JP6988594B2 - Resin compositions, films and composites - Google Patents

Description

The present invention relates to a resin composition made of super engineering plastic, which can be applied to insulating films, printed circuit boards, spacers, housings, surface materials, etc. in electric / electronic devices, automobiles, aircraft, and the like.

In recent years, as a film for applications such as electrical and electronic equipment, automobiles, and aircraft, it has excellent heat resistance, mechanical properties, chemical resistance, and durability. Therefore, polyetherimide (PEI) and polyethersalphon (PES) are used. , Polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), polyetherketone etherketoneketone (PEKEKK), and other super-engineering plastics have been widely adopted. ing.

Among them, polyetherketone ketone is particularly excellent in chemical resistance and adhesiveness to reinforcing fibers, and can exhibit excellent mechanical properties when used as a composite material with reinforcing fibers. Therefore, in recent years, it has been attracting attention as a matrix material for fiber reinforced plastics, but further improvement in heat resistance and rigidity has been required.

On the other hand, semipregs are used as precursors (intermediates) of fiber reinforced plastics. This is typically a case where a thermoplastic resin film is temporarily adhered to both sides or one side of a unidirectional or woven sheet of reinforcing fibers such as carbon fibers by heat fusion, and this semipreg is finally used. By subjecting it to a process such as a hot press or a belt press, a completely impregnated prepreg can be obtained, or a composite material can be directly obtained. The resin film used for semi-preg production is required to have heat-sealing properties with the reinforcing fiber sheet, but from the viewpoint of productivity and safety, a material with high heat-sealing properties that can be temporarily bonded at the lowest possible temperature is particularly suitable. I was asked.

Patent Document 1 states that by blending polyetherimide with a polyetherketone resin such as PEEK or polyetherketone ketone, the glass transition temperature (Tg) of the polyarylketone resin is improved, and thus heat resistance. There is a description that it will improve. Further, in Patent Document 2, tensile elastic modulus and folding resistance are improved by blending a polyarylketone resin such as PEEK and polyetherketone ketone with a resin having a higher Tg than the polyarylketone resin. There is a description that mechanical properties and heat resistance will be improved.

Japanese Patent Application Laid-Open No. 2002-053749 Japanese Unexamined Patent Publication No. 2015-049269

However, PEEK described in Patent Document 1 has high crystallinity among polyarylketone resins, and even if the temperature is raised above the softening temperature, the heat fusion property with a carbon fiber sheet or the like at the time of producing a semipreg is not sufficient. No. On the other hand, if the amount of polyetherimide is increased in order to reduce the crystallinity, Tg rises too much and the temperature at the time of heat fusion also rises, which has a demerit that it is not preferable from the viewpoint of safety and energy saving. Further, the composition described in Patent Document 1 is described as having at least two peaks of loss tangent (tan δ) obtained by dynamic viscoelasticity measurement, that is, PEEK and poly used. It shows that etherimide is phase-separated, and in general, compositions that cause phase separation tend to cause deterioration of mechanical properties, transparency, and heat resistance, which may be a problem depending on the application. .. In addition, Patent Document 1 discloses only PEEK as a polyarylketone resin, and a machine having heat resistance, rigidity, impact resistance, etc. with respect to a blend of another polyarylketone resin and polyetherimide. No description or suggestion has been made as to how the properties or the heat-sealing property with the reinforcing fiber sheet or the like is improved.

Further, the invention described in Patent Document 2 also has a concern that the heat fusion property, the mechanical physical characteristics due to the phase separation, the heat resistance, the impact resistance, etc. are deteriorated as in the case of Patent Document 1. In addition, in addition to the fact that there is only a description of PEEK, only the value at high temperature is described as the tensile elastic modulus, and it is also described and suggested whether the rigidity at the time of actual use (room temperature) is improved. No.

The present invention has been made under such circumstances, and has high rigidity, heat resistance, impact resistance and heat fusion property, specifically, during secondary processing, for example, a reinforced fiber composite such as carbon fiber. It is an object of the present invention to provide a resin composition having excellent heat-sealing properties with a reinforcing fiber sheet in a material manufacturing process or the like.

The present invention contains a polyetherketoneketone resin (A) and a specific polyetherimide resin (B) as means for solving the above-mentioned problems, thereby improving the rigidity, which was not sufficient by itself, and at the same time. It is an object of the present invention to provide a resin composition capable of improving heat resistance, impact resistance and heat fusion property at the time of secondary processing.

