JP2001234053A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition capable of exhibiting excellent fluid stability with time when heating and melting the composition, having improved moldability, excellent in mechanical strength, heat resistance and fluid characteristics, and capable of enabling a fabricated product having precise and fine shape to be produced. SOLUTION: This resin composition is obtained by compounding 1-95 pts.wt. aromatic polyetherketone resin having repeating units represented by chemical formulas (4) to (6) as the component (A), 99-5 pts.wt. polyetherimide resin having a repeating unit represented by chemical formula (7) as the component (B), with 0.1-10 pts.wt. oxides represented by chemical formulas (1) to (3) as the component (C) based on 100 pts.wt. total of the components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for producing a molded article, a film, a sheet, a fiber, etc. having excellent mechanical properties and heat resistance. (Stability).

More specifically, the present invention provides a resin composition comprising an aromatic polyetherketone resin and a polyetherimide resin, wherein the resin composition comprises an acid compound as a melt fluidity stabilizer. Composition.

[0003] The present invention also relates to molded articles, films, sheets, fibers (filaments, fibers, textiles, etc.) comprising the above resin composition and having excellent mechanical properties and heat resistance.

[0004]

2. Description of the Related Art [Technical Background on Aromatic Polyether Ketone Resin] Aromatic polyether ketone resin is a thermoplastic crystalline resin having high impact properties, heat resistance, hydrolysis resistance, radiation resistance, and the like. It has excellent properties such as chemical resistance, and is widely applied to mechanical parts, automobile parts, aviation parts, electric / electronic parts and the like. However, aromatic polyetherketone resins, despite having such excellent properties, are unfortunately inferior in fluidity at the time of melting compared to general-purpose engineering plastics, expensive, and Therefore, its use has been limited by disadvantages such as a relatively low glass transition temperature (about 143 ° C.) as compared to other common amorphous engineering plastics.

[Technical background on resin composition containing aromatic polyetherketone resin and polyetherimide resin] In view of such technical background, in order to improve the above-mentioned drawbacks of aromatic polyetherketone resin, Attempts have been made to add inexpensive polyetherimide resins to aromatic polyetherketone resins, which have excellent melt flow properties, high glass transition temperatures (about 210 ° C.).
For example, JP-A-56-098257 and JP-A-59-1
No. 84254, JP-A-59-187054 and the like show that a resin composition having high heat resistance can be obtained by blending a polyetherimide resin with a polyetherketone resin.

However, although a polymer alloy (resin composition) containing such an aromatic polyetherketone resin and a polyetherimide resin is excellent in heat resistance, it is unfortunately disappointed that the polymer alloy is not heat-meltable. It lacks fluidity stability over time, and its melt fluidity gradually decreases, so that it has a serious problem with respect to moldability.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned problems in the prior art, the present invention provides a resin composition containing an aromatic polyetherketone resin and a polyetherimide resin. Another object of the present invention is to provide remarkably excellent flow stability over time during heating and melting, which has been extremely difficult.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the problems to be solved by the above-mentioned invention, and as a result, have found that aromatic polyetherketone resins and polyetherimide resins are contained. It has been found that the incorporation of an acid compound into the resin composition of the formula (1) significantly improves the flow stability over time during heating and melting of the resin composition, thereby completing the present invention.

The resin composition according to the present invention has remarkably excellent flow stability over time during heating and melting and has significantly improved moldability, so that the resin composition according to the present invention can be molded and processed. In addition to providing excellent mechanical strength, heat resistance, and flow characteristics, molded products that have precise and fine shapes (eg, structural members, machine parts, automotive parts, base materials for space aircraft, etc.) It has become possible to manufacture.

That is, the present invention provides the following [1] to [1]
7].

[1] A resin composition comprising (A) an aromatic polyetherketone resin and (B) a polyetherimide resin, comprising (C) an acid compound. .

[2] The resin composition according to [1], wherein the (C) acid compound is an acid and / or an acid anhydride.

[3] The acid compound (C) is an organic acid and / or
Or the resin composition according to [1], which is an organic acid anhydride.

[4] The resin composition according to [1], wherein the (C) acid compound is a carboxylic acid and / or a carboxylic anhydride.

