Resin compositions, films, composite materials, moving objects and 3D modeling materials

Abstract

Provided is a resin composition having excellent heat resistance, melt moldability and secondary processability. A resin composition comprising a polyaryletherketone resin (A) and a poly(ether imide sulfone) resin (B), wherein the polyaryletherketone resin (A) and the poly(ether imide sulfone) resin (B) are dissolved in each other. The polyaryletherketone resin (A) is preferably a polyetherketoneketone resin having a repeating unit (a-1) represented by formula (1A) and a repeating unit (a-2) represented by formula (2A), and the resin composition has a single glass transition temperature.

Description

[Technical field]

[0001] The present invention relates to a resin composition made of a super engineering plastic that can be used for insulating films, printed circuit boards, spacers, housings, surface materials, packaging materials, etc. in electric / electronic devices, automobiles, aircraft, etc. The present invention also relates to a film, composite material, mobile object, material for three-dimensional modeling, filament for three-dimensional modeling, and molded article that use this resin composition. [Background technology]

[0002] In recent years, super engineering plastics such as polyetherimide sulfone (PEI), polyethersulfone (PES), polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK), and polyetherketoneetherketoneketone (PEKEKK) have been widely adopted as films and 3D modeling materials in electrical and electronic devices, automobiles, aircraft, and other applications due to their excellent heat resistance, mechanical properties, chemical resistance, and durability.

[0003] Among these, polyetherketoneketone is expected to be used primarily as a matrix material for speaker diaphragms and fiber-reinforced materials, as it is a material that combines heat resistance and melt moldability, as its glass transition temperature and crystalline melting temperature can be controlled by the primary structure.Since polyetherketoneketone has excellent adhesion to glass fiber and carbon fiber, it can exhibit excellent mechanical properties when used as a matrix resin for fiber-reinforced materials.

[0004] Polyetherketoneketone was required to have improved heat resistance so that it could withstand use in even harsher environments.

[0005] Patent Document 1 discloses a multi-component phase-separated polymer blend in which polyaryl ether ketones are blended with polyetherimide sulfone, and describes that the blend system can improve the heat resistance of polyaryl ether ketones.

[0006] [Patent Document 1] Special Publication No. 2009-508997 Summary of the Invention

[0007] In the course of researching the present invention, the inventors found that the blend of polyaryl ether ketone and polyetherimide sulfone described in Patent Document 1 is phase-separated and softens at the glass transition temperatures of each component, resulting in poor secondary processability. Incidentally, although Patent Document 1 describes that polyether ketone ketone may be used as the polyaryl ether ketone, it does not describe anything about the repeating units constituting the resin, in particular, a preferred ratio of repeating units derived from terephthalic acid and repeating units derived from isophthalic acid. Similarly, Patent Document 1 lists many monomer components that can be used for polyetherimide sulfone, but makes no mention of a structure that can exhibit excellent performance in combination with polyether ketone ketone.

[0008] Therefore, an object of the present invention is to provide a resin composition having high heat resistance and excellent melt moldability and secondary processability.

[0009] In the present invention, a polyaryl ether ketone resin (A) and a polyetherimide sulfone resin (B) are combined and made compatible with each other, thereby providing a resin composition that further improves the heat resistance of the polyaryl ether ketone resin (A), which has excellent heat resistance and melt moldability, and also has excellent secondary processability due to the compatibility of the two.

[0010] The present invention also provides a material for three-dimensional modeling that contains a polyaryl ether ketone resin (A) in which the ratio of the number of ether groups to the number of ketone groups is less than 2, and a resin (A') other than this polyaryl ether ketone resin (A), and that has a crystallization heat (ΔHc) of 5 J / g or more and 40 J / g or less in differential scanning calorimetry, and that is compatible with the polyaryl ether ketone resin (A) and the resin (A') other than the resin (A). The material has excellent heat resistance and modeling ability.

[0011] The polyaryletherketone resin (A) is compatible with the resin (A') other than the resin (A), and thus the material has excellent secondary processability, and a material for three-dimensional modeling having excellent uniformity in shape and size can be obtained. Furthermore, a three-dimensional model having excellent appearance and mechanical properties such as tensile strength can be obtained.

[0012] The present invention provides the following [1] to

[26] .

[0013] [1] A resin composition comprising a polyaryletherketone resin (A) and a polyetherimide sulfone resin (B), wherein the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) are compatible with each other.

[0014] [2] The resin composition according to [1], wherein the polyaryletherketone resin (A) is a polyetherketoneketone resin.

[0015] [3] The resin composition according to [1] or [2], wherein the polyaryl ether ketone resin (A) has a repeating unit (a-1) represented by the following general formula (1) and / or a repeating unit (a-2) represented by the following general formula (2):

[0016] [ka]

[0017] In the general formulas (1) and (2), Ar 1 ~Ar 6Each of (1,4)Ar in the general formula (1) independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. 3 The ketone group is Ar 3 The (1,3)Ar groups in the general formula (2) are bonded to the 1st and 4th positions of the 6 The ketone group is Ar 6 are attached to the 1st and 3rd positions of the group.

[0018] [4] The resin composition according to [3], wherein the polyaryl ether ketone resin (A) has a repeating unit (a-1) represented by the general formula (1) and a repeating unit (a-2) represented by the general formula (2), and the unit molar ratio of the repeating unit (a-1) to the repeating unit (a-2), [(a-1) / (a-2)], is 1 or more and 5 or less.

[0019] [5] The resin composition according to [3] or [4], wherein the repeating unit (a-1) represented by the general formula (1) is a repeating unit represented by the following structural formula (1A), and the repeating unit (a-2) represented by the general formula (2) is a repeating unit represented by the following structural formula (2A):

[0020] [ka]

[0021] [6] The resin composition according to any one of [1] to [5], wherein the polyetherimide sulfone resin (B) has a repeating unit (b-1) represented by the following general formula (3):

[0022] [ka]

[0023] In the general formula (3), Y 1 ~Y 6 each independently represents a hydrogen atom, an alkyl group, or an alkoxy group. 7 ~Ar 10each independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. X 1 represents a direct bond, or a divalent aliphatic hydrocarbon group, -O-, -SO2-, -S-, or -C(=O)-.

[0024] [7] The resin composition according to [6], wherein the repeating unit (b-1) represented by the general formula (3) is a repeating unit represented by the following structural formula (3A):

[0025] [ka]

[0026] [8] The resin composition according to any one of [4] to [7], wherein the unit molar ratio [(a-1) / (a-2)] of the repeating unit (a-1) and the repeating unit (a-2) constituting the polyaryletherketone resin (A) is 1 or more and 2 or less, and the polyetherimide sulfone resin (B) has a repeating unit (b-2) represented by the following general formula (4):

[0027] [ka]

[0028] In the general formula (4), Y 7 ~Y 12 each independently represents a hydrogen atom, an alkyl group, or an alkoxy group. 11 ~Ar 14 each independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. X 2 represents a direct bond, or a divalent aliphatic hydrocarbon group, -O-, -SO2-, -S-, or -C(=O)-.

[0029] [9] The resin composition according to [8], wherein the repeating unit (b-2) represented by the general formula (4) is a repeating unit represented by the following structural formula (4A):

[0030] [ka]

[0031]

[10] The resin composition according to any one of [1] to [9], wherein the content ratio of the polyaryletherketone resin (A):polyetherimide sulfone resin (B) in a total of 100 mass% of the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) is in the range of 90:10 to 10:90 (mass%).

[0032]

[11] The resin composition according to any one of [1] to

[10] , wherein the polyaryl ether ketone resin (A) and the polyetherimide sulfone resin (B) have a single glass transition temperature.

[0033]

[12] The resin composition according to

[11] , wherein the glass transition temperature is 180°C or higher and 260°C or lower.

[0034]

[13] The resin composition according to

[11] or

[12] , wherein the ratio E'(Tg-20°C) / E'(Tg+20°C) of the tensile modulus E'(Tg-20°C) at a temperature 20°C lower than the glass transition temperature to the tensile modulus E'(Tg+20°C) at a temperature 20°C higher than the glass transition temperature is 100 or more and 1,000 or less.

[0035]

[14] 360°C, shear rate 1000s -1 The resin composition according to any one of [1] to

[13] , having a melt viscosity of 100 Pa·s or more and 1000 Pa·s or less.

[0036]

[15] A film made of the resin composition according to any one of [1] to

[14] .

[0037]

[16] A composite material obtained by combining the resin composition according to any one of [1] to

[14] or the film according to

[15] with reinforcing fibers.

[0038]

[17] The composite material according to

[16] , which is a prepreg or semipreg.

[0039]

[18] A moving body, which is an aircraft, automobile, ship or rail vehicle, comprising the composite material according to

[16] or

[17] .

[0040]

[19] A material for three-dimensional modeling, comprising the resin composition according to any one of [1] to

[14] .

[0041]

[20] A material for three-dimensional modeling comprising a polyaryletherketone resin (A) in which the ratio of the number of ether groups to the number of ketone groups is less than 2, and a resin (A') other than the polyaryletherketone resin (A), wherein the heat of crystallization (ΔHc) measured by differential scanning calorimetry is 5 J / g or more and 40 J / g or less, and the polyaryletherketone resin (A) and the resin (A') other than the resin (A) are compatible with each other.

[0042]

[21] The material for three-dimensional modeling according to

[20] , wherein the resin (A') is at least one of polyetherimide sulfone (PEIS) (resin (B)) or polyetherimide (PEI) (resin (C)).

[0043]

[22] A filament for three-dimensional printing, comprising the material for three-dimensional printing according to any one of

[19] to

[21] .

[0044]

[23] The filament for three-dimensional printing according to

[22] , having a filament diameter of 1.0 mm or more and 5.0 mm or less.

[0045]

[24] A wound body of a filament for three-dimensional printing according to

[22] or

[23] .

[0046]

[25] A cartridge for three-dimensional modeling, comprising a container containing a filament for three-dimensional modeling according to

[22] or

[23] .

[0047]

[26] A molded body made of the material for three-dimensional modeling according to any one of

[19] to

[21] . Effect of the Invention

[0048] The present invention provides a resin composition having high heat resistance as well as excellent melt moldability and secondary processability, and a film, a composite material, a moving body, a material for three-dimensional modeling, a filament for three-dimensional modeling, and a molded body using the same. The reason why the resin composition of the present invention exhibits such effects is not yet clear, but is presumed to be as follows. In other words, by kneading polyetherketoneketone resin and polyetherimide sulfone resin in a specific combination, it is presumed that a resin composition is obtained that has only one higher glass transition temperature than the polyetherketoneketone resin alone and also has a lower melt viscosity, thereby combining high heat resistance with excellent melt moldability and secondary processability. The reason why the material for three-dimensional modeling of the present invention is effective is not yet clear, but is presumed to be as follows. In other words, by using a polyetherketoneketone resin with an optimal ratio of chemically stable ether groups and ketone groups that impart high heat resistance for 3D modeling, and by reducing the crystallinity of the polyetherketoneketone resin, crystallization shrinkage of the modeled object during 3D modeling is reduced, resulting in a resin composition that combines high heat resistance with excellent melt moldability and secondary processability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0049] The present invention will be described in detail below.

[0050] The resin composition of the present invention contains a polyaryl ether ketone resin (A) and a polyetherimide sulfone resin (B), and is characterized in that the polyaryl ether ketone resin (A) and the polyetherimide sulfone resin (B) are compatible with each other.

[0051] The three-dimensional modeling material of the present invention comprises a polyaryl ether ketone resin (A) in which the ratio of the number of ether groups to ketone groups is less than 2, and a resin (A') other than the polyaryl ether ketone resin (A), and is characterized in that the heat of crystallization (ΔHc) measured by differential scanning calorimetry is 5 J / g or more and 40 J / g or less, and the polyaryl ether ketone resin (A) and the resin (A') other than the resin (A) are compatible with each other.

