, Tetracarboxylic dianhydrides having two or more independent aromatic rings, such as 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride;
1,2,5,6-naphthalenedicarboxylic dianhydride, 1,4,5,8-naphthalenedicarboxylic dianhydride, 2,3,6,7-naphthalenedicarboxylic dianhydride, 3,4,9 , 10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracarboxylic dianhydride Tetracarboxylic dianhydride; and the like.

(Aromatic tetracarboxylic dianhydrides containing fluorine groups)
Examples of the aromatic tetracarboxylic dianhydride containing a fluorine group include 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, 1,4-difluoropyromellitic dianhydride, 1, 4-ditrifluoromethylpyromellitic dianhydride, etc. are mentioned.

(Aliphatic tetracarboxylic dianhydride)
Examples of the aliphatic tetracarboxylic dianhydride include chains such as ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, and the like. Aliphatic aliphatic tetracarboxylic dianhydrides;
1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1 , 2,3,4-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, bicyclo [2.2.1] Heptane-2,3,5,6-tetracarboxylic dianhydride, 3,3 ′, 4,4′-biscyclohexanetetracarboxylic dianhydride, 1,1′-bicyclohexane Alicyclic tetracarboxylic dianhydrides such as −3,3 ′, 4,4′-tetracarboxylic dianhydride; and the like.

  In the above, since ΔT of the polyimide resin composition is represented by the formula (I) and To tends to be 150 ° C. or higher, 1,1′-bicyclohexane-3,3 ′, 4,4 ′ -Tetracarboxylic acid-3,3 ', 4,4'-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid Use each structural unit of anhydride, pyromellitic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride Is preferred. Among these, 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride, 3,3 ′, 4,4′-biphenyl It is preferable to use each structural unit of tetracarboxylic dianhydride and 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, Furthermore, it is particularly preferable to use a structural unit of 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride.

When R ² is a structural unit of a diamine compound or a structural unit of a diisocyanate compound, the solubility in an organic solvent is improved when R ² is a divalent organic group represented by the general formula (2). In addition, the thermoplasticity is also improved, which is preferable. Moreover, it is preferable at the point from which the heat resistant and tough resin molding is obtained and the solubility to an organic solvent improves. Moreover, it is preferable at the point which colorless transparency becomes high, the coloring by time-dependent deterioration can be reduced, and the solubility to an organic solvent improves.

[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 which may have a substituent. Group,
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 alicyclic hydrocarbon group for ring A ¹ and ring A ² is not particularly limited, but is cyclobutanylene group, cyclopentalene group, cyclohexylene group, cycloheptalene group, cyclooctalene group, norbornalene group, norbornylene. And a divalent group having 3 to 30 carbon atoms such as a group, hydrinylene group, decahydronaphthalene group, and adamantalene group. Among these, a cyclohexylene group, a cyclopentalene group, and a norbornalene group are preferable from the viewpoint of easy molding of the polyimide resin composition.

The aromatic group for ring A ¹ and ring A ² is not particularly limited, and examples thereof include an aromatic hydrocarbon group and an aromatic heterocyclic group. Specific examples of the aromatic hydrocarbon group include divalent groups such as 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. It exists in the tendency for the moldability of a polyimide resin composition to improve because carbon number is this range.
Specific examples of the aromatic heterocyclic group include divalent groups such as 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. It exists in the tendency for the moldability of a polyimide resin composition to improve because carbon number is this range.
Among the aromatic groups of ring A ¹ and ring A ² , a phenylene group, a biphenylene group, and a terphenyl group are preferable. Further, the aromatic group or an aliphatic hydrocarbon group 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 group or aliphatic hydrocarbon group 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 easy molding of the polyimide resin, it is preferably a direct bond, an oxygen atom, an alkylene group which may have a substituent, a sulfinyl group, or a sulfonyl group. An alkylene group or a sulfinyl group that may have 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 from the viewpoint of easy molding of the polyimide resin composition, and is an alkylene group having 1 to 10 carbon atoms. More preferably. 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 it has the same meanings as those mentioned ring A ^1, also synonymous substituent which may have.
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 easy molding of the polyimide resin composition. 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 easy molding of the polyimide resin. 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 and 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 or the like.