[5] The resin composition according to [4], wherein the carboxylic acid is at least one selected from the group consisting of maleic acid, propylmaleic acid, chloromaleic acid, and citraconic acid.

[6] The carboxylic acid anhydride according to [4] or [5], wherein the carboxylic anhydride is at least one selected from the group consisting of maleic anhydride, propyl maleic anhydride, chloromaleic anhydride, and citraconic anhydride. The described resin composition.

[7] The acid compound (C) is represented by the chemical formula (1)
An unsaturated cyclic acid anhydride represented by the following chemical formula (5), chemical formula (2):
[4] at least one selected from the group consisting of a saturated cyclic acid anhydride represented by [Chemical Formula 5] and an aromatic cyclic acid anhydride represented by Chemical Formula (3) [Chemical Formula 5]. Or the resin composition described in [5] (in the chemical formulas (1) and (2), R ₁ is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, hydrogen, or In the chemical formula (3), R ₂ is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 96 carbon atoms, hydrogen, , A halogen group, or a carboxyl group, p is
It is a number from 1 to 4. ).

[0018]

Embedded image [8] (A) A polymer in which the aromatic polyetherketone resin has a repeating unit represented by the chemical formula (4) [Chemical formula 6], or a polymer having a repeating unit represented by the chemical formula (5) [Chemical formula 6] And at least one polymer selected from the group consisting of polymers having a repeating unit represented by Chemical Formula (6) [Formula 6].
The resin composition according to any one of [1] to [7].

[0019]

Embedded image [9] (A) The aromatic polyetherketone resin is a repeating unit represented by the chemical formula (4) [Formula 7], a repeating unit represented by the chemical formula (5) [Formula 7], and a chemical formula (6) The resin composition according to any one of [1] to [7], comprising a polymer having at least one kind of repeating unit selected from the group consisting of repeating units represented by [Chemical Formula 7]. object.

[0020]

Embedded image [10] The method according to any one of [1] to [9], wherein the (B) polyetherimide resin comprises a resin having a repeating unit represented by the chemical formula (7) [formula 8]. Resin composition.

[0021]

Embedded image [11] (A) Aromatic polyetherketone resins 1 to 9
9 parts by weight and 100 parts by weight of the resin composition containing 99 to 1 parts by weight of the polyetherimide resin (B),
(C) The resin composition according to any one of [1] to [10], wherein 0.1 to 10 parts by weight of an acid compound is added.

[12] 100 parts by weight of the resin composition according to any one of [1] to [11], and fillers 5 to 1
A resin composition comprising 00 parts by weight.

[13] The filler is a carbon fiber [1]
2].

[14] A molded article comprising the resin composition according to any one of [1] to [13].

[15] A film or sheet comprising the resin composition according to any one of [1] to [13].

[16] A resin composition comprising (A) an aromatic polyetherketone resin and (B) a polyetherimide resin, characterized by containing (C) a melt fluidity stabilizer. Resin composition.

[17] The resin composition according to [16], wherein (C) the melt fluidity stabilizer is an acid compound.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION [Acid Compound] The acid compound used in the present invention is not particularly limited as long as it is an acid and / or an acid anhydride. The acid compound used in the present invention is appropriately selected in consideration of the properties of the obtained resin composition (for example, heat resistance, heat decomposition resistance, stability over time of melt flow, etc.). Here, the “acid” is not particularly limited, and may be an organic acid or an inorganic acid. Here, the “acid anhydride” is not particularly limited, and may be a linear anhydride or a cyclic anhydride. In the present invention, a preferred form of the acid compound is an organic acid and / or an organic acid anhydride. Here, the organic acid is not particularly limited, and may be an aliphatic acid or an aromatic acid. In the present invention, a preferred form of the organic acid is a carboxylic acid. The carboxylic acid is not particularly limited as long as it has a carboxyl group and / or a salt thereof in the molecule. The number of carboxyl groups and / or salts thereof in the molecule is not particularly limited,
Usually, the number is about 1 to 8, preferably 1 to 2. Specific examples of the carboxylic acid include, for example, maleic acid, propylmaleic acid, chloromaleic acid, citraconic acid and the like.