[0052] [Polyaryletherketone resin (A)] The polyaryl ether ketone resin (A) used in the present invention may be a resin having at least an aryl group, an ether group and a ketone group as structural units. Examples of the polyaryletherketone resin (A) include polyetherketoneketone (PEKK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneetherketoneketone (PEKEKK), polyaryletherketoneetherketoneketone (PAEKEKK), polyaryletherketone (PAEK), polyaryletheretherketone (PAEEK), polyetheretherketoneketone (PEEKK), polyaryletherketoneketone (PAEKK), polyaryletheretherketoneketone (PAEEKK), and the like.

[0053] Among these, polyetherketoneketone resins, polyetherketone resins, polyetheretherketone resins, polyetherketoneetherketoneketone resins, polyetheretherketoneketone resins, and polyetheretherketoneketone resins are preferred because of their excellent mechanical properties, thermal stability, and melt moldability, and polyetherketoneketone resins and polyetherketone resins are more preferred, and polyetherketoneketone resins are particularly preferred because of their excellent thermal stability and melt moldability, and polyetherketoneketone resins having repeating units (a-1) represented by the following general formula (1) and / or repeating units (a-2) represented by the following general formula (2) are preferred, and polyetherketoneketone resins having repeating units (a-1) represented by the following general formula (1) and repeating units (a-2) represented by the following general formula (2) are more preferred. It is particularly preferred that each of these repeating units (a-1) and (a-2) has one ether group and two ketone groups.

[0054] In the three-dimensional modeling material of the present invention, among the above polyaryletherketone resins (A), a polyaryletherketone resin is used in which the ratio of the number of ether groups to the number of ketone groups is less than 2. Since three-dimensional modeling requires a longer heating time during molding processing than film formation or injection molding, and voids are likely to form inside the molded product, it is possible to obtain a molded product with excellent heat resistance and chemical resistance by optimizing the ratio of ether groups to ketone groups in the polyaryletherketone resin used in the three-dimensional modeling material.

[0055] [ka]

[0056] In the general formulas (1) and (2), Ar 1 ~Ar 6 Each of (1,4)Ar in the general formula (1) independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. 3 The ketone group is Ar 3 The (1,3)Ar groups in the general formula (2) are bonded to the 1st and 4th positions of the 6The ketone group is Ar 6 are attached to the 1st and 3rd positions of the group.

[0057] In the general formulas (1) and (2), Ar 1 ~Ar 6 The arylene groups in may be different from each other, but are preferably the same. 1 ~Ar 6 Specific examples of the arylene group include a phenylene group and a biphenylene group. Among these, a phenylene group is preferred, and Ar 1 ,Ar 2 ,Ar 4 ,Ar 5 is preferably a p-phenylene group. 3 is a p-arylene group, preferably a p-phenylene group. 6 is a m-arylene group, preferably a m-phenylene group.

[0058] Ar 1 ~Ar 6 Examples of the substituent that the arylene group may have include an alkyl group having 1 to 20 carbon atoms, such as a methyl group or an ethyl group, and an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group or an ethoxy group. 1 ~Ar 6 When has a substituent, there is no particular limitation on the number of the substituents.

[0059] From the viewpoints of mechanical properties, thermal stability, and melt moldability, it is preferred that the repeating unit (a-1) represented by the general formula (1) constituting the polyaryl ether ketone resin (A) is a repeating unit represented by the following structural formula (1A), and that the repeating unit (a-2) represented by the general formula (2) is a repeating unit represented by the following structural formula (2A).

[0060] [ka]

[0061] The lower limit of the unit molar ratio [(a-1) / (a-2)] of the repeating unit (a-1) and the repeating unit (a-2) in the polyaryl ether ketone resin (A) is preferably 1 or more, more preferably 1.1 or more, even more preferably 1.2 or more, particularly preferably 1.3 or more, and particularly preferably 1.4 or more. If the unit molar ratio is 1 or more, the glass transition temperature is less likely to decrease, and excellent heat resistance is easily maintained. On the other hand, the unit molar ratio [(a-1) / (a-2)] is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, particularly preferably 2 or less, particularly preferably 1.7 or less, and most preferably 1.5 or less. If the unit molar ratio is 5 or less, the glass transition temperature and crystal melting temperature do not become too high, so that the melt moldability is excellent, and the heat fusion property when combined with reinforcing fibers and the interlayer adhesion property when three-dimensionally modeled are also excellent, which is preferable.

[0062] Although details will be described later, when the polyetherimide sulfone resin (B) to be blended with the polyaryletherketone resin (A) is a polyetherimide sulfone resin (B) having a repeating unit (b-2) represented by general formula (4) described later, as long as the unit molar ratio [(a-1) / (a-2)] is in the range of 1 or more and 2 or less, the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) do not undergo phase separation and tend to exhibit compatibility, resulting in excellent secondary processability.

[0063] From the viewpoint of ensuring mechanical properties, the total number (degree of polymerization) of the repeating units (a-1) and (a-2) in the polyaryl ether ketone resin (A) is preferably 10 or more, more preferably 20 or more. From the viewpoint of melt moldability, the degree of polymerization is preferably 100 or less, more preferably 50 or less.

[0064] The polyaryletherketone resin (A) may have repeating units other than the repeating units (a-1) and (a-2), but in that case, in order to reliably obtain the above-mentioned effects due to the repeating units (a-1) and (a-2) in the polyaryletherketone resin (A), the ratio of the other repeating units to the total of the repeating units (a-1), (a-2) and the other repeating units is 20 mol % or less, particularly 10 mol % or less. It is most preferable that the polyaryletherketone resin (A) does not contain other repeating units.

[0065] The glass transition temperature of the polyaryl ether ketone resin (A) is preferably 150°C or higher, more preferably 153°C or higher, and even more preferably 155°C or higher. If the glass transition temperature is the above lower limit or higher, a resin composition having sufficient heat resistance is easily obtained. On the other hand, the glass transition temperature of the polyaryl ether ketone resin (A) is preferably 200°C or lower, more preferably 195°C or lower, even more preferably 190°C or lower, particularly preferably 185°C or lower, and especially preferably 180°C or lower. If the glass transition temperature is the above upper limit or lower, it is preferable because it has excellent melt moldability, is easily heat fused at low temperatures when combined with reinforcing fibers, and is easily bonded between layers when performing three-dimensional modeling.

[0066] The crystallinity of the polyaryletherketone resin (A) varies depending on the unit molar ratio [(a-1) / (a-2)] of the repeating unit (a-1) and the repeating unit (a-2). For example, when the polyaryletherketone resin (A) is a resin having a repeating unit represented by the structural formula (1A) and a repeating unit represented by the structural formula (2A), the resin generally exhibits crystallinity when the unit molar ratio is 1.5 or more, and exhibits amorphousness when it is less than 1.5. In the present invention, the polyaryletherketone resin (A) may be crystalline or amorphous. In the case of the crystallinity, the crystal melting temperature of the polyaryletherketone resin (A) is preferably 280°C or more, more preferably 285°C or more, even more preferably 290°C or more, particularly preferably 295°C or more, and particularly preferably 300°C or more. If the crystal melting temperature is the above lower limit or more, a resin composition having excellent heat resistance is easily obtained. On the other hand, the crystal melting temperature is preferably 400° C. or less, more preferably 380° C. or less, even more preferably 360° C. or less, particularly preferably 340° C. or less, and particularly preferably 335° C. or less. When the crystal melting temperature is the above upper limit or less, the melt moldability is excellent.

[0067] The heat of crystal fusion of the polyaryl ether ketone resin (A) is preferably 60 J / g or less, more preferably 50 J / g or less, even more preferably 40 J / g or less, particularly preferably 30 J / g or less, and particularly preferably 26 J / g or less. If the heat of crystal fusion is below the upper limit, crystallization is suppressed, so that molding shrinkage and deterioration of transparency due to crystallization can be suppressed, and the heat fusion property when combined with reinforcing fibers and the interlayer adhesion property during three-dimensional modeling tend to be excellent. On the other hand, the heat of crystal fusion is preferably 1 J / g or more, more preferably 2 J / g or more, even more preferably 3 J / g or more, particularly preferably 4 J / g or more, and particularly preferably 5 J / g or more. If the heat of crystal fusion is above the lower limit, heat resistance is easily maintained.

[0068] The glass transition temperature in the present invention refers to the peak top temperature of the loss tangent (tan δ) in dynamic viscoelasticity measurement according to JIS K7244-4:1999. The crystal melting temperature and the heat of crystal melting are determined from a DSC (Differential Scanning Calorimetry) curve detected when the temperature is increased in the temperature range of 25 to 400°C at a heating rate of 10°C / min using a differential scanning calorimeter in accordance with JIS K7121:2012 and JIS K7122:2012. The same applies below.

[0069] The polyaryl ether ketone resin (A) can be produced by known methods (for example, see JP-A-61-195122, JP-A-62-129313, US Pat. No. 4,175,175, etc.).

[0070] In addition, commercially available products can be used as the polyaryletherketone resin (A). Commercially available polyaryletherketone resins (A) include, for example, the "KEPSTAN" series manufactured by Arkema, the "KSTONE" series manufactured by SHANDONG KAISHENG NEW MATERIALS, and the "NovaSpire" series manufactured by SOLVAY. Commercially available polyetherketone resins include the "VICTREX HT" series manufactured by Victrex and the "G-PAEK" series manufactured by Garda Plastics.

[0071] The polyaryl ether ketone resin (A) may be used alone or in combination of two or more kinds.

[0072] [Resin (A') other than polyaryletherketone resin (A)] The resin (A') other than the polyaryl ether ketone resin (A) used in the material for three-dimensional modeling of the present invention is It is a resin that is compatible with the polyaryl ether ketone resin (A).

[0073] Examples of resins that can be used as the resin (A') include polyetherimide sulfone (PEIS) (polyetherimide sulfone resin (B)), polyetherimide (PEI) (resin (C)), etc. In particular, by using polyetherimide sulfone (PEIS) (polyetherimide sulfone resin (B)) as the resin (A'), better heat resistance can be obtained, which is preferable.

[0074] [Polyetherimide sulfone resin (B)] The polyetherimide sulfone resin (B) used in the present invention is not particularly limited and any known resin can be used. Preferred examples include those having a repeating unit (b-1) represented by the following general formula (3) and / or a repeating unit (b-2) represented by the following general formula (4).

[0075] [ka]

[0076] In the general formula (3), Y 1 ~Y 6 each independently represents a hydrogen atom, an alkyl group, or an alkoxy group. 7 ~Ar 10 each independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. X 1 represents a direct bond, or a divalent aliphatic hydrocarbon group, -O-, -SO2-, -S-, or -C(=O)-.

[0077] [ka]

[0078] In the general formula (4), Y 7 ~Y 12 each independently represents a hydrogen atom, an alkyl group, or an alkoxy group. 11 ~Ar 14 each independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. X2 represents a direct bond or a divalent aliphatic hydrocarbon group, -O-, -SO2-, -S-, or -C(=O)-.

[0079] In the above general formula (3), Ar 7 ~Ar 10 The arylene groups in may be different from each other, but are preferably the same. 7 ~Ar 10 Specific examples of the arylene group include a phenylene group, a biphenylene group, etc. Among these, a phenylene group is preferred, and a p-phenylene group is more preferred.

[0080] Ar 7 ~Ar 10 Examples of the substituent that the arylene group may have include an alkyl group having 1 to 20 carbon atoms, such as a methyl group or an ethyl group, and an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group or an ethoxy group. 7 ~Ar 10 When has a substituent, there is no particular limitation on the number of the substituents.

[0081] In the above general formula (4), Ar 11 ~Ar 14 The arylene groups in may be different from each other, but are preferably the same. 11 ~Ar 14 Specific examples of the arylene group include a phenylene group, a biphenylene group, etc. Among these, a phenylene group is preferred, and a p-phenylene group is particularly preferred.