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 the general formula (3), ring ^{A 22} and ring ^{A 23} is ring ^{A 1} in the general formula (2), ring ^{A 24} and ring ^{A 25} are the same meaning as ^the ring ^{A 2} in the general formula (2). Moreover, Y < ¹² > and Y < ¹³ > are synonymous with Y < ² > in General formula (2), Y < ¹ >, Y < ¹⁴ > and Y < ¹⁵ > in General formula (2). Further, ^{X 5} has the same meaning as ^{X 1} in the general formula (2).
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 group which may have a substituent. It is preferable from the point. 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 easy molding of the polyimide resin, Y ¹² and Y ¹³ are preferably direct bonds, oxygen atoms or sulfur atoms, and Y ¹⁴ and Y ¹⁵ are preferably direct bonds.

Equation (4) corresponds to the case where p = 1 and q = 1 in Equation (2). In Formula (4), Ring A ²⁶ and Ring A ²⁷ represent the same structure as Ring A ¹ and Ring A ² in Formula (2). Y ¹⁶ and Y ¹⁷ represent the same structure as Y ¹ and Y ² in Formula (2). 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 group or a substituent that may have a substituent from the viewpoint of easy molding of the polyimide resin composition. It is preferably an aliphatic hydrocarbon group. 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 or diisocyanate compounds shown below. That is, the divalent groups derived by removing two primary amino groups or isocyanate groups from a diamine compound shown below, or diisocyanate compound can be used as R ^2.
Specific examples of such compounds include the following compounds.

(Aromatic diisocyanate compound)
Examples of the aromatic diisocyanate compound include 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 4,4′-diisocyanato-3,3. '-Dimethyldiphenylmethane, 1,5-diisocyanatonaphthalene, methylenediphenyl 4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-bis (isocyanatomethyl) ) Benzene, toluene diisocyanate and the like.

(Aliphatic diisocyanate compound)
Examples of the aliphatic diisocyanate compound include 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, and isophorone diisocyanate.

(Aromatic diamine compound)
Examples of the aromatic diamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 3-aminobenzylamine, 2,5-dimethyl-1,4-phenylenediamine, p A diamine compound having one aromatic ring in the molecule, such as xylylenediamine, m-xylylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine;
4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) neopentane, 4,4′-diamino-3,3′-dimethylbiphenyl, 4,4′-diamino -2,2'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (4-amino-3-carboxyphenyl) methane, 4,4'-diaminodiphenyl sulfone, 4,4 ' -Diaminodiphenyl sulfide, N- (4-aminophenoxy) -4-aminobenzamide, 2,7-diaminofluorene, 1,1-bis (4-aminophenyl) cyclohexane, bis (3-aminophenyl) sulfone, 3, 3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diamino-3,3'-dimethyldipheni Methane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-ethylenedianiline, 4,4′-methylenebis (2,6-diethylaniline), 4,4′-methylenebis (2-ethyl-6-methylaniline), 4,4′-diamino-2,2′-dimethoxybiphenyl, 2,3′-diaminodiphenyl ether, bis (
4-aminophenoxy) methane, 1,3′-bis (4-aminophenoxy) propane,
, 4′-bis (4-aminophenoxy) butane, 1,5′-bis (4-aminophenoxy) pentane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, bis (3
A diamine compound having two independent aromatic rings such as -amino-4-hydroxyphenyl) sulfone, N, N-bis (4-aminophenyl) piperazine, 4-aminobenzoic acid-4-aminophenyl;
1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) -2,5-di-t-butylbenzene, 1 , 4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene, N, N-bis (4-aminophenyl) terephthalamide, 1,3-bis (3-aminophenoxy) benzene, α, α Diamine compounds having three independent aromatic rings such as' -bis (4-aminophenyl) -1,4-diisopropylbenzene and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene ;
2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 4,4 ′ -Bis (4-aminophenoxy) biphenyl, 4,4 '-(9-fluorenylidene) dianiline, 4,4'-(biphenyl-2,5-diylbisoxy) bisaniline, 4,4'-bis (4-aminobenzamide) ) Diamine compounds having four independent aromatic rings such as -3,3'-dihydroxybiphenyl, 4,4'-bis (4-aminophenoxy) benzophenone, and the like;
2- (4-aminophenyl) -6-aminobenzoxazole, 2- (4-aminophenyl) -5-aminobenzoxazole, 5-amino-2- (4-aminophenyl) -1H-benzimidazole, 1, And a diamine compound having a condensed aromatic ring such as 5-diaminonaphthalene and 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide.