In the present invention, a preferred form of the acid anhydride is an organic acid anhydride. Here, the organic acid anhydride is not particularly limited, and may be an aliphatic acid anhydride or an aromatic acid anhydride. In the present invention, a more preferred form of the organic acid anhydride is a carboxylic acid anhydride. The carboxylic anhydride is not particularly limited as long as it has an acid anhydride group in the molecule. The number of acid anhydride groups in the molecule is not particularly limited, but is usually about 1 to 4, preferably 1 to 2. Specific examples of the carboxylic anhydride include a cyclic dimer anhydride in which two molecules of a dicarboxylic acid having two carboxyl groups are dehydrated and condensed, and an anhydride in which two carboxyl groups of a dicarboxylic acid are dehydrated and condensed. Specific examples of carboxylic anhydrides include, for example, anhydrides such as maleic anhydride, propyl maleic anhydride, chloromaleic anhydride and citraconic anhydride. Specific examples of the carboxylic anhydride include, for example, chemical formulas (1) [formula 9] to chemical formula (3).
An unsaturated cyclic acid anhydride represented by the following [Chemical formula 9] can be mentioned.

[0030]

Embedded image

In the chemical formulas (1) and (2),
R ₁ is an alkyl group having 1 to 3 carbon atoms, 1 carbon atom
Alkenyl group, hydrogen or halogen group.
In the chemical formula (3), R ₂ is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, an aromatic hydrocarbon group having 6 to 96 carbon atoms, hydrogen, a halogen group, or A carboxyl group, and p is a number from 1 to 4.

[Carboxylic anhydride represented by chemical formula (1)] Specific examples of the unsaturated cyclic acid anhydride represented by chemical formula (1) [Formula 9] include, for example, maleic anhydride and propyl anhydride. Maleic acid, chloromaleic anhydride, citraconic anhydride and the like can be mentioned.

[Carboxylic anhydride represented by chemical formula (2)] Specific examples of the saturated cyclic acid anhydride represented by chemical formula (2) [Formula 9] include, for example, itaconic anhydride and succinic anhydride. And butynyl succinic anhydride.
These can be used alone or in combination of two or more.

[Carboxylic Anhydride Represented by Chemical Formula (3)] Specific examples of the aromatic cyclic acid anhydride represented by Chemical Formula (3) include, for example, phthalic anhydride, trimellitic anhydride, and tetrahydroanhydride. Chlorophthalic acid, tetrabromophthalic anhydride and the like can be mentioned. These can be used alone or in combination of two or more.

[Composition ratio of acid compound] The composition ratio of the acid compound [component (C)] used in the present invention is as follows: polyetherimide resin [component (A)], aromatic polyether ketone resin [component (B) )]] And the composition ratio. The composition ratio of the acid compound [component (C)] used in the present invention is such that the resin composition contains an aromatic polyetherketone resin [component (A)] and a polyetherimide resin [component (B)]. The amount is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight. If the amount is less than 0.1 part by weight, the improvement of the flow stability during heating and melting, which is a feature of the present invention, may not be remarkable.
If it exceeds 10 parts by weight, the deflection temperature under load may be significantly reduced.

[Melt Flow Stabilizer] The melt flow stabilizer [Component (C)] used in the present invention comprises a polyetherimide resin [Component (A)] and an aromatic polyether ketone resin [Component (B) )] Is not particularly limited as long as it suppresses the change over time of the melt fluidity of the resin composition containing the resin composition. Here, the melt fluidity stabilizer given to the resin composition comprising the polyetherimide resin [component (A)] and the aromatic polyetherketone resin [component (B)] is as follows. It is evaluated by a spiral flow test (spiral flow) and a staying spiral flow test (retention spiral flow retention) described later. Preferred embodiments of the melt flow stabilizer [component (C)] used in the present invention include, for example, the above-mentioned acid compounds.