That is, the present invention provides the following [1] to [9].
[1] Polyetherketone ketone resin (A) having a repeating unit (a-1) represented by the following structural formula (1) and a repeating unit (a-2) represented by the following structural formula (2), and the following. A resin composition comprising a polyetherimide resin (B) having a repeating unit (b-1) represented by the structural formula (3).

[2] The mixing ratio of the polyetherketone ketone resin (A) and the early polyetherimide resin (B) is in the range of (A) :( B) = 80: 20 to 20: 80% by mass, [1]. The resin composition according to.

[3] The resin composition according to [1] or [2], which is measured according to JIS K7124-2: 1999 and has an impact strength of 1 J or more at 23 ° C and −20 ° C.

[4] The resin composition according to any one of [1] to [3], wherein the amount of heat of crystal melting measured according to JIS K7122: 2012 is 25 J / g or less.

[5] The resin composition according to any one of [1] to [4], wherein the tensile elastic modulus measured according to JIS K7127: 1999 is 3200 MPa or more.

[6] The resin composition according to any one of [1] to [5], wherein the softening temperature measured according to JIS K7196: 2012 is 160 ° C. or higher and 200 ° C. or lower.

[7] A film comprising the resin composition according to any one of [1] to [6].

[8] A composite material obtained by combining the resin composition or film according to any one of [1] to [7] with reinforcing fibers.

[9] The composite material according to [8], which is a prepreg or a semi-preg.

According to the present invention, it is possible to provide a resin composition having high rigidity, impact resistance and heat resistance. Further, since the resin composition of the present invention has excellent heat-sealing properties with reinforcing fibers such as carbon fibers, it can be suitably used for composite materials, and in particular, it is also preferably used as a matrix for fiber reinforced plastics. It can also be done.

Hereinafter, the present invention will be described in detail.
The resin composition of the present invention contains a polyetherketone ketone resin (A) and a polyetherimide resin (B). By using these in combination, a high level of rigidity (tensile modulus) that could not be achieved by each of them alone is exhibited, and heat resistance and polyetherimide resin that are insufficient with the polyetherketoneketone resin (A) alone are exhibited. It is possible to improve the heat-sealing property at the time of secondary processing, which is insufficient only with (B).

[Polyetherketone Ketone Resin (A)]
The polyetherketone ketone resin (A) used in the present invention is a repeating unit (a-1) represented by the following structural formula (1) and a repeating unit (a-2) represented by the following structural formula (2). It has at least two types of repeating units. The repeating units (a-1) and (a-2) both have one ether group and two ketone groups.

The unit molar ratio [(a-1) / (a-2)] of the repeating unit (a-1) and (a-2) in the polyetherketone ketone resin (A) is not particularly limited, but may be 1 or more. It is preferably 4 or less, more preferably 2.5 or less, and even more preferably 1.5 or less. When the unit molar ratio is 1 or more, the glass transition temperature (Tg) is unlikely to decrease, and it becomes easy to maintain excellent heat resistance. Further, when it is 4 or less, the crystallinity does not become excessive and sufficient heat fusion property can be obtained at the time of secondary processing or the like. The polyetherketoneketone resin (A) having the above-mentioned structure may be used alone or in combination of two or more. Further, it may have a structural unit other than the repeating unit (a-1) and (a-2) as long as the effect of the present invention is not impaired.

The total number (degree of polymerization) of the repeating units (a-1) and (a-2) is preferably 10 or more, more preferably 20 or more, from the viewpoint of ensuring mechanical properties. Further, it is preferably 100 or less, more preferably 50 or less.

The Tg of the polyetherketoneketone resin (A) is preferably 150 ° C. or higher, more preferably 153 ° C. or higher, and even more preferably 155 ° C. or higher. When Tg is 150 ° C. or higher, a resin composition having sufficient heat resistance can be easily obtained. On the other hand, the upper limit of Tg is preferably 200 ° C., more preferably 190 ° C., in order to develop heat-sealing properties at a lower temperature.

The heat of crystal melting (ΔHm) of the polyetherketoneketone resin (A) is preferably 40 J / g or less, more preferably 35 J / g or less. When ΔHm is 40 J / g or less, crystallization is suppressed, so that the heat fusion property during secondary processing is likely to be excellent. From this point of view, the lower limit of ΔHm is not particularly limited, but if ΔHm is 30 J / g or more, it has crystallinity and can be suitably used for applications requiring particularly high heat resistance.

