JP6780440B2 - Polyimide resin composition - Google Patents

Description

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

Polyetherimide resin is an amorphous super engineering plastic with a glass transition temperature of over 200 ° C. Taking advantage of its excellent heat resistance, flame retardancy, and moldability, automobile parts, aircraft parts, electrical / electronic parts, etc. Widely used in. However, the polyetherimide resin is a very brittle material, and there is a problem that it is difficult to use it in applications that require impact resistance. Further, since it has high rigidity and low flexibility, there is a problem that it is difficult to use it in an application where the original flexibility (suppleness) of a plastic film is required.

To address these issues, 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 tabbing resistance (bending resistance).

Special Table 2002-532599

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

On the other hand, the crystalline polyimide resin composed of tetracarboxylic acid and aliphatic diamine has an excellent balance between heat resistance and impact resistance. However, although it is excellent in impact resistance, it has a relatively low rigidity, so that there is a problem that it is inferior in handleability when used as a thin film depending on the application. Further, since an expensive monomer such as an alicyclic diamine is used, there is a problem that the unit price of the raw material becomes high and the use is limited.

As a result of diligent studies, the present inventor has found that a crystalline polyimide resin having a specific structure has high compatibility with a polyetherimide resin, and therefore these blends can solve the above-mentioned problems. It came to.

That is, the first aspect of the present invention is a crystalline polyimide resin (B) containing a polyetherimide resin (A) and 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% by mass in the polyimide resin composition containing the above. It is a polyimide resin composition characterized by the above.

In the first aspect of the present invention, it is preferable that the aliphatic diamine component (b-2) contains a linear aliphatic diamine having at least 4 to 12 carbon atoms.

In the first aspect of the present invention, it is preferable that the aliphatic diamine component (b-2) contains at least an alicyclic diamine.

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 the temperature dispersion measurement of dynamic viscoelasticity described in JIS K7244-4. ) Is preferably present at one peak value.

In the first aspect of the present invention, the temperature (Tg) indicated by the peak value of the loss tangent (tan δ) is preferably 150 ° C. or higher and 300 ° C. or lower.

In the first aspect of the present invention, the tensile elastic modulus measured according to JIS K7127 is preferably 2200 MPa or more and 3100 MPa or less.

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

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

In the second aspect of the present invention, it is preferable that the molded product is a film.

According to the present invention, it is possible to provide a polyimide-based resin composition having excellent heat resistance, rigidity, and impact resistance, and a molded product or film using the composition.

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 the numerical values A and B means "A or more and B or less". When a unit is attached only to the numerical value B in such a notation, the unit shall be applied to the numerical value A as well.

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 well-known compound can be used, and the production method and properties thereof 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) in that it has an 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 (formulation 1), n (repetition number) is usually an integer in the range of 10 to 1,000, preferably 10 to 500. When n is in such a range, the balance between moldability and heat resistance is excellent.

The above formula (Chemical bond 1) can be classified into the structures represented by the following (Chemical bond 2) and (Chemical bond 3), respectively, based on the difference in bond mode, specifically, the difference between meta-bond and 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 (Chemical formula 2) and (Chemical formula 3), n (repetition number) is usually an integer in the range of 10 to 1,000, preferably 10 to 500. When n is in such a range, the balance between moldability and heat resistance is excellent.

As a specific example of the polyetherimide resin (A) having such a structure, for example, it is commercially available from SABIC Innovative Plastics Co., Ltd. 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 further preferably 180 ° C. or higher and 280 ° C. or lower. , 190 ° C. or higher and 270 ° C. or lower, and particularly preferably 200 ° C. or higher and 260 ° C. or lower. When the glass transition temperature of the polyetherimide resin (A) is 160 ° C. or higher, the heat resistance of the polyimide resin composition becomes sufficient. On the other hand, since the glass transition temperature of the polyetherimide resin (A) is 300 ° C. or lower, molding or secondary processing can be performed at a relatively low temperature. Therefore, when blending 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, Alicyclic tetracarboxylic acids 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. Further, these alkyl esters can also be used.

Among them, it is preferable that the component exceeding 50 mol% of the tetracarboxylic acid component (b-1) is pyromellitic acid. Since the tetracarboxylic acid component (b-1) contains pyromellitic acid as the main component, the polyimide resin composition of the present invention is excellent in heat resistance, secondary processability and low water absorption. From this point of view, the pyromellitic acid in the tetracarboxylic acid component (b-1) is more preferably 60 mol% or more, further preferably 80 mol% or more, and more preferably 90 mol% or more. 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) contains an aliphatic diamine (b-2) as a main component. That is, it is important that the component exceeding 50 mol% of the diamine component is an aliphatic diamine (b-2), more preferably 60 mol% or more, still more preferably 80 mol% or more. , 90 mol% or more is particularly preferable, and it is particularly preferable that all of the diamine components (100 mol%) are aliphatic diamines (b-2). This makes it possible to impart heat resistance, low water absorption, moldability and secondary processability to the polyimide resin composition of the present invention. The aliphatic diamine in the present invention also includes an alicyclic diamine.