(Aromatic diamine compounds containing fluorine groups)
As an aromatic diamine compound containing a fluorine group, for example, 5-trifluoromethyl-1,3-benzenediamine, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4 '-Diamino-2,2'-bis (trifluoromethyl) biphenyl ether, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 4,4′-diaminooctafluorobiphenyl, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4, 4′-diamino-2- (trifluoromethyl) diphenyl ether, 1,4-bis {4-amino-2- (trifluoromethyl) phenoxy Si} benzene, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoro Examples include propane.

(Aliphatic diamine compound)
Examples of the aliphatic diamine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 4 , 4′-methylenebis (2-methylcyclohexylamine) and the like.

In the above, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diamino-3,3′-dimethylbiphenyl, 2,2-bis (4- (4-aminophenoxy) phenyl) Propane, N- (4-aminophenoxy) -4-aminobenzamide, 1,3-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-diamino- Using each structural unit of 2,2′-bis (trifluoromethyl) biphenyl and 4-aminobenzoic acid-4-aminophenyl indicates that ΔT of the polyimide resin composition is represented by the formula (I) and To Is preferable because it tends to be 150 ° C. or higher.

Moreover, in the above, when colorless transparency is especially required as the performance of the molded body using the polyimide resin composition, combinations of the following structural units are preferred examples.
A. B. Combinations of aromatic tetracarboxylic dianhydrides and aliphatic diamines or aliphatic diisocyanates Aliphatic tetracarboxylic dianhydrides and aromatic diamines and / or aliphatic diamines C.I. C. Combinations of aliphatic tetracarboxylic dianhydrides with aromatic diisocyanates and / or aliphatic isocyanates Combination of fluorine-containing aromatic tetracarboxylic dianhydrides with fluorine-containing aromatic diamines or fluorine-containing aromatic isocyanates

  Further, in the above, when heat resistance and dimensional stability are particularly required as the performance of the molded body using the polyimide resin composition, each configuration of aromatic tetracarboxylic dianhydrides and aromatic diamines It is preferable to use units. By using these, the molding obtained using the polyimide resin composition tends to have a glass transition point of 300 ° C. or higher, and tends to have a linear expansion coefficient of 10 ppm or lower.

Among the polyimide resins used in the molded article of the polyimide resin composition of the present invention, ΔT of the polyimide resin composition is represented by the formula (I), and To tends to be 150 ° C. or higher, and the obtained polyimide Since colorless transparency can be imparted to a molded article such as a film, 1,1′-bicyclohexane-3,3 constituted by a tetracarboxylic acid residue having a bicyclohexane skeleton represented by the general formula (5) It is preferable to use a structural unit of ', 4,4'-tetracarboxylic acid-3,3', 4,4'-dianhydride.
Thus, the polyimide resin constituted by a tetracarboxylic acid residue having a bicyclohexane skeleton is a polyimide constituted by an aromatic ring such as biphenyl or a tetracarboxylic acid residue having a monocyclic aliphatic ring as a skeleton. Compared to a resin, the effects of reduced coloring, improved solubility, and low retardation can be obtained. Moreover, these polyimide resins are excellent in moldability, 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. ]

A divalent organic group R ³ has the same meaning as R ² in the general formula (1) may substituent and preferred examples have 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 represented by the general formula (5) is preferably 40000 or more, and more preferably. It is preferable from the viewpoint of the strength of the molded body using the polyimide resin composition that a is determined to be 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 the extent that various physical properties such as moldability, heat resistance, and colorless transparency of the polyimide resin composition according to this embodiment are not impaired. . The tetracarboxylic dianhydride to be mixed may be one type or two or more types.