[Composition Ratio of Melt Fluidity Stabilizer] The composition ratio of the melt fluidity stability [component (C)] used in the present invention is a polyetherimide resin [component (A)], an aromatic polyether It is appropriately selected according to the type and composition ratio of the ketone resin (component (B)). The composition ratio of the melt fluidity stabilizer [component (C)] used in the present invention includes an aromatic polyetherketone resin [component (A)] and a polyetherimide resin [component (B)]. Resin composition 100
0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, even more preferably 0.2 to 10 parts by weight with respect to parts by weight.
３3 parts by weight. If the amount is less than 0.1 part by weight, the improvement of the flow stability during heating and melting, which is a feature of the present invention, may not be remarkable. If it exceeds 10 parts by weight, the deflection temperature under load may be significantly reduced.

[Aromatic polyetherketone resin] The aromatic polyetherketone resin used in the present invention includes:
It is not particularly limited as long as it is a thermoplastic resin having a repeating unit in which a phenyl group is bonded with an ether group and a ketone group.

[Specific Examples of Aromatic Polyether Ketone Resin] Specific examples of the aromatic polyether ketone resin include:
For example, commercially available polyetheretherketone (PEEK, manufactured by Victrex) whose repeating unit is represented by the chemical formula (4) [Chemical Formula 10], and its repeating unit is represented by the chemical formula (5) [Chemical Formula 10]. Polyetherketone (PEK, manufactured by Victorex) and Ultrapepe whose repeating unit is represented by the chemical formula (6)
k (PEKEKK, manufactured by BASF). These may be used alone or in combination of two or more.

[0040]

Embedded image [PEEK] A polyetheretherketone whose repeating unit is an aromatic polyetherketone resin represented by the chemical formula (4) [Formula 10] (PEEK, manufactured by Victorex)
Is 50 to 3000 [Pa · s] (500 to
Those having a range of 30,000 [Poise]) are preferably used. When the melt viscosity is 50 [Pa · s] (500 [Poi
s]], the mechanical strength of the molded product is insufficient, and the melt viscosity is 3000 [Pa · s] (30000 [Pois]
If e]) is exceeded, the melt fluidity will decrease and the moldability will decrease. The melt viscosity at this time is an apparent melt measured when a resin heated to 400 [° C.] is extruded from a nozzle having an inner diameter of 1 [mm] and a length of 10 [mm] with a load of 100 [kg]. Viscosity. Victrex P used in the examples and comparative examples of the present specification.
EEK resin 450P has a melt viscosity of 650 [Pa · s].

[PEK] The repeating unit has the chemical formula (5)
Polyetherketone (PEK, manufactured by Victorex), which is an aromatic polyetherketone resin represented by Chemical Formula 10, has a melt viscosity of 50 to 3000 [Pa · s] (50
Those having a range of 0 to 30,000 [Poise]) are preferably used. As with PEEK, a melt viscosity of 50
If it is less than [Pa · s] (500 [Poise]), the mechanical strength of the molded product is insufficient, and the melt viscosity becomes 3000 [Pa · s].
s] (30000 [Poise]), the melt fluidity decreases, and the moldability decreases. The melt viscosity at this time is the same as in the case of PEEK when extruding a resin heated to 400 [° C] from a nozzle having an inner diameter of 1 [mm] and a length of 10 [mm] with a load of 100 [kg]. Is the apparent melt viscosity measured at Victrex P used in the examples and comparative examples of the present specification.
EK resin P22 has a melt viscosity of 220 [Pa · s].

[PEKEKK] Ultrapek (PEKEKK, BASF), which is an aromatic polyetherketone resin represented by the following chemical formula (6):
Is 50-3000 [Pa · s] (5
A range of from 0.000 to 30000 [Poise]) is preferably used. As in the case of PEEK, the melt viscosity is 5
If it is less than 0 [Pa · s] (500 [Poise]), the mechanical strength of the molded product is insufficient, and the melt viscosity becomes 3000 [Pa · s].
s] (30000 [Poise]), the melt fluidity decreases, and the moldability decreases. The melt viscosity at this time is the same as in the case of PEEK, when extruding a resin heated to 400 ° C. from a nozzle having an inner diameter of 1 mm and a length of 10 mm with a load of 100 kg. Is the apparent melt viscosity measured at PEKEKK resin Ul used in Examples, Comparative Examples, etc. of the specification of the present application
Trapek A1000 (PEKEKK, manufactured by BASF) has a melt viscosity of 180 [Pa · s].