The Tg and ΔHm in the present invention were raised in a temperature range of 25 to 400 ° C. and a heating rate of 10 ° C./min using a differential scanning calorimeter according to JIS K7121: 2012 and JIS K7122: 2012, respectively. It is obtained from the DSC (Differential scanning calorimetry) curve detected at the time.

The polyetherketoneketone resin (A) can be produced by a known production method (see, for example, JP-A-61-195122, JP-A-62-129313, etc.). Further, a commercially available product can also be used. For example, the "KEPSTAN" series manufactured by Arkema, the "KSTONE" series manufactured by SHANDONG KAISHENG NEW MATERIALS, and the "NovaSpire" series manufactured by SOLVAY can be mentioned. The polyetherketoneketone resin (A) may be used alone or in combination of two or more.

[Polyetherimide resin (B)]
The polyetherimide resin (B) used in the present invention has a repeating unit (b-1) represented by the following structural formula (3).

Generally, the structure of a polyetherimide resin is classified according to the difference in the bonding mode, that is, the difference between the meta bond and the para bond. As is clear from the repeating unit (b-1) represented by the structural formula (3), the polyetherimide resin (B) constituting the resin composition of the present invention has the bonding position of the imide group in the para position. be. On the other hand, there are some imide groups having a repeating unit (b-2) represented by the following structural formula (4) in the meta position. The resin composition of the present invention comprises, as the polyetherimide resin (B), a resin having a repeating unit (b-1) represented by the structural formula (3), particularly a resin consisting only of the repeating unit (b-1). Surprisingly, by using it, in addition to being able to improve rigidity and heat resistance, it is possible to exhibit good impact resistance, especially high impact resistance at low temperatures.

The total number of repeating units (b-1) (degree of polymerization) is preferably 10 or more, more preferably 20 or more, because it is excellent in the balance between heat resistance and moldability. Further, it is preferably 1000 or less, and more preferably 500 or less.

The Tg of the polyetherimide resin (B) is preferably 160 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 200 ° C. or higher. When Tg is 160 ° C. or higher, a resin composition having sufficient heat resistance can be obtained. On the other hand, the upper limit of Tg is preferably 250 ° C., more preferably 240 ° C., in order to develop heat-sealing properties at a lower temperature and ensure melt moldability.

The heat of crystal fusion (ΔHm) of the polyetherimide resin (B) is preferably 10 J / g or less, more preferably 5 J / g or less, still more preferably 0 J / g, that is, substantially. It is amorphous. When ΔHm is 10 J / g or less, the crystallinity of the resin composition of the present invention can be reduced, so that the heat fusion property at the time of secondary processing tends to be excellent.

The polyetherimide resin (B) can be produced by a known production method (for example, US Pat. No. 3,803,085, 3,905,942). Moreover, a commercially available product can also be used. For example, the "Ultem" series manufactured by SABIC Innovative Plastics can be mentioned. The polyetherimide resin (B) may be used alone or in combination of two or more.

The polyetherimide resin (B) of the present invention may have a repeating unit other than the repeating unit (b-1) as long as the effect of the present invention is not impaired. For example, it may have a repeating unit (b-2) represented by the structural formula (4), but in that case, the content ratio of the repeating unit (b-2) is impact resistance, heat resistance, and the like. From the viewpoint of chemical resistance, it is preferably 20 mol% or less, more preferably 10 mol% or less in all repeating units.

[Resin composition]
The resin composition of the present invention is a polyetherketone ketone resin having a repeating unit (a-1) represented by the structural formula (1) and a repeating unit (a-2) represented by the structural formula (2). (A) and a polyetherimide resin (B) having a repeating unit (b-1) represented by the structural formula (3).
The polyetherketone ketone resin (A) and the polyetherimide resin (B) constituting the resin composition of the present invention are considered to be completely compatible. This can be evaluated by reading the value of the glass transition temperature (Tg) according to JIS K7121: 2012. Generally, when the Tg of the polymer blend composition is single, it means that the resin to be mixed is in a state of being compatible at the molecular level, and it can be recognized as a compatible system. On the contrary, when two Tg are present even after blending, it is considered to be an incompatible system or a partially compatible 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 tends to cause deterioration of mechanical properties and whitening. Further, since the Tg of the resin having the lower Tg is significantly expressed, the effect of improving the heat resistance by blending is not sufficient, and the heat resistance of the obtained resin composition tends to be insufficient. A resin composition obtained by considering that the polyetherketoneketone resin (A) and the polyetherimide resin (B) constituting the resin composition of the present invention are completely compatible, and a film obtained by using the composition. It is possible to obtain excellent mechanical properties and heat resistance in a molded product.