Moreover, in order to control the fluidity | liquidity at the time of the polyimide resin composition melt | dissolution of the below-mentioned process, the additive may be added to the polyimide resin composition 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 composition 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 composition of the present invention may contain one type of coupling agent or two or more types of coupling agents. The amount of the coupling agent contained in the polyimide resin composition 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 composition 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 composition.

  In addition, the polyimide resin composition according to the present invention may contain an antioxidant in order to suppress coloring during molding, drying, and various processes using the molded body of the polyimide resin composition.

  The antioxidant may be added at any stage of the process of producing the polyimide resin, polyimide resin composition, polyimide resin composition molded body, but as a solution by adding an antioxidant to the polyimide resin solution or polyamic acid resin solution The method to use and the method of mixing antioxidant with polyimide resin powder can be used suitably. When mixing antioxidant with a polyimide resin powder, it is preferable at the point which can suppress both discoloration in shaping | molding of polyimide resin powder, and the time-dependent coloring of the obtained polyimide resin composition molded object.

The addition amount of the antioxidant is not particularly limited, but is 0.001% by mass with respect to the polyimide resin composition.
The above is preferable, 0.005% by mass or more is further preferable, 0.01% by mass or more is further preferable, and 0.05% by mass or more is particularly preferable. 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.
Antioxidants may be used alone or in admixture of two or more, but in the case of mixing, a mixture of hindered phenolic antioxidants and phosphorus antioxidants or hindered phenolic antioxidants And mixtures of sulfur-based antioxidants are preferred. 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 composition 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 composition or a polyimide resin composition molded body.

<Method for producing polyimide resin composition>
The manufacturing method of the polyimide resin composition of this invention is not specifically limited. Since the difference ΔT between Tx and To of the polyimide resin composition is represented by the formula (I) and To is 150 ° C. or higher, it is preferable to obtain a polyimide resin by imidization in the presence of a solvent. Moreover, although the thermal imidation, chemical imidation, etc. can be used for the method of imidation, after passing through a thermal imidation reaction process, it can obtain through an end capping reaction process and / or a chemical imidation process. The end-capping reaction step and the chemical imidization step can be performed in any order, and these may be performed at the same time, but after the end-capping reaction step, the chemical imidization reaction step is performed. Is preferred.
Hereinafter, heating imidization, chemical imidization, and end-capping reaction will be described in detail.

  The polyimide resin contained in the polyimide resin composition used in the present invention includes a polyamic acid resin or a polyamic acid ester resin, a method of dehydrating cyclization or dealcoholization cyclization in the presence of a solvent, and a tetracarboxylic dianhydride and a diisocyanate compound. Is obtained in the presence of a solvent (hereinafter collectively referred to as imidization).

The imidization method is not particularly limited, and can be performed using any conventionally known method. Examples thereof include thermal imidization that causes thermal cyclization and chemical imidization that causes chemical cyclization. These imidization reactions may be used alone or in combination.
Further, after the imidization, an end-capping reaction may be performed. End-capping is preferable in that the polymerizability of each resin terminal is lowered and the solution viscosity of the polyimide resin is stabilized.
The method of terminal sealing is not limited, and any conventionally known method may be used, and sealing may be performed at any stage of preparing the polyimide resin composition. Preferably, after thermal imidization, it is preferable to undergo end-capping process and / or chemical imidization. The end-capping reaction and the chemical imidization can be performed in any order, and these may be performed simultaneously, but it is preferable that the end-capping reaction is followed by chemical imidization.
An example of the imidization method will be described below, but the present invention is not limited to this method.