[Production Method of Aromatic Polyether Ketone Resin] The production method of the aromatic polyether ketone resin is not particularly limited, but generally, dialkali metal salts of various bisphenols and two halogen atoms are ortho to A polycondensation reaction with an aromatic dihalite which has been activated by substitution by a ketone group at the para- or para-position, preferably para-position or, optionally, by a sulfone group, for example in the presence of an aromatic sulfone as a solvent It can be obtained by: Specific examples of the method for producing an aromatic polyetherketone resin include, for example, JP-A-50-27897, JP-A-51-119797, and JP-A-52-38000.
No., JP-A-54-90296, JP-B-55-2357.
No. 4, JP-B-56-2091 and the like.

[Polyetherimide Resin] The polyetherimide resin used in the present invention has both an ether bond and an imide bond in its structure, and is not particularly limited as long as it is thermoplastic. Specific examples of the polyetherimide resin used in the present invention include, for example, Ultem (Ultem, manufactured by GE Plastics) having a repeating unit represented by the chemical formula (7) [Formula 11].

[0045]

Embedded image Specific examples of the method for producing the polyetherimide resin used in the present invention include, for example, JP-A-56-826.
Can be exemplified.

[Polyetherimide resin [component (A)]
The composition ratio of the polyetherimide resin [Component (A)] and the aromatic polyetherketone resin [Component (B)] used in the present invention is as follows. There is no particular limitation, and it is appropriately selected according to the application and required performance. The composition ratio of the polyetherimide resin [component (A)] and the aromatic polyetherketone resin [component (B)] used in the present invention is such that the aromatic polyetherketone resin [component (A)] and the polyether Based on 100 parts by weight of the total weight of the imide resin [Component (B)], the weight part of the polyetherimide resin [Component (A)] is W _A , and the aromatic polyether ketone resin [Component (B)].
When the parts and W _B, preferably Equation (1) [Equation 1], more preferably Equation (2) Equation 2, further preferably Equation (3) [Expression 3], more preferably formula (4 ) [Equation 4].

[0047] [number _{1] W A: W B =} 1~99: 99~ 1 (1)

[0048] [number _{2] W A: W B =} 10~90: 90~10 (2)

[0049] [number _{3] W A: W B =} 20~80: 80~20 (3)

[0050] [number _{4] W A: W B =} 25~75: 75~25 (4)

Both when the polyetherimide resin [component (A)] is used alone and when the aromatic polyetherketone resin [component (B)] is used alone, the polyetherimide resin [component (A)] is used. ] And aromatic polyetherketone resin [component (B)] are mixed and used, the heat resistance (the deflection temperature under load, the spiral flow, the retention spiral flow retention, etc.) is inferior. Improved heat resistance (deflection temperature under load, spiral flow, retention of retained spiral flow, etc.) using a mixture of polyetherimide resin [Component (A)] and aromatic polyetherketone resin [Component (B)] Is done. However, as described above, a polymer alloy (resin composition) containing only a polyetherimide resin [component (A)] and an aromatic polyetherketone resin [component (B)] is not excellent in heat resistance. There is
Unfortunately, it lacks flow stability over time at the time of heating and melting, and the melt flowability gradually decreases, which has a serious problem with respect to moldability.

[Additives / Fillers] The additives used in the present invention are not particularly limited. The filler used in the present invention is not particularly limited. Specific examples of the filler used in the present invention include, for example, carbon fiber, glass fiber, aromatic polyamide fiber, alumina fiber, boron fiber, silicon carbide fiber, potassium titanate whisker, aluminum borate whisker, carbon whisker, asbestos , Metal fibres, fibrous fillers such as ceramic fibers, graphite, carborundum, silica powder, molybdenum disulfide, fluorine resin, etc., abrasion resistant materials, antimony trioxide, magnesium carbonate, calcium carbonate, etc., flame retardancy Improver, clay, mica and other electrical property improvers, asbestos, silica, graphite and other tracking resistance improvers, barium sulfate, silica, calcium metasilicate and other acid resistance improvers, iron powder, zinc powder, aluminum powder, Thermal conductivity improving materials such as copper powder, other glass beads, Click, diatomaceous earth, alumina, Shirasubarun, hydrated alumina, metal oxides, colorants, release agents, various stabilizers, may be mentioned plasticizers.

