JP2018070699A - Polyimide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide-based resin composition excellent in heat resistance, rigidity and impact resistance, and to provide a molded body and a film using the composition.SOLUTION: A polyimide-based resin composition contains a polyether imide resin (A) and a crystalline polyimide resin (B) containing a tetracarboxylic acid component (b-1) and an aliphatic diamine component (b-2), where a content ratio of the polyether imide resin (A) and the crystalline polyimide resin (B) is (A):(B)=1:99 to 99:1. In the polyimide-based resin composition, the aliphatic diamine component (b-2) preferably contains at least C4-12 linear aliphatic diamine, preferably further contains alicyclic diamine, and more preferably is 1,3-bis(aminomethyl)cyclohexane.SELECTED DRAWING: None

Description

  The present invention relates to a polyimide resin composition having excellent heat resistance, rigidity, and impact resistance, and a molded body obtained by molding the polyimide resin composition, particularly a film.

  Polyetherimide resin is a non-crystalline super engineering plastic with a glass transition temperature exceeding 200 ° C. Utilizing its excellent heat resistance, flame retardancy, and moldability, it is an automobile member, aircraft member, electric / electronic member, etc. Widely used in However, polyetherimide resin is a very brittle material, and there is a problem that it is difficult to use in applications that require impact resistance. Moreover, since the rigidity is high and the flexibility is low, there is a problem that it is difficult to use in applications that require the original flexibility (flexibility) of the plastic film.

  In response to these problems, Patent Document 1 discloses a resin composition obtained by blending a polyester resin and an epoxy compound with a polyetherimide resin, and the composition has impact resistance and hydrolysis resistance. There is a description that it is excellent in tab bending resistance (bending resistance).

JP 2002-532599 A

  However, since the polyetherimide resin has a high glass transition temperature and a high molding temperature, the polyester resin may be decomposed and deteriorated during blending. Moreover, polyetherimide resin and polyester resin have many incompatible combinations, and it cannot be said that the impact resistance is necessarily improved by blending. For example, in the examples of Patent Document 1, the impact resistance evaluated by the tensile elongation at break and the bending resistance is improved, and the elastic modulus (rigidity) is reduced and included in an appropriate range. However, there is no example that satisfies all the performance in a well-balanced manner, and it cannot be said that the problems of the polyetherimide resin can be solved satisfactorily.

  On the other hand, a crystalline polyimide resin composed of tetracarboxylic acid and an aliphatic diamine has an excellent balance between heat resistance and impact resistance. However, although it is excellent in impact resistance, since the rigidity is relatively low, there is a problem that it is inferior in handling property when used as a thin film depending on the application. Moreover, since expensive monomers, such as alicyclic diamine, are used, the raw material unit price becomes high and the subject that an application will be limited also occurs.

  As a result of intensive studies, the present inventors have found that crystalline polyimide resins having a specific structure are highly compatible with polyetherimide resins, so that these blends can solve the above problems, and the present invention. It came to.

  That is, the first aspect of the present invention is a polyetherimide resin (A) and a crystalline polyimide resin (B) containing a tetracarboxylic acid component (b-1) and an aliphatic diamine component (b-2). The content ratio of the said polyetherimide resin (A) and the said crystalline polyimide resin (B) is (A) :( B) = 1: 99-99: 1 mass%. It is a polyimide resin composition characterized by being.

  1st aspect of this invention WHEREIN: It is preferable that the said aliphatic diamine component (b-2) contains a C4-C12 linear aliphatic diamine at least.

  1st aspect of this invention WHEREIN: It is preferable that the said aliphatic diamine component (b-2) contains an alicyclic diamine at least.

  In the first aspect of the present invention, the alicyclic diamine is preferably 1,3-bis (aminomethyl) cyclohexane.

  In the first aspect of the present invention, the loss tangent (tan δ) measured at a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3 ° C./min by temperature dispersion measurement of dynamic viscoelasticity described in JIS K7244-4. It is preferable that there is one peak value.