(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, or heating a tetracarboxylic dianhydride and a diisocyanate compound in the presence of a solvent.
When the polyamic acid resin or the polyamic acid ester resin is heated in the presence of a solvent, it is preferable that water or alcohol generated by imidization is discharged out of the reaction system in order to inhibit the ring closure reaction. For example, a method in which water is discharged out of the system by azeotropically boiling an organic solvent such as toluene or xylene with water is often used.

  Examples of the solvent used when imidizing by heating include a solvent 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 resins, polyamic acid ester resins and polyimide resins, and have boiling points. Is high, so that the imidization reaction proceeds efficiently.

  When the polyamic acid resin or the polyamic acid ester resin is heated in the presence of a solvent, the concentration of the polyamic acid resin or the polyamic acid ester resin in the imidization reaction solution is not particularly limited. Usually, it is 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more. Moreover, it is 80 mass% or less normally, Preferably it is 60 mass% or less, More preferably, it is 40 mass% or less. 20 mass% or more is preferable in terms of high production efficiency, and 40 mass% or less is preferable in that the solution viscosity is easy to handle with ordinary production equipment.

When the tetracarboxylic dianhydride and the diisocyanate compound are heated in the presence of a solvent, the amounts of the tetracarboxylic dianhydride and the diisocyanate compound in the imidization reaction solution are not particularly limited. For example, the total mass of the tetracarboxylic dianhydride and the diisocyanate compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, based on the amount of the imidization reaction solution, Usually, it is 70 mass% or less, Preferably it is 30 mass% or less. By setting it in such a range, the solution viscosity is good in yield and easy to handle with ordinary production 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 the temperature is 120 ° C or higher, and it is preferable in that the side reaction other than the imidization reaction is suppressed when the temperature is 250 ° 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. When the polyimide film is required to be colorless and transparent, it is preferably heated in an inert atmosphere such as nitrogen in order to suppress coloring.

  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.
The chemical imidization of the present invention refers to heating a polyamic acid by adding a dehydrating condensing agent 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 heating imidization.

  Although there is no restriction | limiting in particular in the density | concentration of the polyamic acid resin or polyamic acid ester resin of an imidation reaction solution, Usually, 5 mass% or more, Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more. Moreover, it is 80 mass% or less normally, Preferably it is 60 mass% or less, More preferably, it is 40 mass% or less. 20% by mass or more is preferable in terms of high production efficiency, and 40% or less is preferable in that the solution viscosity is easy to handle in normal production 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 the temperature is 120 ° C or higher, and it is preferable in that the side reaction other than the imidization reaction is suppressed when the temperature is 250 ° 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. When the polyimide film is required to be colorless and transparent, it is preferably heated in an inert atmosphere such as nitrogen in order to suppress coloring.
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 diethyl phosphate anide 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.

(End-capping reaction)
In the present invention, the “end-capping reaction” means a step of capping the terminal amino group of polyimide with an end-capping agent.
The end capping agent used in the end capping reaction is not particularly limited as long as it reacts with an amino group to form a stable structure. For example, phthalic anhydride, succinic anhydride, 1,2-cyclohexane Acid anhydrides such as dicarboxylic acid anhydride, 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, (2-methyl-2-propenyl) succinic acid anhydride; organic acid chlorides such as benzoic acid chloride and the like . The end capping agents mentioned above may be used alone or in combination. In addition, when sealing the terminal acid anhydride group of the polyimide of this invention, amine compounds, such as 3-aminophenyl acetylene, aniline, a cyclohexylamine, can also be used as terminal blocker. However, the sealing of the terminal acid anhydride group does not correspond to the sealing of the terminal amino group in the present invention.

  The amount of terminal blocking agent used is preferably 1 to 10 times the number of equivalents of the difference between the number of moles of the diamine compound used as a raw material and the number of moles of acid dianhydride (the amount of unreacted primary amino group). More preferably, the equivalent number is 2 to 8 times. When the amount of the terminal blocking agent used is less than or equal to the above lower limit value, it is preferable for increasing the blocking rate of the terminal amino group. On the other hand, when it is less than or equal to the above upper limit value, there is little purification treatment of unreacted terminal blocking agent. This is preferable. In addition, when not performing the chemical imidation reaction mentioned later, in order to raise the sealing rate of a terminal amino group, increasing the usage-amount of terminal blocker is preferable.