[0082] Ar 11 ~Ar 14 Examples of the substituent that the arylene group may have include an alkyl group having 1 to 20 carbon atoms, such as a methyl group or an ethyl group, and an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group or an ethoxy group. 11 ~Ar 14 When has a substituent, there is no particular limitation on the number of the substituents.

[0083] From the viewpoints of mechanical properties, thermal stability, melt moldability, and compatibility with the polyaryl ether ketone resin (A), the repeating unit (b-1) represented by the above general formula (3) contained in the polyetherimide sulfone resin (B) is preferably a repeating unit represented by the following structural formula (3A), and the repeating unit (b-2) represented by the above general formula (4) is preferably a repeating unit represented by the following structural formula (4A).

[0084] [ka]

[0085] [ka]

[0086] Generally, polyetherimide sulfone resins are classified by structure according to the difference in the bonding mode. As the polyetherimide sulfone resin (B) contained in the resin composition of the present invention, there can be used one having a repeating unit (b-1) represented by the above general formula (3), preferably the above structural formula (3A), and one having a repeating unit (b-2) represented by the above general formula (4), preferably the above structural formula (4A). The former is typically obtained by using 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and 4,4'-diaminodiphenyl sulfone as raw material monomers. The latter is typically obtained by using 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride and 4,4'-diaminodiphenyl sulfone as raw material monomers.

[0087] The polyetherimide sulfone resin (B) having the repeating unit (b-1) represented by the general formula (3) does not phase separate with the polyaryletherketone resin (A) over the entire composition, regardless of the unit molar ratio [(a-1) / (a-2)] of the polyaryletherketone resin (A). On the other hand, the polyetherimide sulfone resin (B) having the repeating unit (b-2) represented by the general formula (4) is likely to be compatible when the unit molar ratio [(a-1) / (a-2)] of the polyaryletherketone resin (A) is 1 or more and 2 or less. In the present invention, by selecting and using the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) having the optimal structure, a resin composition or a material for three-dimensional modeling that does not phase separate and has excellent secondary processability can be obtained.

[0088] The total number (degree of polymerization) of the repeating units (b-1) and / or repeating units (b-2) in the polyetherimide sulfone resin (B) is preferably 10 or more, more preferably 20 or more, in order to achieve an excellent balance between heat resistance and moldability, and is preferably 1,000 or less, more preferably 500 or less.

[0089] The polyetherimide sulfone resin (B) may have repeating units other than the repeating units (b-1) and (b-2) as long as the effects of the present invention are not impaired. For example, the polyetherimide sulfone resin (B) may have repeating units derived from the following dianhydrides as raw material monomers: 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)benzophenone ... ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dian Non dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, cyclobutane tetracarboxylic acid dianhydride, cyclopenta 1,3,3a,5-Dioxo-3-furanyl)-naphtho[1,2,-c]-furan-1,3-dione, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, naphthalic dianhydride (such as 2,3,6,7-naphthalic dianhydride), 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoropyridine diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylsulfine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid) 4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 2,2'-bis-(3,4-dicarboxyphenyl)hexafluoro-propane dianhydride, 4,4'-oxydiphthalic anhydride, pyromellitic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4',4'-bisphenol A dianhydride, hydroquinone diphthalic anhydride, ethylene glycol bistrimellitic anhydride, 6,6'-bis(3,4-dicarboxyphenoxy)-2,2',3,3 '-Tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi[1H-indene]dianhydride, 7,7'-bis(3,4-dicarboxyphenoxy)-3,3',4,4'-tetrahydro-4,4,4',4'-tetramethyl-2,2'-spirobi[2H-1-benzopyran]dianhydride, 1,1'-bis[1-(3,4-dicarboxyphenoxy)-2-methyl-4-phenyl]cyclohexane dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic acid dianhydride Water, 3,3',4,4'-diphenylsulfoxide tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3'-benzophenone tetracarboxylic dianhydride, 4,4'-carbonyldiphthalic anhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2-bis(4-(3,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(4-(3,3-dicarboxyphenyl)hexafluoropropane dianhydride, (3,3',4,4'-diphenyl)phenylphosphine tetracarboxylic dianhydride, (3,3',4,4'-diphenyl)phenylphosphine oxide tetracarboxylic dianhydride, 2,2'-dichloro-3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2'-dimethyl-3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2'-dicyano-3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2'-dibromo-3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2'-diiodo-3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2'-ditrifluoromethyl-3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2'-bis(1-methyl-4-phenyl)-3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2'-bis(1-trifluoromethyl-2-phenyl-3,3',4, A dianhydride selected from the group consisting of 4'-biphenyltetracarboxylic dianhydride, 2,2'-bis(1-trifluoromethyl-3-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'-bis(1-trifluoromethyl-4-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'-bis(1-phenyl-4-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2'-bis(1,3-trifluoromethyl-4-phenyl)-3,3',4,4'-biphenyltetracarboxylic dianhydride, and 5,5'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)]bis[1,3-isobenzofurandione] and all isomers thereof, and mixtures and blends comprising at least one of the foregoing.

[0090] When the polyetherimide sulfone resin (B) has repeating units other than the repeating units (b-1) and (b-2), the amount of the other repeating units is preferably 20 mol % or less, particularly preferably 10 mol % or less, of the total of the repeating units (b-1), (b-2) and the other repeating units, from the viewpoint of maintaining the mechanical properties, thermal stability, melt moldability, and compatibility with the polyaryletherketone resin (A).

[0091] The glass transition temperature of the polyetherimide sulfone resin (B) is preferably 230°C or higher, more preferably 240°C or higher, even more preferably 250°C or higher, particularly preferably 255°C or higher, and particularly preferably 260°C or higher. If the glass transition temperature is above the lower limit, the heat resistance tends to be excellent. On the other hand, the glass transition temperature of the polyetherimide sulfone resin (B) is preferably 310°C or lower, more preferably 300°C or lower, even more preferably 295°C or lower, particularly preferably 290°C or lower, and particularly preferably 285°C or lower. If the glass transition temperature is below the upper limit, the melt moldability tends to be excellent.

[0092] The heat of crystalline fusion of the polyetherimide sulfone resin (B) is preferably 10 J / g or less, more preferably 5 J / g or less, and even more preferably 0 J / g, i.e., substantially amorphous. If the heat of crystalline fusion is equal to or less than the upper limit, the crystallization of the resin composition or the material for three-dimensional modeling of the present invention is suppressed, so that molding shrinkage and deterioration of transparency due to crystallization are easily suppressed.

[0093] The polyetherimide sulfone resin (B) can be produced by a known method.

[0094] Commercially available products can also be used as the polyetherimide sulfone resin (B). Examples of commercially available products of the polyetherimide sulfone resin (B) include the "EXTEM" series manufactured by SABIC Innovative Plastics.

[0095] The polyetherimide sulfone resin (B) may be used alone or in combination of two or more kinds.

[0096] [Polyetherimide resin (C)] The polyetherimide resin (C) used in the present invention has a repeating unit (c-1) represented by the following structural formula (5).

[0097] [ka]

[0098] Generally, polyetherimide resins are classified by their structures according to the difference in the bond type, i.e., the difference between meta bond and para bond. As is clear from the repeating unit (c-1) represented by structural formula (5), the polyetherimide resin (C) used in the present invention has the imide group bonded at the para position.

[0099] On the other hand, there are also those in which the bonding position of the imide group having the repeating unit (c-2) represented by the following structural formula (6) is the meta position.

[0100] [ka]

[0101] In the present invention, by using a resin having a repeating unit (c-1) represented by structural formula (5), particularly a resin consisting only of the repeating unit (c-1), as the polyetherimide resin (C), it is possible to improve rigidity, heat resistance, and chemical resistance, and also to exhibit good impact resistance, particularly high impact resistance at low temperatures. The total number (degree of polymerization) of the repeating units (c-1) of the polyetherimide resin (C) is preferably 10 or more, more preferably 20 or more, in order to obtain an excellent balance between heat resistance and moldability. Also, the total number (degree of polymerization) is preferably 1000 or less, more preferably 500 or less.

[0102] The polyetherimide resin (C) may have a repeating unit other than the repeating unit (c-1) as long as the effect of the present invention is not impaired. For example, the polyetherimide resin (C) may have a repeating unit (c-2) represented by the structural formula (6). In this case, the content of the repeating unit (c-2) is preferably 20 mol % or less, more preferably 10 mol % or less, of the total repeating units in terms of impact resistance, heat resistance, and chemical resistance.

[0103] The glass transition temperature of the polyetherimide resin (C) is preferably 160° C. or higher, more preferably 180° C. or higher, and even more preferably 200° C. or higher. If the glass transition temperature is equal to or higher than the lower limit, a resin composition or a material for three-dimensional modeling having sufficient heat resistance can be obtained. On the other hand, the upper limit of the glass transition temperature is preferably 250° C., more preferably 240° C., in order to exhibit heat fusion properties at a lower temperature and ensure melt moldability.

[0104] The heat of crystalline fusion of the polyetherimide resin (C) is preferably 10 J / g or less, more preferably 5 J / g or less, and even more preferably 0 J / g, i.e., substantially amorphous. If the heat of crystalline fusion is equal to or less than the upper limit, the crystallinity of the resin composition or the material for three-dimensional modeling of the present invention can be reduced, and the heat fusion property during secondary processing is easily excellent.

[0105] The polyetherimide resin (C) can be produced by known methods (see, for example, US Pat. Nos. 3,803,085 and 3,905,942).

[0106] The polyetherimide resin (C) may be a commercially available product. Examples of commercially available polyetherimide resins (C) include the "Ultem" series manufactured by SABIC Innovative Plastics.

[0107] The polyetherimide resin (C) may be used alone or in combination of two or more kinds.

[0108] [Resin composition / 3D modeling material] The resin composition of the present invention contains a polyaryletherketone resin (A) and a resin (A') other than the polyaryletherketone resin (A), such as a polyetherimide sulfone resin (B). By containing the polyaryletherketone resin (A), a resin composition excellent in melt moldability, heat resistance, and mechanical properties can be obtained. In addition, by containing the polyetherimide sulfone resin (B), the heat resistance of the polyaryletherketone resin (A) can be further improved.

[0109] Below, we will describe the resin composition of the present invention, as well as a resin composition when polyetherimide sulfone resin (B) is used as an example of resin (A') other than polyaryl ether ketone resin (A) in the three-dimensional modeling material of the present invention. In the following description, "the resin composition of the present invention" can be read as "the material for three-dimensional modeling of the present invention." In the following description, the term "resin composition of the present invention" can be read as the "material for three-dimensional modeling of the present invention." In addition, the term "polyetherimide sulfone resin (B)" can be replaced with "resin (A')," "polyetherimide resin (C)," and "polyetherimide sulfone resin (B) and polyetherimide resin (C)."

[0110] In the resin composition of the present invention, it is important that the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) are compatible with each other. Here, compatibility means that in dynamic viscoelasticity measurement, the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) have one glass transition temperature, that is, the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) have one loss tangent (tan δ) peak, or the formation of a structural period or a dispersed structure cannot be confirmed by observation with an electron microscope (for example, a magnification of 3,000 to 30,000 times). In particular, it is important that the glass transition temperature is one.

[0111] Having one glass transition temperature means that all the resin components constituting the resin composition are completely compatible and not phase-separated. On the other hand, having two or more glass transition temperatures means that it is an incompatible or partially compatible system and phase-separated. The glass transition temperature of a resin composition can be evaluated by reading the peak of the loss tangent (tan δ) in dynamic viscoelasticity measurement according to JIS K7244-4:1999. That is, if there is a single peak of tan δ, there is a single glass transition temperature and no phase separation, and if there are multiple peaks of tan δ, there are multiple glass transition temperatures and phase separation.