The content ratio of the polyetherketone ketone resin (A) and the polyetherimide resin (B) constituting the resin composition of the present invention is in the range of (A) :( B) = 80: 20 to 20:80 mass%. It is preferably in the range of (A): (B) = 75:25 to 25:75 mass%, and more preferably in the range of (A) :( B) = 70:30 to 30:70 mass%. Is more preferable. As long as the content ratio of the polyetherketone ketone resin (A) and the polyetherimide resin (B) is within such a range, the balance between heat resistance and heat fusion property is likely to be excellent. In addition, by blending the polyether ketone ketone resin (A) and the polyetherimide resin (B) in such a range, surprisingly, the rigidity (elastic modulus) of the resin composition is improved as compared with each resin alone. Can be made to. This is because the ketone group and aromatic ring of the polyether ketone ketone resin (A) and the imide group and aromatic ring of the polyetherimide resin (B) are electrostatically attracted to each other, and the molecular chains are densely packed with each other. It is thought that it will be.

[Other ingredients]
In addition to the polyether ketone ketone resin (A) and the polyetherimide resin (B), the resin composition includes the polyether ketone ketone resin (A) and the polyetherimide resin as long as the effects of the present invention are not impaired. It may contain a resin component other than (B). When other resin components are contained, it is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less in the total resin components. Further, as long as the effect of the present invention is not impaired, reinforcing fibers such as carbon fiber, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antibacterial / antifungal agents, antistatic agents, lubricants, pigments and dyes Various additives such as may be contained. Among them, reinforcing fibers may be contained, and the content ratio when the reinforcing fibers are contained is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 90 in the resin composition. It is mass% or less, more preferably 80% by mass or less.

[Impact strength]
The resin composition of the present invention preferably has an impact strength of 1 J or more, preferably 1.1 J / g or more, as measured according to JIS K7124-2: 1999, at 23 ° C. and −20 ° C. More preferably, it is more preferably 1.2 J / g or more. In general, the polyetherimide resin (B) is inferior in impact strength to the polyetherketoneketone resin (A), and therefore, when these are blended, the impact resistance of the polyetherketoneketone resin (A) tends to decrease. be. This tendency is particularly remarkable at low temperatures. However, since the resin composition of the present invention uses the polyetherimide resin (B) having the repeating unit (b-1) represented by the structural formula (3), it has high impact strength regardless of the measurement temperature. Can be demonstrated. The impact strength is an index indicating the impact resistance of the material, and specifically, it is measured by the method described in Examples described later. When the impact strength is within the above range, the impact resistance is superior and it becomes easy to apply to articles in a wide range of fields.

[Crystal melting heat (ΔHm)]
In the resin composition of the present invention, the amount of heat of crystal melting (ΔHm) measured according to JIS K7122: 2012 is preferably 25 J / g or less, more preferably 20 J / g or less, and 15 J / g or less. Is more preferable. ΔHm is an index indicating the degree of crystallization, and specifically, it is measured by the method described in Examples described later. When ΔHm is within the above range, the heat-sealing property is likely to be excellent at the time of secondary processing or the like, for example, when composited with a reinforcing fiber sheet such as carbon fiber.

[Tension modulus]
The resin composition of the present invention preferably has a tensile elastic modulus of 3200 MPa or more, more preferably 3250 MPa or more, and further preferably 3300 MPa or more, as measured according to JIS K7127: 1999. Specifically, the tensile modulus is measured by the method described in Examples described later. As long as the tensile elastic modulus is within the above range, for example, even when the film made of the resin composition of the present invention is used alone or when it is combined with other materials such as reinforcing fibers such as carbon fibers. , It becomes easy to develop sufficient rigidity. In particular, if the product has sufficient rigidity, the product can be easily thinned, which can contribute to space saving and resource saving. Further, there is an advantage that the film is easier to handle when the film is thinned. When the film is oriented by the manufacturing method, for example, in the film obtained by extrusion molding, the tensile elastic modulus in the extrusion direction from the mold is preferably within the above range.