[Polymer Blend] The thermoplastic resin of the third component used in the present invention is not particularly limited.
Depending on the purpose of use, a polymer blend in which a thermoplastic resin other than the component (A) or the component (C) is appropriately blended as the third component with the resin composition according to the present invention can be prepared.
Specific examples of thermoplastic resins that can be blended,
For example, polyethylene, polypropylene, polystyrene, polycarbonate, polyamide, polyamide imide, polyether nitrile, polyphenylene ether,
Examples include polyacetal, polyphenylene sulfide, polysulfone, polyethersulfone, polyethylene terephthalate, polybutylene terephthalate, and liquid crystal polymer.

The thermosetting resin of the third component used in the present invention is not particularly limited. Depending on the purpose of use, a polymer blend in which the thermosetting resin of the third component is appropriately blended with the resin composition according to the present invention can be prepared. Specific examples of the thermosetting resin that can be blended include, for example, a phenol resin and an epoxy resin.

[Method for Producing Resin Composition] The method for producing the resin composition according to the present invention is not particularly limited, and any known and publicly-known production method may be used. Preferred specific examples of the method for producing the resin composition according to the present invention are shown below. Pre-mix the high heat resistant resin powder and carbon fiber using a mortar, Henshal mixer, drum blender, tumbler blender, ball mill, ribbon blender, etc., and then use a commonly known melt extruder, melt mixer, hot roll, etc. After kneading, pelletize or powder. High heat resistant resin powder is dissolved or suspended in an organic solvent in advance, carbon fiber is immersed in this solution or suspension, and then the solvent is removed in a hot air oven, and then pelletized or powdered. . In this case, as other examples of the solvent used, for example,
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N −
Methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2
-Methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, tetrahydrofuran,
1,3-dioxane, 1,4-dioxane, pyridine,
Picoline, dimethyl sulfoxide, dimethyl sulfone,
Examples include tetramethylurea and hexamethylphosphoramide. These organic solvents can be used alone or in combination of two or more.

[Molded Article] The molded article comprising the resin composition according to the present invention is not particularly limited. Specific examples of the molded article comprising the resin composition according to the present invention, for example,
Examples include films, sheets, filaments, fibers, textiles, containers, trays, and the like. These compacts can be further heat-treated at an appropriate temperature for the purpose of removing residual stress and / or crystallization, thereby further improving mechanical properties and heat resistance.

[Method for Producing Molded Article] The method for molding the resin composition according to the present invention is not particularly limited. Specific examples of the molding method of the resin composition according to the present invention, for example, injection molding method, extrusion molding method, compression molding method, transfer molding method, vacuum molding method, pressure molding method, known and publicly known molding methods such as Can be mentioned. The molded body obtained by these molding methods can be further heat-treated at an appropriate temperature for the purpose of removing residual stress and / or crystallization, thereby further improving mechanical properties and heat resistance. When forming a film, sheet, filament, fiber, or the like, one or more stages of stretching can be performed as appropriate. When forming a film, a sheet, or the like, one or more stages of stretching can be appropriately performed not only in the length direction but also in the width direction.

[Uses of Molded Articles] Molded articles containing the resin composition according to the present invention are excellent in heat resistance and mechanical properties, and can be used for producing structural members, machine parts, automobile parts and the like. Useful.

[0059]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, each test was evaluated by the following method.

Tensile Test (Tensile Strength) Based on ASTM D-638. Bending test (flexural modulus, bending rupture strength) It was based on ASTM D-790. Deflection temperature under load According to ASTM D-648. The bending stress was 18.6 kg / cm ² . The higher the deflection temperature under load, the better the heat resistance.