[0112] When the resin components constituting the resin composition are phase-separated, there are multiple glass transition temperatures, which leads to poor secondary processability. Specifically, at a processing temperature that matches a resin with a low glass transition temperature, the elastic modulus of the resin with a high glass transition temperature remains high, which causes problems such as difficulty in shaping. On the other hand, when the processing temperature is matched to a resin with a high glass transition temperature, the resin with a low glass transition temperature undergoes dimensional changes before reaching that temperature, which causes problems such as wrinkles due to shrinkage, and fluctuations in thickness and wire diameter. The single peak may have a shoulder at its base, and all are treated as compatible systems except when two or more peaks derived from the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) are clearly observed.

[0113] The polyaryl ether ketone resin (A) and the polyetherimide sulfone resin (B) constituting the resin composition of the present invention are a completely compatible system and do not undergo phase separation. Therefore, the resulting resin composition and films and three-dimensional modeling materials obtained using the composition have excellent heat resistance and secondary processability.

[0114] The content ratio of the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) constituting the resin composition of the present invention is preferably in the range of polyaryletherketone resin (A): polyetherimide sulfone resin (B) = 90: 10 to 10: 90 (mass%) in the total of 100 mass% of the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B), more preferably in the range of polyaryletherketone resin (A): polyetherimide sulfone resin (B) = 80: 20 to 20: 80 (mass%), further preferably in the range of polyaryletherketone resin (A): polyetherimide sulfone resin (B) = 75: 25 to 25: 75 (mass%), and particularly preferably in the range of polyaryletherketone resin (A): polyetherimide sulfone resin (B) = 70: 30 to 30: 70 (mass%). If the content ratio of the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) is in such a range, it becomes easy to achieve both heat resistance and melt moldability.

[0115] [Other ingredients] The resin composition of the present invention may contain, in addition to the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B), a resin component other than the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) within a range that does not impair the effects of the present invention. When the resin composition of the present invention contains other resin components, the content of the other resin components is preferably 30 mass % or less, more preferably 20 mass % or less, and even more preferably 10 mass % or less of the total resin components.

[0116] The resin composition of the present invention may contain various additives such as reinforcing fibers such as carbon fibers, heat stabilizers, antioxidants, UV absorbers, light stabilizers, antibacterial and antifungal agents, antistatic agents, lubricants, pigments, dyes, etc., within the scope of not impairing the effects of the present invention. Among them, the resin composition of the present invention may contain reinforcing fibers, and when reinforcing fibers are contained, the content ratio of the reinforcing fibers in the resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and on the other hand, is preferably 90% by mass or less, more preferably 80% by mass or less.

[0117] [Glass transition temperature] The resin composition of the present invention has a glass transition temperature derived from the polyaryl ether ketone resin (A) and the polyetherimide sulfone resin (B), which is measured by reading the peak of the loss tangent (tan δ) of dynamic viscoelasticity measurement in accordance with JIS K7244-4:1999, of preferably 180 ° C. or more, more preferably 185 ° C. or more, even more preferably 190 ° C. or more, particularly preferably 195 ° C. or more, and particularly preferably 200 ° C. or more. The glass transition temperature is an index of the heat resistance of a film or a three-dimensional molded object, and can also be an index of the heat fusion property when temporarily bonding with reinforcing fibers such as carbon fibers during secondary processing. If the glass transition temperature is above the above lower limit, the heat resistance and heat fusion tend to be excellent. On the other hand, the glass transition temperature is preferably 260 ° C. or less, more preferably 255 ° C. or less, even more preferably 250 ° C. or less, particularly preferably 245 ° C. or less, and particularly preferably 240 ° C. or less. If the glass transition temperature is below the above upper limit, the melt moldability tends to be excellent.

[0118] [Crystal melting temperature] In the case where the resin composition of the present invention has a crystalline melting peak obtained from a DSC (Differential Scanning Calorimetry) curve detected when the resin composition is heated at a temperature range of 25 to 400 ° C. at a heating rate of 10 ° C. / min using a differential scanning calorimeter in accordance with JIS K7121:2012, the crystalline melting temperature of the peak top is preferably 280 ° C. or higher, more preferably 285 ° C. or higher, even more preferably 290 ° C. or higher, particularly preferably 295 ° C. or higher, and particularly preferably 300 ° C. or higher. If the crystalline melting temperature is above the lower limit, the heat resistance tends to be excellent. On the other hand, the crystalline melting temperature is preferably 370 ° C. or lower, more preferably 360 ° C. or lower, even more preferably 350 ° C. or lower, particularly preferably 340 ° C. or lower, and particularly preferably 330 ° C. or lower. If the crystalline melting temperature is below the upper limit, the melt moldability is excellent.

[0119] [Crystal melting heat] When the resin composition of the present invention has a crystalline melting peak obtained from a DSC (Differential Scanning Calorimetry) curve detected when the resin composition is heated at a temperature range of 25 to 400 ° C. and a heating rate of 10 ° C. / min using a differential scanning calorimeter according to JIS K7122: 2012, the crystalline melting heat of the peak is preferably 25 J / g or less, more preferably 20 J / g or less, even more preferably 15 J / g or less, particularly preferably 10 J / g or less, and particularly preferably 5 J / g or less. If the crystalline melting heat is below the above upper limit, crystallization is suppressed, so that molding shrinkage and deterioration of transparency due to crystallization can be suppressed. On the other hand, there is no particular restriction on the lower limit of the crystalline melting heat, but if it is 1 J / g or more, the heat resistance tends to be excellent.

[0120] [Melt Viscosity] The resin composition of the present invention has a viscosity of 360° C. at a shear rate of 1000 s , as measured in accordance with JIS K7199:1999. -1The melt viscosity in is preferably 100 Pa·s or more, more preferably 200 Pa·s or more, even more preferably 300 Pa·s or more, particularly preferably 400 Pa·s or more, and particularly preferably 500 Pa·s or more. If the melt viscosity is above the lower limit, for example, stable extrusion is easy when forming a film or spinning a filament of a material for three-dimensional modeling. On the other hand, the melt viscosity is preferably 1000 Pa·s or less, more preferably 950 Pa·s or less, even more preferably 900 Pa·s or less, particularly preferably 850 Pa·s or less, and particularly preferably 800 Pa·s or less. If the melt viscosity is below the upper limit, the flowability is excellent and tends to lead to improved productivity.

[0121] [Tensile modulus ratio at 20℃ before and after glass transition temperature] The resin composition of the present invention preferably has a ratio E'(Tg-20°C) / E'(Tg+20°C) of the tensile modulus E'(Tg-20°C) at a temperature 20°C lower than the glass transition temperature to the tensile modulus E'(Tg+20°C) at a temperature 20°C higher than the glass transition temperature, which is within a specific range. A large E'(Tg-20°C) / E'(Tg+20°C) means that the change in modulus of elasticity is large around the glass transition temperature. If this ratio is too large, for example, when forming a speaker diaphragm made of a film using the resin composition of the present invention or performing three-dimensional modeling, or when impregnating a film using the resin composition of the present invention into carbon fiber to obtain a composite material, the dimensional change may be too large, which may cause defects such as wrinkles and distortion. Therefore, it is preferable that E'(Tg-20°C) / E'(Tg+20°C) is not too large. Specifically, it is preferably 1000 or less, more preferably 900 or less, even more preferably 800 or less, particularly preferably 700 or less, especially preferably 600 or less, and most preferably 500 or less. On the other hand, a small E'(Tg-20°C) / E'(Tg+20°C) means that the change in elastic modulus around the glass transition temperature is small, and if this ratio is too small, for example, when molding a speaker diaphragm made of a film using the resin composition of the present invention or performing three-dimensional modeling, or when impregnating a film using the resin composition of the present invention into carbon fiber to obtain a composite material, it is necessary to significantly increase the temperature to sufficiently deform or flow the resin, which is not preferable from the standpoint of safety and economy. From this standpoint, E'(Tg-20°C) / E'(Tg+20°C) is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, particularly preferably 250 or more, particularly preferably 300 or more, and most preferably 350 or more. When E'(Tg-20°C) / E'(Tg+20°C) is in the above specific range, the resin composition of the present invention has excellent secondary processability.

[0122] The tensile modulus of the resin composition of the present invention is measured by the method described later in the Examples section in accordance with JIS K7127:1999. The tensile modulus at a temperature 20°C lower than the glass transition temperature of the resin composition of the present invention is preferably 1000 MPa or more, particularly 1500 MPa or more. If the tensile modulus is the above lower limit or more, for example, when the film or three-dimensional modeling material 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 is easy to exhibit sufficient rigidity. In particular, if the product has sufficient rigidity, it is easy to make the product thin, which can contribute to space saving and resource saving. In addition, there is also an advantage that the film handling property when thinned is also excellent. In addition, when the film or three-dimensional modeling material has orientation due to the manufacturing method, for example, in a film obtained by extrusion molding, the tensile modulus in the extrusion direction from the mold is preferably the above lower limit or more.

[0123] [Method of producing resin composition] There is no limitation on the method for producing the resin composition of the present invention, and a wide variety of known methods for producing thermoplastic resin compositions can be used. For example, the components such as the polyaryl ether ketone resin (A), the polyetherimide sulfone resin (B), and other additives to be blended as necessary are premixed using various mixers such as a tumbler or a Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. Among these, the melt-kneading method using a twin-screw kneading extruder is preferred from the viewpoint of the dispersibility of each component.

[0124] In addition, for example, a master batch obtained by premixing some of the components (e.g., additive components blended as necessary) and feeding them to an extruder and melt-kneading them can be mixed again with the remaining components and melt-kneaded to produce the resin composition of the present invention.

[0125] The melt-kneading temperature is not particularly limited, but is usually 320° C. or higher, preferably 330° C. or higher, and usually 400° C. or lower, preferably 380° C. or lower.

[0126] In order to produce the resin composition of the present invention having one glass transition temperature derived from the polyaryl ether ketone resin (A) and the polyetherimide sulfone resin (B), it is preferable to employ, for example, any of the following methods (1) to (5).

[0127] (1) An appropriate combination of polyaryletherketone resin (A) and polyetherimide sulfone resin (B) is selected. For example, as described above, the unit molar ratio [(a-1) / (a-2)] of the repeating unit (a-1) to the repeating unit (a-2) in the polyaryletherketone resin (A) is controlled so that the polyaryletherketone resin (A) is compatible with the polyetherimide sulfone resin (B).

[0128] (2) Another resin compatible with both the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B), such as a resin having an imide group or a sulfonyl group, is mixed in. In particular, when the polyaryletherketone resin (A) has repeating units represented by the structural formula (1A) and the structural formula (2A), and the polyetherimide sulfone resin (B) has repeating units represented by the structural formula (3A) or the structural formula (4A), it is effective to use the polyetherimide resin (C) or polybiphenylethersulfone (PPSU) as the other resin.

[0129] (3) The polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) are thoroughly kneaded using a single-screw or twin-screw extruder, and in particular, in the case of a combination of resins with poor compatibility, a twin-screw extruder is used. Among them, a method using a twin-screw extruder in which the ratio L / D, which is the ratio of the screw length L (mm) to the screw diameter D (mm), is preferably 15 or more, more preferably 20 or more, preferably 50 or less, and more preferably 40 or less, can be mentioned. By making such a ratio 15 or more, it becomes easier to further improve the compatibility between the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B). By making such a ratio 50 or less, it tends to be easier to suppress the generation of discoloration, outgassing, gel-like foreign matter, etc., due to thermal degradation caused by a long resin residence time or an excessively high resin temperature. As the screw configuration of the extruder, a structure having a kneading unit, especially a spiral kneading unit, is preferable for improving kneading. One or two kneading units are preferable.

[0130] The resin temperature during melt kneading is 320° C. or higher, more preferably 330° C. or higher, preferably 400° C. or lower, more preferably 380° C. or lower, as measured at the outlet of the extruder. By setting the resin temperature at 320° C. or higher, compatibility can be further improved. If the resin temperature is 400° C. or lower, discoloration of the resin composition and generation of burnt foreign matter can be easily suppressed, and this is therefore preferred.