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, both ends of the cyclic hydrocarbon are used. It preferably contains an aliphatic 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, and 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-based resin composition of the present invention, when impact resistance, moldability, and secondary processability are emphasized, the aliphatic diamine (b-2) is used at the end of the amount of the linear hydrocarbon. It preferably contains 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, but specific examples thereof include ethylenediamine (2 carbon atoms), propylene diamine (3 carbon atoms), and the like. Butane diamine (4 carbon atoms), pentan diamine (5 carbon atoms), hexane diamine (6 carbon atoms), heptane diamine (7 carbon atoms), octane diamine (8 carbon atoms), nonane diamine (9 carbon atoms), decane diamine (decane diamine) Carbon number 10), undecane diamine (carbon number 11), dodecane diamine (carbon number 12), tridecane diamine (carbon number 13), tetradecane diamine (carbon number 14), pentadecane diamine (carbon number 15), hexadecane diamine (carbon number 15) Number 16), heptadecanediamine (17 carbons), octadecanediamine (18 carbons), nonadecandiamine (19 carbons), eikosan (20 carbons), triacantane (30 carbons), tetracontan (30 carbons) 40), pentacontan (50 carbon atoms) and the like. Among these, linear aliphatic diamines having 4 to 12 carbon atoms can be mentioned from the viewpoint of excellent moldability, secondary processability, and low hygroscopicity. Further, 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 contained. 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 '-Diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, p- Examples include aromatic diamine components such as xylylene diamine and m-xylylene diamine, ether diamine components such as polyethylene glycol bis (3-aminopropyl) ether and polypropylene glycol bis (3-aminopropyl) ether, and siloxane diamines. ..

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, the aliphatic diamine and the alicyclic diamine It is preferable to contain both linear aliphatic diamines. When both alicyclic diamine and linear aliphatic diamine are contained, the content of each is preferably in the range of alicyclic diamine: linear aliphatic diamine = 99: 1-1: 99 mol%. , 90:10 to 10:90 mol%, more preferably 80:20 to 20:80 mol%, particularly preferably 70:30 to 30:70 mol%, 60. : 40-40: 60 mol% is particularly preferable. The polyimide resin composition of the present invention has heat resistance, impact resistance, and moldability as long as the ratio of the alicyclic diamine and the linear aliphatic diamine contained in the aliphatic diamine (b-2) is within such a range. 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 preferably 280 ° C. or higher and 340 ° C. or lower. More preferred. When the crystal melting temperature of the crystalline polyimide resin (B) is 260 ° C. or higher, the heat resistance of the polyimide resin composition is sufficient. On the other hand, when the crystal melting temperature is 350 ° C. or lower, for example, when molding using the polyimide resin composition of the present invention, molding or secondary processing can be performed at a relatively low temperature, which is preferable.

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 preferably 170 ° C. or higher and 280 ° C. or lower. More 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, when the glass transition temperature is 300 ° C. or lower, molding can be performed at a relatively low temperature when molding using the polyimide resin composition of the present invention, which is preferable. Further, when the obtained molded product is secondarily processed, it is also preferable for the same reason.

<Polyimide-based 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% by mass. It is characterized by that.

The content ratio of the polyetherimide resin (A) and the crystalline polyimide resin (B) can be appropriately adjusted according to the required application. In the polyimide resin composition of the present invention, for example, when heat resistance and rigidity are emphasized, the content ratio of the polyetherimide resin (A) and the crystalline polyimide resin (B) is (A) :( B). = 60:40 is preferable, 70:30 is more preferable, and 80:20 is even more preferable. On the other hand, when impact resistance is important, the content ratio of the polyetherimide resin (A) and the crystalline polyimide resin (B) is preferably (A) :( B) = 40: 60. It is more preferably 30:70 and even more preferably 20:80.

The polyimide resin composition of the present invention has a loss tangent 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. It is characterized in that 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). Further, the existence of one peak value of loss tangent (tan δ) can be rephrased as having a single glass transition temperature (Tg). Further, 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 according to JIS K7121, only one inflection point indicating the glass transition temperature appears.