  The reaction temperature in the end-capping reaction is usually 80 to 200 ° C, preferably 120 to 200 ° C. The thermal imidization reaction may be performed under normal pressure (0.1 MPa), reduced pressure, or increased pressure, but is usually performed under normal pressure. The reaction time for the end-capping reaction is usually 1 hour or longer, preferably 2 hours to 10 hours.

<Process for melt-molding a polyimide resin composition>
A process for obtaining a molded body using the polyimide resin composition by melting and molding the polyimide resin composition of the present invention will be described.
First, the process of melting the polyimide resin composition 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 composition of the present invention, but is preferably equal to or higher than the melting point and lower than the decomposition temperature of the polyimide resin.

The polyimide resin composition of this invention can mix | blend components other than the polyimide resin mentioned above in the range which does not impair the objective of this invention as desired. The polyimide resin may be a thermoplastic resin, and may be prepared by mixing fillers and various additional components used as desired, and kneading with a kneader, or may be used in advance as a thermoplastic resin and as desired. The additive component to be obtained may be quantitatively supplied to an extruder and kneaded, and the filler may be prepared by side-feeding and kneading the filler into the melted portion.

  Furthermore, what processed the filler into flat form, such as a nonwoven fabric, may be laminated with the softened polyimide resin composition of the present invention. The kneader is not particularly limited as long as it can knead the polyimide resin composition, the filler, and the additive. For example, a screw extruder such as a single screw extruder or a multi-screw extruder, an elastic extruder, or the like. And non-screw extruders such as hydrodynamic extruders, ram-type continuous extruders, roll-type extruders and gear-type extruders.

Next, the process of shape | molding a polyimide resin composition melt is demonstrated. The polyimide resin composition of the present invention obtained above is an injection molding method, extrusion molding method, hollow molding method, compression molding method, lamination molding method, roll processing method, stretching processing method, stamp processing method, hot press method or It is molded into a desired molded product by various molding methods such as a T-die method. Among these, when it is set as a film use, it can be manufactured using an extrusion molding method, a lamination molding method, a stretching method, or the like. Also, 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 of the polyimide resin, and is usually not higher than the decomposition temperature of the polyimide resin.
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. .

The molded body using the polyimide resin composition of the present invention can produce 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 molded body using the polyimide resin composition obtained by the present invention can have a three-dimensionally complicated shape that cannot be achieved by existing polyimide resins, and is excellent in transparency, heat resistance, mechanical properties, and the like. Tend to be obtained.
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, according to the present invention, there is no time for contact with the support or the like in the heated state, or the time is short, which is preferable in that the difference in performance between the front side and the back side of the film hardly occurs.

  The polyimide resin composition obtained in the present invention can be formed into various shaped polyimide resin composition molded bodies by the above-described various molding methods. Accordingly, the present invention can be applied to a wide range of uses as well as a film use which is a typical use of a molded article of a polyimide resin composition. 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 production of a recording base, a film for a capacitor or a flexible printed circuit board, and the like. Moreover, it is used also for manufacture of the molded member of the structural member reinforced with glass fiber, carbon fiber, etc., the bobbin of a small coil, or the terminal insulation 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.

[Storage modulus measurement]
Using a dynamic viscoelasticity analyzer (DMS200 manufactured by Seiko Electronics Co., Ltd.) (sample size width 9 mm, length 40 mm), frequency 0.1, 1.0, 10 Hz, temperature increase rate 3 ° C./mi
n was measured in a temperature range of 50 to 350 ° C. Temperature (T ₀ ) that is the inflection point of the curve plotting storage modulus against temperature (T ₀ ), storage modulus at T ₀ (E ' _To ), temperature at which E' _Tx = E ' _To / 100 (Tx )

[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 added dropwise, 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 step: preparation of polyamic acid resin solution)
H-BPDA obtained in the first step 36.0. g (0.118 mol) was added to 180 g of N, N-dimethylacetamide and 24.03 g (0.12 mol) of 4,4′-diaminodiphenyl ether (manufactured by Wakayama Seika Co., Ltd.), and the mixture was heated and stirred at 80 ° C. for 6 hours. A polyamic acid resin solution was obtained.