[Softening temperature]
The resin composition of the present invention preferably has a softening temperature of 160 ° C. or higher, more preferably 165 ° C. or higher, and even more preferably 170 ° C. or higher, as measured according to JIS K7196: 2012. The upper limit is preferably 200 ° C, more preferably 195 ° C, and even more preferably 190 ° C. The softening temperature is an index of heat resistance, and can also be used as an index of heat fusion property at the time of secondary processing or the like, for example, when temporarily adhering to a reinforcing fiber such as carbon fiber. Specifically, it is measured by the method described in Examples described later. If the temperature is within the above range, it can be said that excellent heat resistance and heat fusion property can be achieved at the same time.

[Glass transition temperature (Tg)]
The resin composition of the present invention preferably has a glass transition temperature (Tg) of 160 ° C. or higher, more preferably 165 ° C. or higher, and even more preferably 170 ° C. or higher, as measured according to JIS K7121: 2012. The upper limit is preferably 210 ° C, more preferably 205 ° C, and even more preferably 200 ° C. Similar to the softening temperature, Tg is an index of heat resistance of the film, and can also be used as an index of heat fusion property at the time of secondary processing, for example, when temporarily adhering to reinforcing fibers such as carbon fibers. can. Specifically, it is measured by the method described in Examples described later. If the temperature is within the above range, it can be said that it is easy to achieve both excellent heat resistance and heat fusion property.

[Manufacturing method of resin composition]
The method for producing the resin composition of the present invention is not limited, and a known method for producing a thermoplastic resin composition can be widely adopted. For example, components such as polyetherketoneketone resin (A), polyetherimide resin (B) and other additives to be blended as needed are premixed using various mixers such as a tumbler and a henschel mixer. After that, a method of melt-kneading with a mixer such as a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader can be mentioned. Above all, the melt kneading method using a twin-screw kneading extruder is preferable from the viewpoint of dispersibility of each component.
Further, for example, a masterbatch obtained by premixing some components (for example, additive components to be blended as needed), supplying the mixture to an extruder, and melt-kneading the mixture is mixed with the remaining components again. The resin composition of the present invention can also be produced by melt-kneading.
The temperature of melt-kneading is not particularly limited, but is usually 320 ° C. or higher, preferably 330 ° C. or higher, and usually 380 ° C. or lower, preferably 360 ° C. or lower.

The resin composition of the present invention can be molded and used by a general molding method, for example, extrusion molding, injection molding, blow molding, vacuum molding, pressure molding, press molding or the like. In each molding method, the apparatus and processing conditions are not particularly limited, and a known method can be adopted. In particular, from the viewpoint of processability when forming a composite material described later, it is preferable to form the resin composition of the present invention into a film by extrusion molding or the like.
The film made of the resin composition of the present invention includes a sheet. Generally, 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 (Japanese Industrial Standards). JIS K6900: 1994), a sheet generally refers to a product that is thin by definition in JIS and whose thickness is generally small for length and width and flat. However, since the boundary between the sheet and the film is not clear, the film includes the sheet in the present invention. Therefore, the "film" may be a "sheet".

[Film manufacturing method]
When the resin composition of the present invention is used as a film, the method for producing the film is not particularly limited, and for example, it can be obtained as a non-stretched or stretched film, and can be obtained as a non-stretched film from the viewpoint of secondary processability. Is preferable. The non-stretched film is a film that is not positively stretched for the purpose of suppressing the orientation of the sheet, but here, a film having a stretch ratio of less than 2 times on a stretch roll in extrusion molding or the like is also included. ..

In the case of a non-stretched film, for example, as described above, each constituent material can be melt-kneaded, then extruded and cooled. A known kneader such as a single-screw or twin-screw extruder can be used for melt-kneading. The melting temperature is appropriately adjusted according to the type and mixing ratio of the resin, the presence or absence of additives, and the type, but from the viewpoint of productivity and the like, it is preferably 320 ° C. or higher, more preferably 330 ° C. or higher. .. Further, it is preferably 380 ° C. or lower, more preferably 360 ° C. or lower. Molding can be performed, for example, by extrusion molding using a mold such as a T-die.

Cooling can be performed, for example, by bringing the film into contact with a cooler such as a cooled cast roll and quenching the film. As a result, the molded product is solidified and a non-stretched film is obtained. The cooling temperature is not limited as long as it is lower than the melting temperature, but is preferably 200 ° C. or lower, more preferably 180 ° C. or lower. Further, the temperature is preferably 120 ° C. or higher, more preferably 140 ° C. or higher.

The thickness of the film made of the resin composition of the present invention is not particularly limited, but the thickness is 1 μm or more from the viewpoints of film strength, handleability, film forming property, processability when forming a composite material described later, and the like. It is preferable to use 3 μm or more, and more preferably 3 μm or more. The upper limit of the thickness is preferably 3 mm, more preferably 2 mm.