Generally, if the glass transition temperature of the polymer blend composition is single, it means that the resins to be mixed are in a state of being compatible at the molecular level, and can be recognized as a compatible system. In addition, although there are two peak values of loss tangent (tan δ) after blending, when each peak is closer to the center, specifically, the peak on the high temperature side becomes low temperature and the peak on the low temperature side becomes high temperature, respectively. When shifting, it can be said that these are partially compatible systems. If there are two peak values of loss tangent (tan δ) even after blending, it can be said that the system is incompatible. In a partially compatible system, one peak may not be clear and it may be difficult to clearly distinguish it from the compatible system. Therefore, in the present invention, all phases are used except when two or more peaks are clearly observed. Treat as a melt system.

Generally, in the case of an incompatible system, peeling occurs at the interface when an external force such as tension or bending is applied, which causes deterioration of mechanical properties and whitening. Since the polyetherimide resin (A) and the crystalline polyimide resin (B) constituting the polyimide-based resin composition of the present invention show 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, when the glass transition temperature is 300 ° C. or lower, molding can be performed at a relatively low temperature when molding using the polyimide resin composition, which is preferable. Further, when the obtained molded product is secondarily processed, it is also preferable for the same reason.

The polyimide resin composition of the present invention preferably has a tensile elastic modulus of 2200 MPa or more and 3100 MPa or less in accordance with JIS K7127. When the tensile elastic modulus is 2200 MPa or more, the film obtained by using the polyimide resin composition has sufficient rigidity and is excellent in handleability. From this point of view, the tensile elastic modulus is more preferably 2250 MPa or more, and particularly preferably 2300 MPa or more. On the other hand, when the tensile elastic modulus is less than 3100 MPa, it is preferable because it has sufficient flexibility as a film. From this point of view, the tensile elastic modulus is more preferably 3050 MPa or less, and particularly preferably 3000 MPa or less.

The polyimide-based resin composition of the present invention preferably has a tensile elongation at break of 130% or more, more preferably 135% or more, as measured in accordance with JIS K7127. As long as the tensile elongation at break is applied, the polyimide resin composition of the present invention is excellent in impact resistance when used as a film. In addition, it can be stably molded or secondary processed into various shapes without causing troubles such as breakage.

Further, the polyimide resin composition of the present invention has other resins, fillers and various additives other than the above-mentioned components, as long as the gist of the present invention is not exceeded, for example, a heat stabilizer, an ultraviolet absorber, and light. Stabilizers, nucleating agents, coloring agents, lubricants, flame retardants and the like may be appropriately added.

<Molded body>
Examples of the molded product formed by using the polyimide resin composition of the present invention include molded products having shapes such as films, plates, pipes, rods, caps, and bolts. Among them, the polyimide-based resin composition of the present invention is excellent in heat resistance, rigidity, and impact resistance, and therefore can be suitably used as a film.

Examples of the use of the molded product and the film include applications in which heat resistance, rigidity, and impact resistance are required for automobile members, aircraft members, electrical / electronic members, and the like.

<Manufacturing method of molded product>
The method for producing the molded body is not particularly limited, but known methods such as extrusion molding, injection molding, blow molding, vacuum forming, compressed air molding, press molding and the like can be adopted.

Further, the film forming (film forming) method is not particularly limited, but a known method, for example, an extrusion casting method using a T-die, a calender method, a casting method, or the like can be adopted. Of these, the extrusion casting method using a T-die is preferably used from the viewpoint of film productivity and the like.

Further, the film may be a uniaxial or biaxially stretched film stretched in one or two directions, and the stretched film can be produced by a T-die casting method, a pressing method, a calendar method or the like as a precursor. A method of stretching and molding by a roll stretching method, a tenter stretching method, or the like, or a method of integrally performing melt extrusion and stretching molding by an inflation method, a tubular method, or the like can be mentioned. ..

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 to be used, but is generally 280 ° C. or higher and 350 ° C. or lower. Generally used single-screw extruders, twin-screw extruders, kneaders, mixers, and the like can be used for melt-kneading, 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, crystallized by heating with a casting roll, or after being collected in an amorphous state. It may be collected in a crystallized state after being heat-treated. Generally, an amorphous film has excellent durability and secondary processability, and a crystallized film has excellent heat resistance and rigidity (stiffness). Therefore, it is possible to use a film in an optimum crystallized state according to the application. is important.

The thickness of the film formed by using the polyimide resin composition of the present invention is not particularly limited, but is usually 1 to 200 μm. It is also important to form the film so that the anisotropy of the physical properties in the flow direction (MD) from the extruder and the orthogonal direction (TD) of the film is minimized.

In general, a "film" is a thin flat product whose thickness is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll. (JIS K6900), and generally, "sheet" means a product that is thin by definition in JIS and whose thickness is small for its length and width and is flat. However, the boundary between the sheet and the film is not clear, and it is not necessary to distinguish between the two in the present invention. Therefore, in the present invention, even when the term "film" is used, the term "sheet" is included and the term "sheet" is used. Even if it is, it shall include "film".