[0131] The ratio Q / Ns of the discharge rate Q (kg / hr) during melt kneading to the screw rotation speed Ns (rpm) is preferably 0.1 or more, more preferably 0.2 or more, and preferably 10 or less, more preferably 5 or less. By setting this value within the above range, discoloration of the resin composition and generation of foreign matter caused by an excessively high resin temperature or an excessively long residence time can be suppressed, while the polyaryl ether ketone resin (A) and the polyetherimide sulfone resin (B) can be easily made sufficiently compatible with each other.

[0132] A continuous kneader is also preferably used as a kneader. A continuous kneader is a kneader in which a screw rotatably attached in the cylinder of an extruder is provided with a plurality of rotating blades, and a fixed blade is further provided in the cylinder in a state inserted between the plurality of rotating blades. When the screw rotates, the raw material moving along the screw axis passes through the gap formed between the rotating blade and the fixed blade in a zigzag manner, from the center side to the outer periphery side, and then from the outer periphery side to the center side, and is kneaded. Therefore, the three actions of compression, shearing, and replacement can be efficiently given to the raw material, and the dispersion of each component can be improved more effectively than in a single-screw or twin-screw extruder. There is no particular restriction on the shape of the blade, but for example, a fan-shaped, chrysanthemum-shaped, or mortar-shaped blade can be used. For example, the "NES·KO series" manufactured by Chemical Engineering Co., Ltd. is an example of such a continuous kneader.

[0133] (4) The melt viscosities of the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) are made close to each other. Specifically, at 360°C and a shear rate of 1000 s -1 The difference in melt viscosity between the two is preferably 1000 Pa·s or less. The melt viscosity can be controlled by the molecular weight and branched structure.

[0134] (5) Mixing a compatibilizer to increase compatibility.

[0135] [Method of molding resin composition] The resin composition of the present invention can be molded and used by a general molding method, such as extrusion molding, injection molding, blow molding, vacuum molding, pressure molding, press molding, etc. In each molding method, the apparatus and processing conditions are not particularly limited, and known methods can be adopted. In particular, from the viewpoint of processability when forming a composite material as described below, it is preferable to form the resin composition of the present invention into a film by extrusion molding, etc. Moreover, the resin composition of the present invention can be made into pellets or filaments, preferably by extrusion molding, to provide the three-dimensional modeling material of the present invention.

[0136] The film made of the resin composition of the present invention includes sheets. 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 Standard JISK6900:1994). Generally, a sheet, as defined in JIS, is a thin, flat product whose thickness is generally small compared to its length and width. However, since the boundary between a sheet and a film is unclear, in the present invention, a film includes sheets. Therefore, "film" may also be "sheet".

[0137] [Film manufacturing method] When the resin composition of the present invention is used as a film, the method of producing the film is not particularly limited, and for example, it can be obtained as a non-stretched or stretched film. From the viewpoint of secondary processability, it is preferable to obtain it as a non-stretched film. The non-stretched film is a film that is not actively stretched in order to suppress the orientation of the sheet, and here includes a film whose stretch ratio with a stretch roll in extrusion molding or the like is less than 2 times.

[0138] The non-stretched film can be produced, for example, by melt-kneading each constituent material as described above, followed by extrusion molding and cooling. For melt-kneading, a known kneader such as a single-screw or twin-screw extruder can be used. The melting temperature is appropriately adjusted depending on the type and mixing ratio of the resin, the presence or absence and type of additives, and is preferably 320°C or higher, more preferably 330°C or higher, from the viewpoint of productivity and suppressing crosslinking or decomposition of the resin. On the other hand, the melting temperature is preferably 400°C or lower, more preferably 380°C or lower. The molded film can be produced, for example, by extrusion molding using a mold such as a T-die.

[0139] The cooling can be performed, for example, by contacting the film with a cooling machine such as a cooled cast roll to rapidly cool it. This solidifies the molded product, and an unstretched film is obtained. The cooling temperature (cast roll temperature) is not limited as long as it is lower than the melting temperature, but is preferably 260°C or lower, more preferably 250°C or lower, even more preferably 240°C or lower, particularly preferably 230°C or lower, and especially preferably 220°C or lower. On the other hand, the cooling temperature (cast roll temperature) is preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, particularly preferably 150°C or higher, and especially preferably 160°C or higher. If the cooling temperature is within this range, a film with a good appearance that is free from wrinkles or sticking due to rapid cooling is easily obtained.

[0140] The thickness of the film made of the resin composition of the present invention is not particularly limited, but from the viewpoints of film strength, handling properties, film formability, secondary processability, etc., the thickness is preferably 1 μm or more, more preferably 3 μm or more, even more preferably 6 μm or more, particularly preferably 12 μm or more, and especially preferably 20 μm or more. On the other hand, the thickness of the film is preferably 3 mm or less, more preferably 1 mm or less, even more preferably 500 μm or less, particularly preferably 300 μm or less, and especially preferably 100 μm or less.

[0141] The film made of the resin composition of the present invention can be laminated with other layers to form a multi-layer film, as long as the effects of the present invention are not impaired. The multi-layering method can be, for example, a known method such as coextrusion, extrusion lamination, heat lamination, or dry lamination.

[0142] [Use and mode of use] The resin composition of the present invention or a molded article such as a film made of the resin composition of the present invention can be used for a composite material, for example, as a matrix of a fiber-reinforced plastic, which is a composite material with reinforcing fibers. The fiber-reinforced plastic obtained has excellent heat resistance and mechanical properties.

[0143] The type of reinforcing fiber is not particularly limited, and examples thereof include inorganic fibers such as carbon fibers, glass fibers, boron fibers, and alumina fibers, organic fibers such as liquid crystal polymer fibers, polyethylene fibers, aramid fibers, and polyparaphenylenebenzoxazole fibers, and metal fibers such as aluminum fibers, magnesium fibers, titanium fibers, SUS fibers, and copper fibers. Among these, carbon fibers are preferred from the viewpoints of rigidity and light weight.

[0144] The shape of the reinforcing fibers is not particularly limited, and can be appropriately selected as needed from among fiber bundles such as chopped strands and rovings, woven fabrics such as plain weave and twill weave, knitted fabrics, nonwoven fabrics, fiber papers, and reinforcing fiber sheets such as UD materials (unidirectional materials).

[0145] The method of compounding the resin composition of the present invention with the reinforcing fiber is not particularly limited, and a conventionally known method can be adopted. For example, when melt-kneading the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B), a chopped strand of reinforcing fiber or the like is compounded to compound, or a roving-shaped continuous reinforcing fiber is impregnated with the resin composition of the present invention, thereby obtaining a composite material of the resin composition and the reinforcing fiber.

[0146] The method for compounding the film made of the resin composition of the present invention with the reinforcing fiber is not particularly limited, and a conventionally known method can be adopted. For example, a composite material in a prepreg state or semi-preg state (state in which voids exist) can be produced by impregnating or semi-impregnating a reinforcing fiber bundle or a reinforcing fiber sheet with the resin composition of the present invention.

[0147] Specifically, a film made of the resin composition of the present invention is superimposed on one or both sides of the aforementioned reinforcing fiber sheet, and the film is melted by heating and pressing, and the reinforcing fiber sheet is impregnated with the resin component to form a prepreg or semipreg state. At this time, it is possible to select whether to form a prepreg or a semi-impregnated (temporarily bonded) semipreg by adjusting the heating and pressing conditions. It is also possible to form a semipreg by omitting the pressing step and temporarily bonding a sheet made of the resin composition of the present invention to the reinforcing fiber sheet by heat fusion. This semipreg has the advantage of shortening the time required for production, leading to reduced production costs, and being semi-impregnated, the reinforcing fibers inside are easily movable with each other, making them flexible.

[0148] In recent years, semipregs have been attracting attention as precursors (intermediates) of fiber-reinforced plastics. As described above, a typical semipreg is one in which a thermoplastic resin film is temporarily bonded to both sides or one side of a reinforcing fiber sheet in one direction or in a woven form by heat fusion. By finally subjecting the semipreg to a process such as heat pressing or belt pressing, a completely impregnated prepreg can be obtained, or a composite product can be obtained directly. The resin film used in the production of semipregs is required to have heat fusion properties with the reinforcing fiber sheet. The resin composition of the present invention is particularly suitable for use in that it has excellent heat fusion properties with reinforcing fibers and can be heat fused at a lower temperature while maintaining heat resistance.

[0149] The content of the reinforcing fibers in the composite material thus obtained is preferably 20% by volume or more, more preferably 30% by volume or more, and even more preferably 40% by volume or more, while the content of the reinforcing fibers in the composite material is preferably 90% by volume or less, more preferably 80% by volume or less, and even more preferably 70% by volume or less.

[0150] A composite material obtained by combining the resin composition of the present invention or a film made of the resin composition of the present invention with reinforcing fibers is industrially useful as a component of a moving body such as an aircraft, an automobile, a ship, or a railway vehicle because of its heat resistance, light weight, mechanical strength, etc.

[0151] [Crystallization heat of materials for 3D modeling] When the resin composition of the present invention is used as a material for three-dimensional modeling, it is important that the heat of crystallization (ΔHc) measured at a cooling rate of 10° C. / min in differential scanning calorimetry of the resin composition is 5 to 40 J / g. If the heat of crystallization (ΔHc) is within this range, it is preferable because it has an excellent balance of modeling properties as a material for three-dimensional modeling and heat resistance of a molded body modeled using the same. From the viewpoint of heat resistance, the lower limit of the heat of crystallization (ΔHc) of the material for three-dimensional modeling of the present invention is 5 J / g or more, preferably 10 J / g or more, more preferably 15 J / g or more, and more preferably 18 J / g or more. On the other hand, from the viewpoint of modeling properties (warping suppression), the upper limit of the heat of crystallization (ΔHc) of the material for three-dimensional modeling of the present invention is 40 J / g or less, preferably 35 J / g, more preferably 32 J / g or less, and particularly preferably 30 J / g or less.

[0152] [Method of manufacturing 3D modeling materials] When the resin composition of the present invention is used as a material for three-dimensional modeling, the method for producing the material for three-dimensional modeling is not particularly limited, and the material can be obtained, for example, as filaments, pellets, or powder. From the viewpoint of handling, it is preferable to obtain the material as filaments.

[0153] In the case of pellets, for example, each constituent material is melt-kneaded as described above, then extrusion-molded, pelletized so as to maintain a certain size and shape, and cooled to produce the pellets. A known kneader such as a single-screw or twin-screw extruder can be used for melt-kneading. When an extruder is used, the ratio (L / D) of the screw length (L) of the extruder to the screw bore (D) is not particularly limited, but is preferably 20 to 80, more preferably 25 to 70, more preferably 30 to 60, and particularly preferably 35 to 50, from the viewpoint of mutual dispersibility of the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B). A twin-screw extruder is preferred as the extruder.

[0154] Examples of pulverization methods for producing the powder include melt granulation, in which the resin composition of the present invention melted near the melting point is shaped into fibers and then cut, and pulverization, in which a resin material made of the resin composition of the present invention is cut or destroyed by applying impact or shear. In order to improve the coatability of the powder in three-dimensional modeling, it is preferable that the shape of the powder is rounded, i.e., that the degree of circularity is large. Therefore, it is preferable to select a pulverization method suitable for the resin composition of the present invention so that a powder of such a suitable shape can be obtained.

[0155] As the pulverizing means, for example, a stamp mill, a ring mill, a stone mill, a mortar, a roller mill, a jet mill, a high-speed rotary mill, a hammer mill, a pin mill, a container-driven mill, a disk mill, a media stirring mill, or the like can be used.