  1st aspect of this invention WHEREIN: It is preferable that the temperature (Tg) which the peak value of the said loss tangent (tan-delta) shows is 150 to 300 degreeC.

  1st aspect of this invention WHEREIN: It is preferable that the tensile elasticity modulus measured based on JISK7127 is 2200 Mpa or more and 3100 Mpa or less.

  In the first aspect of the present invention, the tensile elongation at break measured in accordance with JIS K7127 is preferably 130% or more.

  The second aspect of the present invention is a molded body formed by using the polyimide resin composition according to the first aspect of the present invention.

  2nd aspect of this invention WHEREIN: It is preferable that the said molded object is a film.

  ADVANTAGE OF THE INVENTION According to this invention, the polyimide resin composition excellent in heat resistance, rigidity, and impact resistance, and the molded object and film using this composition can be provided.

  Hereinafter, the present invention will be described in detail, but the present invention is not limited to the embodiments described below. Unless otherwise specified, the notation “A to B” for numerical values A and B means “A to B”. In this notation, when a unit is attached to only the numerical value B, the unit is also applied to the numerical value A.

  The polyimide resin composition of the present invention contains a polyetherimide resin (A) and a crystalline polyimide resin (B).

<Polyetherimide resin (A)>
The polyetherimide resin (A) is not particularly limited, and a known compound can be used, and its production method and characteristics are described in, for example, US Pat. Nos. 3,803,085 and 3,905,942. ing.

  Specifically, the polyetherimide resin (A) used in the present invention preferably has a structure represented by the following formula (1) from the viewpoint of excellent balance between heat resistance and moldability. .

上記式（化１）において、ｎ（繰り返し数）は通常１０〜１，０００の範囲の整数であり、好ましくは１０〜５００である。ｎがかかる範囲にあれば、成形性と耐熱性のバランスに優れる。

In the above formula (Formula 1), n (the number of repetitions) is usually an integer in the range of 10 to 1,000, preferably 10 to 500. If n is in such a range, the balance between moldability and heat resistance is excellent.

  The above formula (Chemical Formula 1) can be classified into the structures represented by the following (Chemical Formula 2) and (Chemical Formula 3), respectively, from the difference in the bonding mode, specifically, the difference between the meta bond and the para bond.

上記（化２）及び（化３）において、ｎ（繰り返し数）は通常１０〜１，０００の範囲の整数であり、好ましくは１０〜５００である。ｎがかかる範囲にあれば、成形性と耐熱性のバランスに優れる。

In the above (Chemical Formula 2) and (Chemical Formula 3), n (the number of repetitions) is usually an integer in the range of 10 to 1,000, preferably 10 to 500. If n is in such a range, the balance between moldability and heat resistance is excellent.

  Specific examples of the polyetherimide resin (A) having such a structure are commercially available, for example, from the Subic Innovative Plastics Corporation under the trade name “Ultem” series.

  The glass transition temperature of the polyetherimide resin (A) is preferably 160 ° C. or higher and 300 ° C. or lower, more preferably 170 ° C. or higher and 290 ° C. or lower, and still more preferably 180 ° C. or higher and 280 ° C. or lower. 190 ° C. or higher and 270 ° C. or lower is particularly preferable, and 200 ° C. or higher and 260 ° C. or lower is particularly preferable. When the glass transition temperature of the polyetherimide resin (A) is 160 ° C. or higher, the heat resistance of the polyimide-based resin composition becomes sufficient. On the other hand, when the polyetherimide resin (A) has a glass transition temperature of 300 ° C. or lower, it can be molded or secondary processed at a relatively low temperature. Therefore, when blended with the crystalline polyimide resin (B), the crystalline polyimide It does not cause decomposition or deterioration of the resin (B).

<Crystalline polyimide resin (B)>
The crystalline polyimide resin (B) used in the present invention is obtained by polymerizing a tetracarboxylic acid component and a diamine component.