Further, the film made of the resin composition of the present invention may be a multilayer film in which other layers are laminated as long as the effects of the present invention are not impaired. As the method of multi-layering, for example, known methods such as coextrusion, extrusion laminating, thermal laminating, and dry laminating can be used.

[Usage / Usage]
The molded product such as the resin composition and the film of the present invention thus obtained can be used as a composite material, and can be used, for example, as a matrix of fiber reinforced plastic which is a composite material with reinforcing fibers. .. The fiber reinforced plastic is obtained as having excellent heat resistance, impact resistance and rigidity.

The type of reinforcing fiber is not particularly limited, but for example, inorganic fiber such as carbon fiber, glass fiber, boron fiber, alumina fiber, liquid crystal polymer fiber, polyethylene fiber, aramid fiber, polyparaphenylene benzoxazole fiber and the like. Organic fiber, aluminum fiber, magnesium fiber, titanium fiber, SUS fiber, copper fiber and the like can be mentioned. Among these, carbon fiber is preferable from the viewpoint of rigidity and lightness.

The shape of the reinforcing fiber is also not particularly limited, and is not particularly limited, and fiber bundles such as chopped strands and rovings, woven fabrics such as plain weave and twill weave, knitted fabrics, non-woven fabrics, fiber papers, and UD materials (unidirectional) materials. ) And the like, it can be appropriately selected from the reinforcing fiber sheets as needed.

The method for compositing the resin composition of the present invention and the reinforcing fiber is not particularly limited, and a conventionally known method can be adopted. For example, at the time of melt-kneading the polyetherketone-ketone resin (A) and the polyetherimide resin (B), chopped strands of reinforcing fibers or the like may be blended and composited, or the resin of the present invention may be added to a roving-like continuous reinforcing fiber. By impregnating the composition, a composite material of the resin composition and the reinforcing fiber can be obtained.

The method of combining the film made of the resin composition of the present invention and the reinforcing fiber is not particularly limited, and by adopting a conventionally known method, the resin composition of the present invention is impregnated in the reinforcing fiber bundle / reinforcing fiber sheet. Alternatively, a semi-impregnated prepreg state or semi-preg state (state in which voids are present) composite material can be produced.

Specifically, a film made of the resin composition of the present invention is superposed on one side or both sides of the above-mentioned reinforcing fiber sheet, and the film is melted by heating and pressurizing, and the reinforcing fiber sheet is impregnated with the resin component. It can be in a prepreg state or a semi-preg state. By adjusting the heating and pressurizing conditions, it is possible to select whether to use a prepreg or a semi-preg in a semi-impregnated state (temporarily bonded state). Further, the semipreg can also be obtained by temporarily adhering the sheet made of the resin composition of the present invention to the reinforcing fiber sheet by heat fusion, omitting the pressurizing step. This semi-preg has an advantage that the time required for manufacturing can be shortened, which leads to a reduction in manufacturing cost, and because it is semi-impregnated, the reinforcing fibers easily behave with each other inside and have flexibility.

In recent years, semipregs have been attracting attention as precursors (intermediates) of fiber reinforced plastics. As described above, a typical example of this is a semi-preg in which a thermoplastic resin film is temporarily adhered to both sides or one side of a reinforcing fiber sheet such as one-way or woven-like reinforcing fiber by heat fusion. Finally, by subjecting it to a process such as a hot press or a belt press, a completely impregnated prepreg can be obtained, or a composite product can be directly obtained. The resin film used for producing the semipreg is required to have heat-sealing properties with the reinforcing fiber sheet. However, as described above, the resin composition of the present invention has excellent heat-sealing properties with the reinforcing fibers. It can be used particularly preferably because it can be heat-sealed at a lower temperature while maintaining heat resistance.

The content ratio of the reinforcing fibers in the composite material thus obtained is preferably 20% by volume or more, more preferably 30% by volume or more, preferably 90% by volume or less, and more preferably 80% by volume. % Or less.

The use of the resin composition of the present invention is not particularly limited, but as described above, since it has high rigidity (elastic modulus) and heat resistance, it is suitably used in various applications requiring these characteristics. be able to. Examples thereof include insulating films, printed circuit boards, spacers, housings, surface materials and the like used in electric / electronic devices, automobiles, aircraft and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

[Manufacturing of film]
In Examples and Comparative Examples, the following raw materials were used to produce films having the composition shown in Tables 1 and 2 below.