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Various measurements were made on the raw materials described in the present specification and the films used in the polyimide resin composition of the present invention as follows.

(1) Glass transition temperature For the raw material pellets and the obtained film, using a viscoelastic spectrometer DVA-200 (manufactured by IT Measurement Control Co., Ltd.), strain 0.1%, frequency 10 Hz, temperature rise rate 3 ° C / min The temperature dispersion measurement of the dynamic viscoelasticity (dynamic viscoelasticity measurement by the JIS K7244-4 method) was performed at the above, and the temperature showing the peak of the main dispersion of the loss tangent (tan δ) was defined as the glass transition temperature.

(2) Tension elastic modulus The obtained film was measured under the condition of a temperature of 23 ° C. in accordance with JIS K7127.

(3) Tensile elongation at break The obtained film was measured in accordance with JIS K7127 under the 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 Co., Ltd., Ultem1000, glass transition temperature: 232 ° C.)
(A) -2: Polyetherimide (manufactured by SABIC Innovative Plastics Co., Ltd., UltramCRS5001, glass transition temperature: 240 ° C.)

[Crystalline polyimide resin (B)]
(B) -1: Crystalline polyimide resin (manufactured by Mitsubishi Gas Chemicals, Ltd., trade name: Serprim 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, kneaded at 340 ° C. using a Φ40 mm isodirectional twin-screw extruder, and then extruded from a T-die. Then, it was rapidly cooled with a casting roll at about 200 ° C. to prepare a film having a thickness of 0.1 mm. The obtained film was evaluated for glass transition temperature, tensile elastic modulus, and tensile elongation at break. The results are shown in Table 1.

(Example 2)
Films were prepared and evaluated in the same manner as in Example 1 except that the mixed 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 mixed mass ratio of (A) -1 and (B) -1 was set to 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 mixed mass ratio of (A) -1 and (B) -1 was set to 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 was prepared in the same manner as in Example 1 except that the mixed mass ratio of (A) -2 and (B) -1 was 60:40. It was prepared and evaluated. The results are shown in Table 1.

(Example 7)
(A) -2 was used instead of (A) -1, and the film was prepared in the same manner as in Example 1 except that the mixed mass ratio of (A) -2 and (B) -1 was 40:60. It was prepared and evaluated. The results are shown in Table 1.

(Example 8)
(A) -2 was used instead of (A) -1, and the film was prepared in the same manner as in Example 1 except that the mixed mass ratio of (A) -2 and (B) -1 was 20:80. It was prepared and evaluated. 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 film composed of the compositions of Examples 1 to 8 is a blend of the polyetherimide resin (A) and the crystalline polyimide resin (B), the glass transition temperature represented by the peak of the main dispersion is All of them were single and could be recognized as a compatible system. The film contains all physical properties in an appropriate range.

On the other hand, the films of Comparative Examples 1 and 2 have a high tensile elastic modulus, insufficient flexibility, a 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 handleability 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). Te, the content of the polyether imide resin (a) and the crystalline polyimide resin (B) is (a) :( B) = 1 : 99~99: 1 % by mass is, the aliphatic diamine component ( b-2) comprises a cycloaliphatic diamine and a linear aliphatic diamine, each content alicyclic diamine: linear aliphatic diamines = 99: 1 to 40: Ru 60 mole percent ranges der A polyimide-based resin composition characterized by this. The polyimide-based resin composition according to claim 1 , wherein the alicyclic diamine is 1,3-bis (aminomethyl) cyclohexane. The polyimide resin composition according to claim 1 or 2 , wherein the glass transition temperature of the polyetherimide resin (A) is 160 ° C. or higher and 300 ° C. or lower. The polyimide resin composition according to any one of claims 1 to 3 , wherein the crystalline polyimide resin (B) has a glass transition temperature of 150 ° C. or higher. According to the temperature dispersion measurement of dynamic viscoelasticity described in JIS K7244-4, there is one peak value of loss tangent (tan δ) measured at strain 0.1%, frequency 10 Hz, and heating rate 3 ° C./min. The polyimide-based resin composition according to any one of claims 1 to 4 , wherein the polyimide resin composition is characterized by this. The polyimide resin composition according to claim 5 , wherein the temperature (Tg) indicated by the peak value of the loss tangent (tan δ) is 150 ° C. or higher and 300 ° C. or lower. The polyimide-based resin composition according to any one of claims 1 to 6 , wherein the 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 the tensile elongation at break measured in accordance with JIS K7127 is 130% or more. A molded product formed by using the polyimide resin composition according to any one of claims 1 to 8 . The molded product according to claim 9 , wherein the molded product is a film.