  The tetracarboxylic acid component (b-1) constituting the crystalline polyimide resin (B) is cyclobutane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid, Cycloaliphatic tetracarboxylic acid such as cyclohexane-1,2,4,5-tetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetra Examples thereof include carboxylic acid, biphenyltetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, pyromellitic acid and the like. Moreover, these alkyl ester bodies can also be used.

  Especially, it is preferable that the component exceeding 50 mol% among tetracarboxylic acid components (b-1) is pyromellitic acid. When the tetracarboxylic acid component (b-1) is mainly composed of pyromellitic acid, the polyimide resin composition of the present invention is excellent in heat resistance, secondary processability and low water absorption. From this viewpoint, among the tetracarboxylic acid component (b-1), pyromellitic acid is more preferably 60 mol% or more, further preferably 80 mol% or more, and 90 mol% or more. In particular, it is particularly preferable that all (100 mol%) of the tetracarboxylic acid component (a-1) is pyromellitic acid.

  It is important that the diamine component constituting the crystalline polyimide resin (B) is mainly composed of an aliphatic diamine (b-2). That is, it is important that the component exceeding 50 mol% of the diamine component is the aliphatic diamine (b-2), more preferably 60 mol% or more, and still more preferably 80 mol% or more. 90 mol% or more is particularly preferable, and it is particularly preferable that all (100 mol%) of the diamine component is an aliphatic diamine (b-2). Thereby, heat resistance, low water absorption, moldability, and secondary processability can be imparted to the polyimide resin composition of the present invention. The aliphatic diamine in the present invention includes alicyclic diamines.

  The aliphatic diamine (b-2) is not particularly limited as long as it is a diamine component having amine groups at both ends of the hydrocarbon group, but when heat resistance is important, it is added at both ends of the cyclic hydrocarbon. It is preferable to include an alicyclic diamine having an amine group. Specific examples of the alicyclic diamine include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-methylenebis (2- Methylcyclohexylamine), isophoronediamine, norbornanediamine, bis (aminomethyl) tricyclodecane and the like. Among these, 1,3-bis (aminomethyl) cyclohexane is preferably used from the viewpoint of achieving both heat resistance, moldability, and secondary processability.

  On the other hand, in the polyimide resin composition of the present invention, when importance is placed on impact resistance, moldability, and secondary processability, as the aliphatic diamine (b-2), at the end of the linear hydrocarbon amount. It is preferable to include a linear aliphatic diamine having an amine group. The linear aliphatic diamine is not particularly limited as long as it is a diamine component having amine groups at both ends of the alkyl group. Specific examples include ethylene diamine (carbon number 2), propylene diamine (carbon number 3), Butanediamine (carbon number 4), pentanediamine (carbon number 5), hexanediamine (carbon number 6), heptanediamine (carbon number 7), octanediamine (carbon number 8), nonanediamine (carbon number 9), decanediamine ( 10 carbon atoms, undecane diamine (11 carbon atoms), dodecane diamine (12 carbon atoms), tridecane diamine (13 carbon atoms), tetradecane diamine (14 carbon atoms), pentadecane diamine (15 carbon atoms), hexadecane diamine (carbon) 16), heptadecanediamine (carbon number 17), octadecanediamine (carbon number 18) Nona decane diamine (19 carbon atoms), eicosane (20 carbon atoms), triacontane (30 carbon atoms), Tetorakontan (40 carbon atoms), pentacontanoic (number 50 atoms) and the like. Among these, C4-C12 linear aliphatic diamine is mentioned from a viewpoint that it is excellent in a moldability, secondary workability, and low hygroscopicity. These linear aliphatic diamines may have a branched structure having 1 to 10 carbon atoms.