(Third step: a step of imidizing a polyamic acid ester resin in the presence of a solvent to obtain a polyimide resin composition)
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 polyamic acid ester resin solution obtained in the synthesis example was added in its entirety, and 36.0 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 145 ° 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, 5.69 g of phthalic anhydride was added as a terminal blocking agent, followed by heating, refluxing and stirring for 4 hours, and toluene was distilled off. Next, 0.018 g of triethylamine and 0.035 g of acetic anhydride were added, and the mixture was heated and stirred at 60 ° C. for 3 hours to obtain a polyimide resin composition solution. The obtained polyimide resin composition solution was dropped into 3000 ml of isopropyl alcohol, and the deposited polyimide resin composition was collected by filtration to obtain a white powder of the polyimide resin composition. Next, 25 g of the obtained polyimide resin composition was dissolved in 75 g of N, N-dimethylacetamide to obtain an N, N-dimethylacetamide solution containing the polyimide resin composition.

<Example 1>
The obtained N, N-dimethylacetamide solution containing the polyimide resin composition was cast at a thickness of 100 μm on a glass plate using a film applicator, and dried at 80 ° C. for 30 minutes under reduced pressure to form a film. Thereafter, it was dried at 230 ° C. for 1 hour in a nitrogen atmosphere and further at 300 ° C. for 1 hour to prepare a polyimide resin composition film. The obtained polyimide resin composition film was peeled from the glass plate to obtain a polyimide resin composition piece. Table 1 shows the results of storage elastic modulus measurement and total light transmittance measurement performed on the obtained polyimide resin composition pieces.

<Comparative Example 1>
The same test as in Example 1 was performed on a transparent polyimide film (product name: Neoprim L-3430) manufactured by Mitsubishi Gas Chemical Co., Ltd. used as a commercial product. The total light transmittance was measured at 100 μm. The results are shown in Table 1.

<Comparative example 2>
The same test as Comparative Example 1 was performed on a transparent polyimide film (product name: Neoprim L-1000) manufactured by Mitsubishi Gas Chemical Co., Ltd. used as a commercial product. The results are shown in Table 1.

From the results in Table 1, it was shown that the polyimide resin composition of Example 1 rapidly changed its storage elastic modulus by heating, and rapidly softened. On the other hand, it was shown that the polyimide resin compositions of Comparative Example 1 and Comparative Example 2 required strong heating to cause a sufficient change in storage modulus.
From the above results, it was shown that the polyimide resin composition according to the present invention is suitable for melt molding, and a molded body having a desired shape can be produced by a process with less load.

E´; Storage modulus of polyimide resin composition
E ′ _To ; storage modulus at temperature To
E ′ _Tx ; storage elastic modulus at temperature Tx T; temperature rise temperature of polyimide resin composition
To: temperature at which the storage elastic modulus of the polyimide resin composition starts to decrease in the temperature rising process
Tx: Temperature at which E ' _To / 100

Claims (3)

A resin composition containing a polyimide resin, wherein the temperature at which the storage elastic modulus begins to decrease during the temperature rising process is To, the storage elastic modulus at _To is E ' _To , and the storage elastic modulus (E' _Tx ) is E ' _Tx = T 'is the temperature when E' _To / 100, and the difference ΔT between Tx and To is expressed by the following formula (I), and To is 150 ° C
It is the above, The polyimide resin composition characterized by the above-mentioned.
ΔT = Tx-To ≦ 45 (I) The total light transmittance at 400 nm at a thickness of 50 μm of the polyimide resin composition is 60%.
The polyimide resin composition according to claim 1, which is as described above.   A film comprising the polyimide resin composition according to claim 1.

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