[0156] In addition, in order to prevent the resin material from stretching due to shear heat during grinding, there is a method in which the resin temperature during grinding is lowered by cooling the powder system using liquid nitrogen or the like, thereby producing powder through brittle fracture rather than ductile fracture.

[0157] From the viewpoint of removing the elongated powder from the pulverized powder and increasing the circularity, it is preferable to carry out a classification step after pulverization. In this case, examples of the classification method include air classification and sieve classification.

[0158] The content of the resin composition of the present invention in the material for 3D modeling is preferably 50 to 100 mass%, more preferably 80 to 100 mass%, and particularly preferably 95 to 100 mass%, from the viewpoints of the balance between modeling ability and heat resistance, and adhesion between layers, and it is particularly preferable that the material consists of the resin composition of the present invention.

[0159] The three-dimensional modeling material of the present invention may contain components other than the resin composition consisting of the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B) to the extent that the effect of the present invention is not impaired. Examples of components other than the resin composition include polymers other than the polyaryletherketone resin (A) and the polyetherimide sulfone resin (B), heat resistance agents, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, lubricants, slip agents, crystal nucleating agents, tackifiers, sealability improvers, antifogging agents, mold release agents, plasticizers, pigments, dyes, fragrances, flame retardants, organic particles, inorganic particles, and reinforcing materials.

[0160] The moisture content of the material for three-dimensional modeling of the present invention is preferably 2.5% by mass or less. The moisture content is more preferably 2.0% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1.0% by mass or less. The moisture content may be 0.3% by mass or more, or 0.6% by mass or more. This range is preferable because there is little foaming or smoke generation during extrusion, and the dimensions and mechanical strength of the obtained model are stable. The moisture content of the material for three-dimensional modeling is measured by the Karl Fischer method.

[0161] For this reason, it is preferable that the three-dimensional modeling material of the present invention, as well as the three-dimensional modeling filaments described below, be dried after production and stored in moisture-proof packaging materials (aluminum bags, vapor-deposited films, glass containers, etc.).

[0162] [Filament for 3D modeling] The filament for three-dimensional modeling of the present invention is produced using a material for three-dimensional modeling that contains a polyaryletherketone resin (A) in which the ratio of the number of ether groups to ketone groups is less than 2, and a resin (A') other than the polyaryletherketone resin (A).

[0163] The method for producing the filament for three-dimensional printing of the present invention is not particularly limited, and examples thereof include a method in which the above-mentioned material for three-dimensional printing is molded by a known molding method such as extrusion molding, a method in which the filament is directly produced during the production of a resin composition, etc. When the filament for three-dimensional printing of the present invention is obtained by extrusion molding, the temperature condition is appropriately adjusted depending on the flow characteristics and moldability of the resin composition used, but is usually 300 to 400°C, preferably 320 to 380°C.

[0164] [Physical properties of filaments for 3D modeling] The diameter of the filament for three-dimensional modeling of the present invention depends on the specifications of the system used to mold resin molded bodies by the fused deposition modeling method, but is usually 1.0 mm or more, preferably 1.5 mm or more, more preferably 1.6 mm or more, and particularly preferably 1.7 mm or more, while the upper limit is usually 5.0 mm or less, preferably 4.0 mm or less, more preferably 3.5 mm or less, and particularly preferably 3.0 mm or less.

[0165] From the viewpoint of the stability of the supply of raw materials, it is preferable that the accuracy of the filament diameter is within an error of ±5% for any measurement point of the filament. In particular, the filament for three-dimensional modeling of the present invention has a standard deviation of the diameter of preferably 0.07 mm or less, and more preferably 0.06 mm or less.

[0166] The filament for three-dimensional modeling of the present invention preferably has a circularity of 0.93 or more, particularly preferably 0.95 or more. The upper limit of the circularity is 1.0. The circularity of the filament for three-dimensional modeling is measured by the following method.

[0167] <Circularity> The long and short diameters of the filament are measured with a vernier caliper at multiple points at a specified interval, for example 3 cm intervals, and the ratio of the short diameter to the long diameter at each measurement point is calculated. The average of the ratios of the short diameter to the long diameter at the multiple measured points is taken as the circularity. The closer the ratio is to 1.0, the closer the cross-sectional shape of the filament is to a perfect circle.

[0168] In this way, if the filament for 3D modeling has a small standard deviation in diameter and high circularity, uneven extrusion during molding is suppressed, and molded products with excellent appearance and surface properties can be consistently produced. By using the material for three-dimensional modeling of the present invention, filaments for three-dimensional modeling that satisfy such standard deviation and roundness can be produced relatively easily.

[0169] [3D modeling filament roll and 3D modeling cartridge] When manufacturing a molded body by 3D printing using the filament for 3D printing of the present invention, it is required to stably store the filament for 3D printing and stably supply the filament for 3D printing to 3D printing. For this purpose, it is preferable that the filament for 3D printing of the present invention is hermetically packaged as a wound body wound around a bobbin, or the wound body is stored in a cartridge for 3D printing (hereinafter, sometimes simply referred to as a "cartridge") from the viewpoints of long-term storage, stable payout, protection from environmental factors such as moisture, prevention of twisting, etc. Examples of the cartridge include a wound body wound around a bobbin, a cartridge using a moisture-proofing material or a moisture-absorbing material inside, and a structure in which at least the part other than the orifice part for paying out the filament for 3D printing is sealed.

[0170] Typically, a bobbin containing 3D modeling filament wound thereon, or a cartridge containing the bobbin is placed inside or around the 3D printer, and the 3D modeling filament is constantly being introduced into the 3D printer from the cartridge during molding.

[0171] [Molded body made of 3D modeling material] The molded body of the present invention (hereinafter simply referred to as "molded body") made of the three-dimensional modeling material of the present invention can be obtained by molding the three-dimensional modeling filament of the present invention with a three-dimensional printer. Examples of molding methods using a three-dimensional printer include the fused deposition modeling (ME method), powder sintering method, inkjet method, and stereolithography (SLA method). Among these, the three-dimensional modeling filament of the present invention can be suitably used for the fused deposition modeling and powder sintering methods, and is particularly preferably used for the fused deposition modeling. The following will explain the case of the fused deposition modeling as an example.

[0172] A three-dimensional printer generally has a chamber, and in the chamber, there are a heatable base, an extrusion head mounted on a gantry structure, a heat melter, a filament guide, a raw material supply unit such as a filament cartridge mounting unit, etc. Some three-dimensional printers have an extrusion head and a heat melter integrated together.

[0173] The extrusion head is installed in a gantry structure, so that it can be moved arbitrarily on the XY plane of the base. The base is a platform for constructing the desired three-dimensional object or support material, and is preferably designed to obtain adhesion with the laminate by heating and keeping it warm, and to improve the dimensional stability of the resulting molded body as the desired three-dimensional object. In addition, in order to improve adhesion with the laminate, a sticky paste may be applied to the base, or a sheet or the like that has good adhesion with the laminate may be attached. Examples of sheets that have good adhesion with the laminate include sheets with fine irregularities on the surface, such as inorganic fiber sheets, and sheets made of the same type of resin as the laminate. At least one of the extrusion head and the base is usually movable in the Z-axis direction perpendicular to the XY plane.

[0174] The filament for 3D modeling is fed from the raw material supply section and fed to the extrusion head by a pair of opposing rollers or gears, where it is heated and melted, and extruded from the nozzle at the tip. The extrusion head moves in response to a signal sent based on the CAD model, supplying the raw material onto the substrate and depositing it in layers. After this process is completed, the layered deposit is removed from the substrate, and the desired 3D object can be obtained by peeling off the support material or cutting off excess parts as necessary.

[0175] Examples of means for continuously supplying raw material to the extrusion head include a method of feeding a filament or fiber, a method of feeding a powder or liquid from a tank or the like via a fixed amount feeder, a method of extruding pellets or granules plasticized with an extruder or the like, and feeding the same, etc. Among these, from the viewpoints of process simplicity and supply stability, the method of feeding a filament, i.e., the method of feeding the filament of the present invention described above, is most preferred.

[0176] When supplying a filament to a three-dimensional printer, it is common to engage the filament with a driving roll such as a nip roll or a gear roll, and supply it to the extrusion head while pulling it. In order to stabilize the supply of raw material by strengthening the gripping between the filament and the driving roll, it is also preferable to transfer a minute uneven shape to the surface of the filament, or to compound inorganic additives, spreaders, adhesives, rubbers, etc. to increase the friction resistance with the engagement part. If the filament has uneven thickness, it may not be possible to grip the filament by engaging with the driving roll, and the driving roll may spin idly, making it impossible to supply the filament to the extrusion head.

[0177] The three-dimensional modeling material used in the present invention, which contains polyaryl ether ketone resin (A) in which the ratio of the number of ether groups to ketone groups is less than 2, and resin (A') other than polyaryl ether ketone resin (A), typically requires a temperature of about 300 to 400°C to obtain a fluidity suitable for extrusion. In the method for producing a molded body of the present invention, the temperature of the heated extrusion head is typically 450°C or less, preferably 350 to 400°C, and the base temperature is typically 200°C or less, allowing the molded body to be produced stably.

[0178] The temperature of the molten resin discharged from the extrusion head (discharge temperature) is preferably 350°C or higher, more preferably 370°C or higher, and is preferably 420°C or lower, more preferably 400°C or lower, and even more preferably 380°C or lower. If the temperature of the molten resin is equal to or higher than the lower limit, it is preferable for extruding a resin with high heat resistance, and it is also preferable because it is possible to discharge the resin at high speed and the molding efficiency tends to improve. On the other hand, if the temperature of the molten resin is equal to or lower than the upper limit, it is easy to prevent the occurrence of defects such as thermal decomposition, burning, yellowing, smoking, odor, and stickiness of the resin, and is also preferable from the viewpoint of preventing the adhesion of thin pieces of the molten resin called stringiness and lumps of excess resin called lumps to the molded object, which deteriorates the appearance.

[0179] The molten resin is discharged from the extrusion head in the form of strands, preferably with a diameter of 0.01 to 1.0 mm, more preferably with a diameter of 0.02 to 0.5 mm. When the molten resin is discharged in such a shape, it is preferred because the reproducibility of the CAD model tends to be good.

[0180] When manufacturing a molded body using a 3D printer with a 3D modeling filament, when the molded body is made by stacking strands of molten resin discharged from an extrusion head, unevenness (streaks, etc.) may occur on the surface of the obtained molded body due to insufficient adhesion between the strands of molten resin discharged earlier and the strands discharged on top of it, or uneven discharge. If such unevenness exists on the surface of the molded body, not only will the appearance deteriorate, but problems such as the molded body being easily damaged may occur.

[0181] The filament for three-dimensional printing of the present invention has good adhesion between a strand of molten resin previously extruded and a strand extruded on top of it. In addition, the filament for three-dimensional printing of the present invention has high circularity in diameter, so that uneven extrusion during molding is suppressed, and molded products with excellent appearance and surface properties can be stably produced.

[0182] When making a molded product by stacking strands of molten resin discharged from an extrusion head using a 3D printer, there is a process where the nozzle is moved to the next lamination location after stopping the discharge of the molten resin. At this time, the molten resin does not break off and thin resin fibers are generated, which may remain on the surface of the molded product like strings. If strings like the above occur, problems such as a deterioration in the appearance of the molded product may occur.

[0183] The filament for 3D modeling of the present invention has a small standard deviation in diameter and high circularity, as well as an appropriate crystallization rate and high breaking strain, which suppresses stringiness and enables the stable production of molded articles with excellent appearance and surface properties.

[0184] When a 3D printer is used to create a molded product by stacking strands of molten resin discharged from an extrusion head, the resin may adhere to the nozzle of the extrusion head, and the adhered resin may become discolored by heat and turn into black foreign matter (black spots or black streaks). If such foreign matter gets mixed into the molded product, it may not only deteriorate the appearance, but also cause problems such as the molded product becoming easily damaged.