  As a component other than the aliphatic diamine (b-2), another diamine component may be included. Specifically, 1,4-phenylenediamine, 1,3-phenylenediamine, 2,4-toluenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, α, α'-bis (4-aminophenyl) ) 1,4′-diisopropylbenzene, α, α′-bis (3-aminophenyl) -1,4-diisopropylbenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4 '-Diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) Enyl] sulfone, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, aromatic diamine components such as p-xylylenediamine, m-xylylenediamine, polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis Examples include ether diamine components such as (3-aminopropyl) ether, siloxane diamines, and the like.

  The aliphatic diamine (b-2) may contain either or both of an alicyclic diamine and a linear aliphatic diamine, but since it has an excellent balance between heat resistance and moldability, It is preferable to include both linear aliphatic diamines. When both an alicyclic diamine and a linear aliphatic diamine are included, the content of each is preferably in the range of alicyclic diamine: linear aliphatic diamine = 99: 1 to 1:99 mol%. 90:10 to 10:90 mol%, more preferably 80:20 to 20:80 mol%, still more preferably 70:30 to 30:70 mol%, : 40 to 40: 60 mol% is particularly preferable. If the ratio of the alicyclic diamine and the linear aliphatic diamine contained in the aliphatic diamine (b-2) is within such a range, the polyimide resin composition of the present invention has heat resistance, impact resistance and moldability. Excellent balance.

  The crystal melting temperature of the crystalline polyimide resin (B) is preferably 260 ° C. or higher and 350 ° C. or lower, more preferably 270 ° C. or higher and 345 ° C. or lower, and more preferably 280 ° C. or higher and 340 ° C. or lower. Further preferred. If the crystal melting temperature of the crystalline polyimide resin (B) is 260 ° C. or higher, the heat resistance of the polyimide resin composition will be sufficient. On the other hand, a crystal melting temperature of 350 ° C. or lower is preferable because, for example, molding or secondary processing can be performed at a relatively low temperature when molding using the polyimide resin composition of the present invention.

  The glass transition temperature of the crystalline polyimide resin (B) is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 160 ° C. or higher and 290 ° C. or lower, and 170 ° C. or higher and 280 ° C. or lower. Further preferred. When the glass transition temperature of the crystalline polyimide resin (B) is 150 ° C. or higher, the heat resistance of the polyimide resin composition is sufficient. On the other hand, a glass transition temperature of 300 ° C. or lower is preferable because molding can be performed at a relatively low temperature when molding using the polyimide resin composition of the present invention. Moreover, when the obtained molded object is secondary-processed, it is preferable for the same reason.

<Polyimide resin composition>
In the polyimide resin composition of the present invention, the content ratio of the polyetherimide resin (A) and the crystalline polyimide resin (B) is (A) :( B) = 1: 99 to 99: 1 mass%. It is characterized by that.

  The content rate of the said polyetherimide resin (A) and the said crystalline polyimide resin (B) can be suitably adjusted according to the use requested | required. In the polyimide resin composition of the present invention, for example, when importance is attached to heat resistance and rigidity, the content ratio of the polyetherimide resin (A) and the crystalline polyimide resin (B) is (A) :( B). = 60:40 is preferred, 70:30 is more preferred, and 80:20 is even more preferred. On the other hand, when the impact resistance is emphasized, the content ratio of the polyetherimide resin (A) and the crystalline polyimide resin (B) is preferably (A) :( B) = 40: 60, 30:70 is more preferable, and 20:80 is still more preferable.

  The polyimide resin composition of the present invention has a loss tangent (measured by dynamic viscoelastic temperature dispersion measurement described in JIS K7244-4 at a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3 ° C./min ( There is one peak value of tan δ).

  In the present invention, the temperature indicated by the peak value of the loss tangent (tan δ) is defined as the glass transition temperature (Tg). In addition, it can be said that the presence of one peak value of loss tangent (tan δ) means that the glass transition temperature (Tg) is single. Furthermore, according to JISK7121, it can be said that when the glass transition temperature is measured using a differential scanning calorimeter at a heating rate of 10 ° C./min, only one inflection point indicating the glass transition temperature appears.