[Polyetherketone Ketone Resin (A)]
(A) -1: KEPSTAN6002 (manufactured by Arkema, (a-1) / (a-2) = 1.5, ΔHm = 0J / g, Tg = 153 ° C.)
(A) -2: KEPSTAN7002 (manufactured by Arkema, (a-1) / (a-2) = 2.3, ΔHm = 29J / g, Tg = 158 ° C.)

[Polyetherimide resin (B)]
(B) -1: Ultem CRS5011-1000 (manufactured by SABIC Innovative Plastics, polyetherimide resin having a repeating unit (b-1), ΔHm = 0J / g, Tg = 217 ° C.)
(B) -2: Ultem 1010-1000 (manufactured by SABIC Innovative Plastics, polyetherimide resin having a repeating unit (b-2), ΔHm = 0J / g, Tg = 212 ° C.)

[Polyetheretherketone resin]
(N) -1: VESTAKEP 3300G (manufactured by Daicel Evonik, ΔHm = 47J / g, Tg = 143 ° C.)

(Example 1)
(A) -1 and (B) -1 were dry-blended at a mass ratio of 80:20. This resin mixture was kneaded at 350 ° C. with a single-screw extruder having a diameter of 40 mm, and then extruded into a film using a T-die. The obtained molded product was rapidly cooled with a cast roll at about 160 ° C. to prepare a film having a thickness of 0.1 mm.

(Example 2)
A film was prepared in the same manner as in Example 1 except that the mixing ratio of (A) -1 and (B) -1 was 60:40.

(Example 3)
A film was prepared in the same manner as in Example 1 except that the mixing ratio of (A) -1 and (B) -1 was 40:60.

(Example 4)
A film was prepared in the same manner as in Example 1 except that the mixing ratio of (A) -1 and (B) -1 was 20:80.

(Example 5)
A film was prepared in the same manner as in Example 1 except that (A) -2 was used as a raw material instead of (A) -1 and the mixing ratio of (A) -2 and (B) -1 was 60:40. Made.

(Comparative Example 1)
A film was produced by the same method as in Example 1 except that only (A) -1 was used as a raw material.

(Comparative Example 2)
A film was prepared in the same manner as in Example 1 except that only (A) -2 was used as a raw material.

(Comparative Example 3)
A film was prepared in the same manner as in Example 1 except that only (B) -1 was used as a raw material.

(Comparative Example 4)
A film was prepared in the same manner as in Example 1 except that (B) -2 was used as a raw material instead of (B) -1 and the mixing ratio of (A) -1 and (B) -2 was 80:20. Made.

(Comparative Example 5)
A film was prepared in the same manner as in Example 1 except that (B) -2 was used as a raw material instead of (B) -1 and the mixing ratio of (A) -1 and (B) -2 was 60:40. Made.

(Comparative Example 6)
A film was prepared in the same manner as in Example 1 except that (B) -2 was used as a raw material instead of (B) -1 and the mixing ratio of (A) -1 and (B) -2 was 40:60. Made.

(Comparative Example 7)
A film was prepared in the same manner as in Example 1 except that (B) -2 was used as a raw material instead of (B) -1 and the mixing ratio of (A) -1 and (B) -2 was 20:80. Made.

(Comparative Example 8)
Same as Example 1 except that (N) -2 and (B) -1 were used as raw materials, the mixing ratio of (N) -1 and (B) -1 was 60:40, and the kneading temperature was 380 ° C. A film was prepared by the method of.

[Evaluation of film]
For each film produced in the above Examples and Comparative Examples, evaluation and measurement were performed for various items as follows. Here, the "vertical" of the film refers to the direction in which the film-shaped molded product is extruded from the T-die, and the direction orthogonal to this in the film surface is defined as "horizontal".

<Impact strength>
According to JIS K7124-2: 1999, using the high-speed puncture impact tester Hydroshot HITS-P10 (manufactured by Shimadzu Corporation), the punching diameter is 0.5 at 23 ° C and -20 ° C. The measurement was performed under the conditions of inches and a test speed of 3 m / c.

<Crystal melting heat (ΔHm)>
According to JIS K7122: 2012, the temperature was raised in a temperature range of 25 to 400 ° C. and a heating rate of 10 ° C./min using a differential scanning calorimeter Pyris1 DSC (manufactured by PerkinElmer), and crystal melting was performed from the detected DSC curve. The calorific value (ΔHm) was determined.