[0185] The filament for three-dimensional modeling of the present invention has excellent heat resistance and is less likely to become discolored due to heat even if resin adheres to the nozzle part, so that molded articles with excellent appearance can be consistently produced.

[0186] The molded article of the present invention may be heat-treated after shaping to promote or complete crystallization depending on the intended use.

[0187] [Uses of molded products] The molded article of the present invention is also excellent in surface appearance, heat resistance, durability, and the like. The applications of the molded article of the present invention are not particularly limited, and the molded article can be suitably used for applications such as stationery; toys; covers for mobile phones and smartphones; parts such as grips; school teaching materials, home appliances, repair parts for office automation equipment, various parts for automobiles, motorcycles, bicycles, etc.; materials for electrical and electronic equipment, agricultural materials, gardening materials, fishing materials, civil engineering and construction materials, medical supplies, etc. EXAMPLES

[0188] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

[0189] [Raw materials used] The raw materials used in the following Examples and Comparative Examples are as shown in Table 1 below. In Table 1, the ratio of the number of ether groups to the number of ketone groups in the polyaryletherketone resin (A) is shown as "functional group ratio [ether group / ketone group]".

[0190] [Table 1]

[0191] [Examples and Comparative Examples Regarding Film Production] [Film manufacturing] In the examples and comparative examples relating to the production of films, the raw materials shown in Table 1 above were used in the mixing ratios shown in Tables 2 and 3 below to produce films as follows.

[0192] <Example 1> (A)-1 and (B)-1 were dry-blended in a mass ratio of 80:20. This resin mixture was kneaded at 360°C in a single-screw extruder with a cylinder diameter of 40 mm, and then extrusion-molded into a film using a T-die. The molded product obtained was quenched with a cast roll at 170°C to produce a film with a thickness of 100 μm.

[0193] <Example 2> A film was produced in the same manner as in Example 1, except that the mixing ratio of (A)-1 and (B)-1 was 60:40 and the temperature of the casting roll was 190°C.

[0194] <Example 3> A film was produced in the same manner as in Example 1, except that the mixing ratio of (A)-1 and (B)-1 was 40:60 and the temperature of the casting roll was 210°C.

[0195] <Example 4> A film was produced in the same manner as in Example 1, except that the mixing ratio of (A)-1 and (B)-1 was 20:80 and the temperature of the casting roll was 230°C.

[0196] <Example 5> A film was produced in the same manner as in Example 1, except that (A)-2 was used instead of (A)-1 and the mixing ratio of (A)-2 and (B)-1 was 80:20.

[0197] <Example 6> A film was produced in the same manner as in Example 1, except that (A)-2 was used instead of (A)-1, the mixing ratio of (A)-2 and (B)-1 was 60:40, and the temperature of the casting roll was 190°C.

[0198] <Example 7> A film was produced in the same manner as in Example 1, except that (A)-2 was used instead of (A)-1, the mixing ratio of (A)-2 and (B)-1 was 40:60, and the temperature of the casting roll was 210°C.

[0199] <Example 8> A film was produced in the same manner as in Example 1, except that (A)-2 was used instead of (A)-1, the mixing ratio of (A)-2 and (B)-1 was 20:80, and the temperature of the casting roll was 230°C.

[0200] <Example 9> A film was produced in the same manner as in Example 1, except that (B)-2 was used instead of (B)-1 and the mixing ratio of (A)-1 and (B)-2 was 80:20.

[0201] <Example 10> A film was produced in the same manner as in Example 1, except that (B)-2 was used instead of (B)-1, the mixing ratio of (A)-1 and (B-2) was 60:40, and the temperature of the casting roll was 190°C.

[0202] <Example 11> A film was produced in the same manner as in Example 1, except that (B)-2 was used instead of (B)-1, the mixing ratio of (A)-1 and (B-2) was 40:60, and the temperature of the casting roll was 210°C.

[0203] <Example 12> A film was produced in the same manner as in Example 1, except that (B)-2 was used instead of (B)-1, the mixing ratio of (A)-1 and (B-2) was 20:80, and the temperature of the casting roll was 230°C.

[0204] <Comparative Example 1> A film was produced in the same manner as in Example 1, except that (A)-2 was used instead of (A)-1, (B)-2 was used instead of (B)-1, and the mixing ratio of (A)-2 and (B)-2 was 80:20.

[0205] <Comparative Example 2> A film was produced in the same manner as in Example 1, except that (A)-2 was used instead of (A)-1, (B)-2 was used instead of (B)-1, and the mixing ratio of (A)-2 and (B)-2 was 60:40.

[0206] <Comparative Example 3> A film was produced in the same manner as in Example 1, except that (A)-2 was used instead of (A)-1, (B)-2 was used instead of (B)-1, and the mixing ratio of (A)-2 and (B)-2 was 40:60.

[0207] <Comparative Example 4> A film was produced in the same manner as in Example 1, except that (A)-2 was used instead of (A)-1, (B)-2 was used instead of (B)-1, and the mixing ratio of (A)-2 and (B)-2 was 20:80.

[0208] <Comparative Example 5> A film was produced in the same manner as in Example 1, except that (B)-1 was not used and only (A)-1 was used and the temperature of the casting roll was set to 160°C.

[0209] <Comparative Example 6> A film was produced in the same manner as in Example 1, except that (A)-1 and (B)-1 were not used, and only (A)-2 was used, and the temperature of the casting roll was set to 160°C.

[0210] <Comparative Example 7> A film was produced in the same manner as in Example 1, except that (A)-1 was not used and only (B)-1 was used and the temperature of the casting roll was set to 240°C.

[0211] <Comparative Example 8> A film was produced in the same manner as in Example 1, except that (A)-1 and (B)-1 were not used, and only (B)-2 was used, and the temperature of the casting roll was set to 260°C.

[0212] [Film rating] The films produced in the above Examples and Comparative Examples were evaluated and measured for various items as follows. Here, the "vertical" direction of the film refers to the direction in which the film-shaped molded product is extruded from the T-die, and the direction perpendicular to this direction within the film plane is called the "horizontal" direction.

[0213] <Crystal melting temperature> For the 100 μm-thick films produced in the examples and comparative examples, a differential scanning calorimetry (DSC) curve was detected using a differential scanning calorimeter "Pyris1 DSC (manufactured by PerkinElmer)" in accordance with JIS K7121:2012, at a temperature range of 25 to 400° C. and a heating rate of 10° C. / min. The crystalline melting temperature was calculated from the peak top temperature of the endothermic peak corresponding to crystalline melting.

[0214] <Crystal melting heat> For the 100 μm-thick films produced in the examples and comparative examples, a differential scanning calorimetry (DSC) was used in accordance with JIS K7122:2012 to measure the heat of crystalline fusion from the area of ​​the endothermic peak corresponding to crystalline fusion in the DSC (Differential Scanning Calorimetry) curves detected when the films were heated in the temperature range of 25 to 400° C. at a heating rate of 10° C. / min using a differential scanning calorimetry (Pyris1 DSC, manufactured by PerkinElmer).

[0215] <Glass transition temperature> The 100 μm-thick films produced in the Examples and Comparative Examples were heated in the temperature range of 20 to 400° C. at a heating rate of 3° C. / min using a viscoelasticity spectrometer “DVA-200 (manufactured by IT Measurement & Control Co., Ltd.)” in accordance with JIS K7244-4:1999, and the glass transition temperature was determined from the peak top temperature of the loss tangent (tan δ).

[0216] <Melt viscosity> The 100 μm-thick films produced in the examples and comparative examples were subjected to a shear rate test at 360° C. and a shear rate of 1000 s using a capillary rheometer “Capillograph 1D (manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS K7199:1999. -1 The melt viscosity at 100° C. was measured.

[0217] <Tensile modulus at 20℃ above and below the glass transition temperature> The 100 μm thick films produced in the examples and comparative examples were measured in accordance with JIS K7244-4:1999 using a viscoelasticity spectrometer "DVA-200 (manufactured by IT Measurement and Control Co., Ltd.)" at a temperature range of 20 to 400 ° C. and at a heating rate of 3 ° C. / min. The storage modulus was measured at a temperature (Tg-20 ° C.) 20 ° C. lower than the measured glass transition temperature Tg obtained in the above glass transition temperature measurement and at a temperature (Tg+20 ° C.) 20 ° C. higher than the measured glass transition temperature Tg, and the obtained elastic modulus values ​​were defined as the tensile elastic modulus E'(Tg-20 ° C.) and the tensile elastic modulus E'(Tg+20 ° C.), and the ratio E'(Tg-20 ° C.) / E'(Tg+20 ° C.) was calculated.

[0218] The following Tables 2 and 3 show the evaluation and measurement results for Examples 1 to 12 and Comparative Examples 1 to 8. Note that "-" in the evaluation result columns of Tables 2 and 3 indicates that no endothermic peak corresponding to crystal melting was observed in the measurement.

[0219] [Table 2]

[0220] [Table 3]

[0221] [Consideration] As can be seen from the results shown in Tables 2 and 3, Examples 1 to 12, which contain specific combinations of polyether ketone ketone resins (A)-1 and (A)-2 and polyether imide sulfone resins (B)-1 and (B)-2, have only one high glass transition temperature and low melt viscosity, and are therefore excellent in heat resistance, melt moldability, and secondary processability.

[0222] On the other hand, in Comparative Examples 1 to 4 in which the polyether ketone ketone resin (A)-2 and the polyether imide sulfone resin (B-2) were combined, two glass transition temperatures were observed due to phase separation, and secondary processability was poor.

[0223] In Comparative Examples 5 and 6, since only polyether ketone ketone resins (A)-1 and (A)-2 were used, the glass transition temperature was lower and the heat resistance was inferior compared to the examples containing polyether imide sulfone resins (B)-1 and (B)-2.

[0224] In Comparative Examples 7 and 8, since only polyetherimide sulfone resins (B)-1 and (B)-2 were used, the melt viscosity was higher and the melt moldability was poorer than in the Examples containing polyetherketoneketone resins (A)-1 and (A)-2.

[0225] [Examples and Comparative Examples Regarding the Production of Filaments for Three-Dimensional Modeling] [Manufacturing filaments for 3D modeling] In the examples and comparative examples relating to the production of filaments for three-dimensional modeling, the raw materials shown in Table 1 above were used in the mixing ratios shown in Table 4 below to produce filaments for three-dimensional modeling as follows.

[0226] <Example 13> (A)-2 and (B)-1 were dry blended in a mass ratio of 80:20. This resin mixture was kneaded at 360°C using a co-rotating twin screw kneader to produce a resin composition. The resulting resin composition was extruded from a nozzle with a diameter of 2.5 mm using a single screw extruder at a melt temperature of 360°C, and then cooled to produce a filament with a diameter of 1.75 mm.

[0227] <Example 14> A filament was produced in the same manner as in Example 13, except that the mixing ratio of (A)-2 and (B)-1 was 60:40.

[0228] <Example 15> A filament was produced in the same manner as in Example 13, except that (A)-3 was used instead of (A)-2, (C)-1 was used instead of (B)-1, the mixing ratio of (A)-3 and (C)-1 was 60:40, and the kneading and extrusion temperature was 380°C.

[0229] <Comparative Example 9> Filaments were produced in the same manner as in Example 13, except that (A)-4 was used instead of (A)-2, (C)-1 was used instead of (B)-1, and the mixing ratio of (A)-4 and (C)-1 was 60:40.

[0230] <Comparative Example 10> A filament was produced in the same manner as in Example 13, except that (A)-4 was used instead of (A)-2 and the mixing ratio of (A)-4 and (B)-1 was 60:40.

[0231] <Comparative Example 11> A filament was produced in the same manner as in Example 13, except that (B)-1 was not used and only (A)-2 was used.

[0232] [Filament evaluation] Each of the filaments produced in the above Examples and Comparative Examples was evaluated and measured for various items as follows.