  In general, if the polymer blend composition has a single glass transition temperature, it means that the resin to be mixed is in a compatible state at the molecular level, and can be recognized as a compatible system. In addition, when there are two peak values of loss tangent (tan δ) after blending, but each peak is close to the center, specifically, the peak on the high temperature side is at a low temperature and the peak on the low temperature side is at a high temperature. When shifting, it can be said that these are partially compatible systems. When two peak values of loss tangent (tan δ) exist after blending, it can be said that the system is incompatible. In a partially compatible system, one peak is not clear, and it may be difficult to clearly distinguish it from the compatible system. Therefore, in the present invention, all the phases except for the case where two or more peaks are clearly observed are all included. Handle as a solution.

  In general, in the case of an incompatible system, peeling occurs at the interface when an external force such as tension or bending is applied, resulting in a decrease in mechanical properties or whitening. Since the polyetherimide resin (A) and the crystalline polyimide resin (B) constituting the polyimide resin composition of the present invention exhibit a compatible system, each resin can be modified without impairing the impact resistance. .

  As described above, the polyimide resin composition of the present invention is a composition having a characteristic that the glass transition temperature (Tg) is single. The glass transition temperature is preferably 150 ° C. or higher and 300 ° C. or lower, more preferably 160 ° C. or higher and 290 ° C. or lower, and further preferably 170 ° C. or higher and 280 ° C. or lower. When the glass transition temperature of the polyimide resin composition is 150 ° C. or higher, the heat resistance of the polyimide resin composition is sufficient. On the other hand, a glass transition temperature of 300 ° C. or lower is preferable because molding can be performed at a relatively low temperature when molding using a polyimide resin composition. Moreover, when the obtained molded object is secondary-processed, it is preferable for the same reason.

  The polyimide resin composition of the present invention preferably has a tensile elastic modulus based on JIS K7127 of 2200 MPa or more and 3100 MPa or less. If the tensile modulus is 2200 MPa or more, the film obtained using the polyimide resin composition has sufficient rigidity and excellent handling properties. From this viewpoint, the tensile elastic modulus is more preferably 2250 MPa or more, and particularly preferably 2300 MPa or more. On the other hand, a tensile modulus of less than 3100 MPa is preferable because it has sufficient flexibility as a film. From this viewpoint, the tensile elastic modulus is more preferably 3050 MPa or less, and particularly preferably 3000 MPa or less.

  The polyimide resin composition of the present invention preferably has a tensile elongation at break of 130% or more, more preferably 135% or more, measured according to JIS K7127. When the tensile elongation at break is in the range, the impact resistance is excellent when the polyimide resin composition of the present invention is used as a film. Further, it can be stably molded or secondary processed into various shapes without causing troubles such as breakage.

  Furthermore, the polyimide resin composition of the present invention includes other resins, fillers, various additives such as heat stabilizers, ultraviolet absorbers, light, and the like within the scope of the present invention, in addition to the components described above. Stabilizers, nucleating agents, coloring agents, lubricants, flame retardants, and the like may be appropriately blended.

<Molded body>
As a molded object formed using the polyimide resin composition of this invention, the molded object which has shapes, such as a film, a plate, a pipe, a stick | rod, a cap, a volt | bolt, is mentioned, for example. Especially, since the polyimide resin composition of this invention is excellent in heat resistance, rigidity, and impact resistance, it can be used conveniently as a film.

  Applications of the molded body and film include applications that require heat resistance, rigidity, and impact resistance, such as automobile members, aircraft members, and electrical / electronic members.

<Method for producing molded body>
Although it does not specifically limit as a manufacturing method of the said molded object, For example, a well-known method, for example, extrusion molding, injection molding, blow molding, vacuum forming, pressure forming, press molding etc., is employable.

  In addition, the film forming (film forming) method is not particularly limited, but a known method such as an extrusion casting method using a T die, a calendar method, or a casting method can be employed. Among these, an extrusion casting method using a T die is suitably used from the viewpoint of film productivity.