<Tension modulus>
Each film was cut into a length of 400 mm and a width of 10 mm to prepare a test piece (thickness 0.1 mm). The tensile elastic modulus in the vertical direction of the test piece was measured according to JIS K7127: 1999. A tensile compression tester type 205 (manufactured by Intesco) was used as the tensile tester, and the measurement conditions were an atmospheric temperature of 23 ° C. and a tensile speed of 5 mm / min.

<Softening temperature>
Each film was cut into a length of 5 mm and a width of 5 mm to prepare a test piece (thickness 0.1 mm). The softening temperature was determined by thermomechanical analysis (TMA: Thermomechanical Analysis) according to JIS K7196: 2012. A TMA120C (manufactured by Hitachi High-Tech Science Co., Ltd.) was used as the TMA device, and the measurement conditions were an ambient temperature of 23 ° C., a relative humidity of 50%, a pressure on the indenter of 0.5 N, and a temperature rise rate of 5 ° C./min.

<Glass transition temperature (Tg)>
According to JIS K7121: 2012, the temperature was raised in a temperature range of 25 to 400 ° C. and a heating rate of 10 ° C./min using a differential scanning calorimeter Pyris1 DSC (manufactured by PerkinElmer), and the glass transition was performed from the detected DSC curve. The temperature was calculated.

Tables 1 and 2 below summarize the evaluation and measurement results for Examples and Comparative Examples.

As can be seen from the results shown in Tables 1 and 2, the films (Examples 1 to 5) containing the polyetherketoneketone resin (A) and the polyetherimide resin (B) in a predetermined ratio have impact resistance. It is recognized that it is excellent in both heat resistance and rigidity, and it is presumed that the softening temperature is not too high and the heat fusion property is also excellent. In particular, in Examples 2 to 5, the tensile elastic modulus (rigidity) is higher than that of the polyetherketoneketone resin (A) only (Comparative Examples 1 and 2) and the polyetherimide resin (B) only (Comparative Example 3). Can be confirmed to be improved.

On the other hand, only the polyetherketone ketone resin (A) (Comparative Examples 1 and 2) is inferior in tensile elastic modulus (rigidity), and only the polyetherimide resin (B) (Comparative Example 3) has a too high softening temperature and is secondary. It is presumed that the heat fusion property during processing is not sufficient.
Further, when a resin having only the repeating unit (b-2) represented by the structural formula (4) is used as the polyetherimide resin (B) (Comparative Examples 4 to 7), the impact resistance is not sufficient. In particular, the impact strength is significantly reduced at low temperatures (-23 ° C).
Further, the film (Comparative Example 8) containing the polyetheretherketone resin (N) and the polyetherimide resin (B) in a predetermined ratio has a large ΔHm and too high crystallinity, and therefore heat during secondary processing. The fusion property is not sufficient, and the tensile elasticity (rigidity) is also inferior. Further, as can be seen from the fact that two peaks indicating Tg are observed, the polyetheretherketone resin (N) and the polyetherimide resin (B) are phase-separated, and as a result, the heat resistance is inferior.

Claims (9)

Polyetherketone ketone resin (A) having a repeating unit (a-1) represented by the following structural formula (1) and a repeating unit (a-2) represented by the following structural formula (2), and the following structural formula ( A resin composition comprising a polyetherimide resin (B) having a repeating unit (b-1) represented by 3).

The method according to claim 1, wherein the mixing ratio of the polyetherketone ketone resin (A) and the polyetherimide resin (B) is in the range of (A) :( B) = 80:20 to 20:80 mass%. Resin composition. The resin composition according to claim 1 or 2, wherein the impact strength at 23 ° C. and −20 ° C. is 1 J or more, which is measured according to JIS K7124-2: 1999. The resin composition according to any one of claims 1 to 3, wherein the amount of heat of crystal melting measured according to JIS K7122: 2012 is 25 J / g or less. The resin composition according to any one of claims 1 to 4, wherein the tensile elastic modulus measured according to JIS K7127: 1999 is 3200 MPa or more. The resin composition according to any one of claims 1 to 5, wherein the softening temperature measured according to JIS K7196: 2012 is 160 ° C. or higher and 200 ° C. or lower. A film comprising the resin composition according to any one of claims 1 to 6. A composite material obtained by combining the resin composition or film according to any one of claims 1 to 7 with reinforcing fibers. The composite material according to claim 8, which is a prepreg or a semi-preg.