[0233] <Crystal melting temperature (Tm)> Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., product name "Pyris1 DSC", in accordance with JIS K7121, approximately 10 mg of a sample was heated from 25°C to 400°C at a heating rate of 10°C / min, held at that temperature for 1 minute, cooled to 25°C at a cooling rate of 10°C / min, and then heated again to 400°C at a heating rate of 10°C / min. The crystal dissolution temperature (Tm) (°C) (reheating process) was determined from each thermogram measured at this time.

[0234] <Crystallization heat (ΔHc)> Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd., product name "Pyris1 DSC", in accordance with JIS K7122, approximately 10 mg of a sample was heated from 25°C to 400°C at a heating rate of 10°C / min, held at that temperature for 1 minute, and then cooled to 25°C at a cooling rate of 10°C / min. The heat of crystallization (ΔHc) (cooling down process) was calculated from the thermogram measured when the sample was cooled down to 25°C at a cooling rate of 10°C / min.

[0235] <Glass transition temperature (Tg)> The filaments produced in the examples and comparative examples were made into a sheet by a heat transfer press. The sheet was heated in the temperature range of 20 to 400°C at a heating rate of 3°C / min using a viscoelasticity spectrometer "DVA-200 (manufactured by IT Measurement & Control Co., Ltd.)" in accordance with JIS K7244-4:1999, and the glass transition temperature (Tg) was calculated from the peak top temperature of the loss tangent (tan δ).

[0236] <Warping during modeling> As an evaluation sample, a dumbbell-shaped sample with a length of 75 mm, width of 10 mm, and thickness of 5 mm was modeled using a 3D printer (manufactured by MINIFACTORY, product name: miniFactory Ultra) with the thickness direction of the sample as the Z-axis direction (layering direction). At that time, a PEI sheet was attached to the modeling table, and modeling was performed under the following modeling conditions: modeling table temperature 155°C, chamber temperature 155°C, nozzle temperature for each example, modeling speed 30 mm / s, and internal filling rate 100%. (Nozzle temperature) Examples 13 and 14 and Comparative Example 11: 375°C Example 15 and Comparative Examples 9 and 10: 400° C.

[0237] After the evaluation sample was manufactured, it was removed from the modeling table and placed on a horizontal surface, and the distances between the four corners of the sample and the horizontal surface were measured, and the average of the obtained values ​​was taken as the amount of warping. From this amount of warping, the warping during modeling was evaluated according to the following criteria. A: The amount of warping was 1 mm or less. B: The amount of warping was more than 1 mm and 2 mm or less. C: The amount of warping exceeds 2 mm. Or, the printing could not be completed due to a large warp or filament clogging in the nozzle during printing.

[0238] <Interlayer adhesion> The tensile strength was measured and evaluated in accordance with JIS K 7161. As the evaluation sample I, a dumbbell-shaped sample with a length of 75 mm, width of 10 mm, and thickness of 5 mm was modeled using a 3D printer (manufactured by MINIFACTORY, product name: miniFactory Ultra) with the length direction of the sample as the Z-axis direction (lamination direction). At that time, a PEI sheet was attached to the modeling table, and modeling was performed under the following modeling conditions: modeling table temperature 155°C, chamber temperature 155°C, nozzle temperature for each example, modeling speed 30 mm / s, and internal filling rate 100%. (Nozzle temperature) Examples 13 and 14 and Comparative Example 11: 375°C Example 15 and Comparative Examples 9 and 10: 400° C.

[0239] A tensile test was carried out on the obtained evaluation sample I with an initial chuck distance of 45 mm, a speed of 50 mm / min, and 23° C. to measure the tensile strength. Separately, each filament was electrothermally pressed at 380° C. to obtain evaluation sample II, which was then subjected to the same measurement of tensile strength. The ratio of the tensile strength of Evaluation Sample I to the tensile strength of Evaluation Sample II was calculated, and the interlayer adhesion was evaluated from this ratio according to the following criteria. A: Tensile strength ratio is 30% or more. B: Tensile strength ratio is 25% or more and less than 30%. C: The tensile strength ratio was less than 25%, or the molding was not completed and evaluation was not possible.

[0240] <Heat resistance> The dumbbell pieces formed in the above interlayer adhesion test were used as evaluation samples. One dumbbell piece was heated in an oven at 180°C for one hour. After that, the tilt distance of the sample was measured and the amount of deformation from before forming was investigated. From this amount of change, the heat resistance of the formed object was evaluated according to the following criteria. A: The change is less than 2 mm. B: The change is 2 mm or more but less than 10 mm. C: The change was 10 mm or more, or the modeling was not completed and evaluation was not possible.

[0241] <Chemical resistance> The dumbbell pieces formed in the above interlayer adhesion test were used as evaluation samples. One dumbbell piece was immersed in acetone at room temperature for 5 hours, and the weight change rate before and after immersion was measured. From this weight change rate, the chemical resistance of the molded object was evaluated according to the following criteria. A: Weight change rate is less than 0.2%. B: Weight change rate is 0.2% or more and less than 0.4%. C: The weight change rate was 0.4% or more, or the molding was not completed and evaluation was not possible.

[0242] <Overall rating> The above-mentioned warpage, interlayer adhesion, heat resistance and chemical resistance were evaluated according to the following criteria. S: Warpage, interlayer adhesion, heat resistance and chemical resistance all received an "A". A: For the warpage evaluation, interlayer adhesion evaluation, heat resistance evaluation, and chemical resistance evaluation, one of them is "B" and the rest are "A". B: For the warpage evaluation, interlayer adhesion evaluation, heat resistance evaluation, and chemical resistance evaluation, one or more of them were rated "C", or two or more of them were rated "B".

[0243] The evaluation and measurement results for Examples 13 to 15 and Comparative Examples 9 to 11 are summarized in Table 4 below.

[0244] [Table 4]

[0245] [Consideration] As can be seen from the results shown in Table 4, Examples 13 to 15, which contain a specific combination of polyaryletherketone resin (A)-2 or (A)-3 as the polyaryletherketone resin (A) having a ratio of the number of ether groups to ketone groups of less than 2, and polyetherimide sulfone resin (B)-1 or polyetherimide resin (C)-1 as the resin (A') compatible therewith, have only one high glass transition temperature and are excellent in shapeability, interlayer adhesion, heat resistance, and chemical resistance.

[0246] On the other hand, in Comparative Example 9, in which polyaryletherketone resin (A)-4 and polyetherimide resin (C)-1 were combined, the ratio of the number of ether groups to the number of ketone groups in polyaryletherketone resin (A)-4 was 2, and therefore the chemical resistance of the molded object was poor.

[0247] In addition, in Comparative Example 10, which combines polyaryl ether ketone resin (A)-4 and polyetherimide sulfone resin (B-1), two glass transition temperatures are observed due to phase separation, and the wire diameter stability and moldability during filament production are poor. Comparative Example 11, in which only the polyaryl ether ketone resin (A)-2 was used, was poor in heat resistance.

[0248] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2019-181196 filed on October 1, 2019, the entirety of which is incorporated by reference.

Claims

1. A resin composition comprising a polyaryl ether ketone resin (A) and a polyetherimide sulfone resin (B), in which the polyaryl ether ketone resin (A) and the polyetherimide sulfone resin (B) are compatible with each other, The polyaryl ether ketone resin (A) has a repeating unit (a-1) represented by the following general formula (1) and a repeating unit (a-2) represented by the following general formula (2), a molar ratio of the repeating unit (a-1) to the repeating unit (a-2) [(a-1) / (a-2)] of 1 or more and 5 or less; 【Chemistry 1】 In the general formulas (1) and (2), Ar ３ and Ar ６ is a phenylene group, Ar １ , Ar ２ , Ar ４ , Ar ５ Each of (1,4) Ar in the general formula (1) independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. ３ In the formula (2), the ketone group is bonded to the 1-position and the 4-position of the phenylene group. ６ has ketone groups bonded to the 1- and 3-positions of the phenylene group.

2. The repeating unit (a-1) represented by the general formula (1) is a repeating unit represented by the following structural formula (1A), and the repeating unit (a-2) represented by the general formula (2) is a repeating unit represented by the following structural formula (2A). The resin composition according to claim 1. 【Chemistry 2】

3. The resin composition according to claim 1 or 2, wherein the polyetherimide sulfone resin (B) has a repeating unit (b-1) represented by the following general formula (3): 【Chemistry 3】 In the general formula (3), Y １ ~Y ６ each independently represents a hydrogen atom, an alkyl group, or an alkoxy group. ７ ~Ar １０ each independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. １ is a direct bond, or a divalent aliphatic hydrocarbon group, -O-, -SO ２ It represents -, -S-, or -C(=O)-.

4. The resin composition according to claim 3, wherein the repeating unit (b-1) represented by the general formula (3) is a repeating unit represented by the following structural formula (3A): 【Chemistry 4】

5. The polyaryl ether ketone resin (A) has a unit molar ratio [(a-1) / (a-2)] of the repeating unit (a-1) and the repeating unit (a-2) constituting the polyaryl ether ketone resin (A) of 1 or more and 2 or less, and the polyetherimide sulfone resin (B) has a repeating unit (b-2) represented by the following general formula (4): The resin composition according to any one of claims 1 to 4. 【Chemistry 5】 In the general formula (4), Y ７ ~Y １２ each independently represents a hydrogen atom, an alkyl group, or an alkoxy group. １１ ~Ar １４ each independently represents an arylene group having 6 to 24 carbon atoms which may have a substituent. ２ is a direct bond, or a divalent aliphatic hydrocarbon group, -O-, -SO ２ It represents -, -S-, or -C(=O)-.

6. The resin composition according to claim 5, wherein the repeating unit (b-2) represented by the general formula (4) is a repeating unit represented by the following structural formula (4A): 【Chemistry 6】

7. The resin composition according to any one of claims 1 to 6, wherein the content ratio of the polyaryl ether ketone resin (A) to the polyetherimide sulfone resin (B) in a total of 100 mass% is in the range of polyaryl ether ketone resin (A): polyetherimide sulfone resin (B) = 90:10 to 10:90 (mass%).

8. The resin composition according to any one of claims 1 to 7, wherein the glass transition temperature derived from the polyaryl ether ketone resin (A) and the polyetherimide sulfone resin (B) is one.

9. The resin composition according to claim 8, wherein the glass transition temperature is 180°C or higher and 260°C or lower.

10. The resin composition according to claim 8 or 9, wherein the ratio E'(Tg-20°C) / E'(Tg+20°C) of the tensile modulus E'(Tg-20°C) at a temperature 20°C lower than the glass transition temperature to the tensile modulus E'(Tg+20°C) at a temperature 20°C higher than the glass transition temperature is 100 or more and 1000 or less.

11. 360°C, shear rate 1000s －１ The resin composition according to any one of claims 1 to 10, having a melt viscosity of 100 Pa·s or more and 1000 Pa·s or less.

12. A film comprising the resin composition according to any one of claims 1 to 11.

13. A composite material obtained by combining the resin composition according to any one of claims 1 to 11 or the film according to claim 12 with reinforcing fibers.

14. 14. The composite material of claim 13 which is a prepreg or semipreg.

15. A moving body which is an aircraft, an automobile, a ship or a railroad vehicle, comprising the composite material according to claim 13 or 14.

16. A three-dimensional modeling material comprising the resin composition according to any one of claims 1 to 11.

17. A filament for three-dimensional modeling, comprising the material for three-dimensional modeling according to claim 16.

18. The filament for three-dimensional modeling according to claim 17, having a filament diameter of 1.0 mm or more and 5.0 mm or less.

19. A wound body of the filament for three-dimensional modeling according to claim 17 or 18.

20. A cartridge for three-dimensional modeling, comprising a container containing the filament for three-dimensional modeling according to claim 17 or 18.

21. A molded body made of the material for three-dimensional modeling according to claim 16.

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