  Further, the film may be a uniaxial or biaxially stretched film stretched in one direction or in two directions, and a method for producing a stretched film is a precursor by a T-die casting method, a press method, a calendar method, or the like. Examples of a method of forming an unstretched film as a film and then performing a stretch molding method using a roll stretching method, a tenter stretching method, etc., and a method of integrally performing melt extrusion and stretching molding by an inflation method, a tubular method, or the like. .

  The molding temperature in the extrusion casting method using a T-die is appropriately adjusted depending on the flow characteristics and film forming properties of the composition used, but is generally 280 ° C. or higher and 350 ° C. or lower. For melt-kneading, generally used single-screw extruders, twin-screw extruders, kneaders, mixers, and the like can be used, and are not particularly limited.

  In the case of the extrusion casting method using a T-die, the obtained film may be rapidly cooled and collected in an amorphous state, or may be crystallized by heating with a casting roll, or after being collected in an amorphous state. You may extract | collect in the state which gave the heat processing and crystallized. In general, amorphous films are excellent in durability and secondary processability, and films after crystallization are excellent in heat resistance and rigidity (koshi). is important.

  Although the thickness of the film formed using the polyimide resin composition of the present invention is not particularly limited, it is usually 1 to 200 μm. It is also important to form a film so that the anisotropy of the physical properties in the flow direction (MD) from the film extruder (MD) and its orthogonal direction (TD) is as small as possible.

  In general, "film" is a thin flat product whose thickness is extremely small compared to the length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll. (JIS K6900) In general, the term “sheet” refers to a product that is thin according to the definition in JIS, and whose thickness is small for the length and width but flat. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, the various measurement about the film | membrane used for the raw material described in this specification and the polyimide-type resin composition of this invention was performed as follows.

(1) Glass transition temperature About a raw material pellet and the obtained film, using a viscoelastic spectrometer DVA-200 (made by IT measurement control Co., Ltd.), distortion 0.1%, frequency 10Hz, temperature increase rate 3 degree-C / min. Was measured for temperature dispersion of dynamic viscoelasticity (dynamic viscoelasticity measurement according to JIS K7244-4 method), and the temperature showing the peak of the main dispersion of loss tangent (tan δ) was defined as the glass transition temperature.

(2) Tensile modulus The obtained film was measured under the condition of a temperature of 23 ° C. according to JIS K7127.

(3) Tensile elongation at break The obtained film was measured in accordance with JIS K7127 under conditions of a temperature of 23 ° C. and a test speed of 200 mm / min.

[Polyetherimide resin (A)]
(A) -1: Polyetherimide (manufactured by SABIC Innovative Plastics, Ultem 1000, glass transition temperature: 232 ° C.)
(A) -2: Polyetherimide (manufactured by SABIC Innovative Plastics, Ultem CRS 5001, glass transition temperature: 240 ° C.)

[Crystalline polyimide resin (B)]
(B) -1: crystalline polyimide resin (Mitsubishi Gas Chemical Co., Ltd., trade name: Surprim TO65S, tetracarboxylic acid component: pyromellitic acid = 100 mol%, diamine component: 1,3-bis (aminomethyl) cyclohexane / Octamethylenediamine = 60/40 mol%, crystal melting temperature: 322 ° C., glass transition temperature: 208 ° C.)

Example 1
(A) -1 and (B) -1 were dry blended at a mixing mass ratio of 80:20, then kneaded at 340 ° C. using a Φ40 mm same-direction twin screw extruder, and then extruded from a T die. Next, the film was rapidly cooled with a casting roll at about 200 ° C. to produce a film having a thickness of 0.1 mm. The obtained film was evaluated for glass transition temperature, tensile modulus, and tensile elongation at break. The results are shown in Table 1.

(Example 2)
A film was prepared and evaluated in the same manner as in Example 1 except that the mixing mass ratio of (A) -1 and (B) -1 was 60:40. The results are shown in Table 1.

(Example 3)
A film was prepared and evaluated in the same manner as in Example 1 except that the mixing mass ratio of (A) -1 and (B) -1 was 40:60. The results are shown in Table 1.

Example 4
A film was prepared and evaluated in the same manner as in Example 1 except that the mixing mass ratio of (A) -1 and (B) -1 was 20:80. The results are shown in Table 1.

(Example 5)
A film was prepared and evaluated in the same manner as in Example 1 except that (A) -2 was used instead of (A) -1. The results are shown in Table 1.

(Example 6)
(A) -2 was used instead of (A) -1, and the film mass was the same as in Example 1 except that the mixing mass ratio of (A) -2 and (B) -1 was 60:40. Fabrication and evaluation were performed. The results are shown in Table 1.

(Example 7)
(A) -2 was used instead of (A) -1, and the film mass was the same as in Example 1 except that the mixing mass ratio of (A) -2 and (B) -1 was 40:60. Fabrication and evaluation were performed. The results are shown in Table 1.

(Example 8)
(A) -2 was used instead of (A) -1, and the mixture mass ratio of (A) -2 and (B) -1 was set to 20:80. Fabrication and evaluation were performed. The results are shown in Table 1.

(Comparative Example 1)
A film was prepared and evaluated in the same manner as in Example 1 except that (A) -1 was used alone. The results are shown in Table 1.

(Comparative Example 2)
A film was prepared and evaluated in the same manner as in Example 1 except that (A) -2 was used alone. The results are shown in Table 1.

(Comparative Example 3)
A film was prepared and evaluated in the same manner as in Example 1 except that (B) -1 was used alone. The results are shown in Table 1.

  Although the films formed from the compositions of Examples 1 to 8 are blends of polyetherimide resin (A) and crystalline polyimide resin (B), the glass transition temperature represented by the main dispersion peak is Both were single and could be recognized as compatible. The film includes all physical properties within an appropriate range.

  On the other hand, the films of Comparative Examples 1 and 2 have high tensile elastic modulus, insufficient flexibility, low tensile elongation at break, and insufficient impact resistance.

  On the contrary, the film of Comparative Example 3 has a low tensile elastic modulus, and there is a concern about handling properties when used as a thin film.

Claims (10)

  A polyimide-based resin composition containing a polyetherimide resin (A) and a crystalline polyimide resin (B) containing a tetracarboxylic acid component (b-1) and an aliphatic diamine component (b-2). The content ratio of the polyetherimide resin (A) and the crystalline polyimide resin (B) is (A) :( B) = 1: 99 to 99: 1 mass%. Composition.   The said aliphatic diamine component (b-2) contains a C4-C12 linear aliphatic diamine at least, The polyimide resin composition of Claim 1 characterized by the above-mentioned.   The said aliphatic diamine component (b-2) contains an alicyclic diamine at least, The polyimide resin composition of Claim 1 or 2 characterized by the above-mentioned.   The polyimide resin composition according to claim 3, wherein the alicyclic diamine is 1,3-bis (aminomethyl) cyclohexane.   There is one peak value of loss tangent (tan δ) measured at a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3 ° C./min by the temperature dispersion measurement of dynamic viscoelasticity described in JIS K7244-4. The polyimide-type resin composition of any one of Claims 1-4 characterized by the above-mentioned.   6. The polyimide resin composition according to claim 5, wherein a temperature (Tg) indicated by a peak value of the loss tangent (tan δ) is 150 ° C. or more and 300 ° C. or less.   The polyimide resin composition according to any one of claims 1 to 6, wherein a tensile elastic modulus measured in accordance with JIS K7127 is 2200 MPa or more and 3100 MPa or less.   The polyimide resin composition according to any one of claims 1 to 7, wherein a tensile elongation at break measured in accordance with JIS K7127 is 130% or more.   The molded object formed using the polyimide resin composition of any one of Claims 1-8.   The molded body according to claim 9, wherein the molded body is a film.