Spiral Flow Test (Spiral Flow) An Archimedes-type spiral flow mold (150 ° C.) was prepared using an injection molding machine having a cylinder temperature of 360 ° C. and an injection pressure of 1500 kg / cm ^2. Injection molding was performed using a wall thickness of 1 mm and a width of 10 mm), and the flowability was evaluated based on the flow length. The longer the flow length, the better the flowability.

I) Measurement conditions for spiral flow of PEEK / ULTEM system Mold temperature = 150 ° C. Cylinder temperature = 360 ° C. Injection pressure = 1500 kgf / cm ²

Ii) Measurement conditions for spiral flow of PEK / ULTEM system Mold temperature = 150 ° C. Cylinder temperature = 420 ° C. Injection pressure = 1000 kgf / cm ²

Iii) Measuring conditions of spiral flow of PEKEKK / ULTEM system Mold temperature = 150 ° C. Cylinder temperature = 420 ° C. Injection pressure = 1000 kgf / cm ²

Iv) Measurement conditions of PEEK / ULTEM / CF (carbon fiber) based spiral flow Mold temperature = 180 ° C. Cylinder temperature = 420 ° C. Injection pressure = 1500 kgf / cm ²

V)) Measurement conditions for spiral flow of PEK / ULTEM / CF (carbon fiber) system Mold temperature = 150 ° C. Cylinder temperature = 420 ° C. Injection pressure = 1000 kgf / cm ²

Retention Spiral Flow Test (Retention of Retained Spiral Flow) A resin composition using a polyetheretherketone resin as the aromatic polyetherketone resin (“PEE”)
In order to evaluate the thermal stability of the K-based resin composition ”) and the resin composition of the polyetherimide resin alone, the cylinder temperature was 400 ° C. and the injection pressure was 1000 kg / cm.
^With an injection molding machine set at ² , a 150 ° C Archimedean spiral flow mold (1 mm thick, 10 m wide)
m) was used to perform injection molding in a 210 second cycle.

In order to evaluate the result numerically, the initial spiral flow length was set to 10 times as the retained spiral retention.
The value obtained by multiplying the ratio with the spiral flow length in the cycle by 100 is shown. The closer the retention spiral retention rate is to 100, the better the thermal stability. When the retained spiral retention rate is significantly lower than 100, it indicates that gelation of the resin composition is progressing, and the melt viscosity of the resin tends to increase with time. Therefore, if the retention spiral retention rate is significantly lower than 100, the appearance of the molded article due to the generation of a gel-like substance and insufficient filling during injection molding occur, which is not preferable.

If the retained spiral retention rate is significantly higher than 100, it indicates that the thermal decomposition of the resin composition proceeds and a large amount of gas resulting from the decomposition is generated, and insufficient filling or silver occurs during injection molding. And is not preferred.

As the aromatic polyether ketone resin, PE
In order to evaluate the thermal stability of the resin composition when K or PEKEKK resin was used, a retention spiral flow test was performed under the same conditions as for the PEEK-based resin composition except that the cylinder temperature was 420 ° C.

Examples 1 to 4 A polyetheretherketone resin PEEK 450P (Victrex) as an aromatic polyetherketone resin [component (C)],
Ultem 1000 (G
E Plastics Co., Ltd.), phthalic anhydride as an acid compound was mixed and mixed at the ratio shown in Table 1, and then sufficiently mixed with a tumbler mixer to obtain a screw diameter of 37 m.
m, L / D = 32 in a twin screw extruder, cylinder temperature 3
The mixture was melt-mixed and extruded at 40 to 360 ° C and a screw rotation speed of 100 rpm to obtain a pellet-shaped molding material composition. The composition obtained by the above method was molded into a test piece by an injection molding machine set at 360 to 380 ° C., and each physical property was measured. Also, using the composition obtained by the above method,
A spiral flow test and a staying spiral flow test were performed under the conditions described above. The results are shown in Table 1. All of the resin compositions of Examples 1 to 4 exhibited good mechanical properties, heat resistance, fluidity, and thermal stability.

[Comparative Examples 1 and 15] Tables 1 and 2 show the composition ratios and results of Examples 1 to 4 when only polyetheretherketone resin was used. Comparative Example 1 was not preferable because heat resistance and melt fluidity were lower than those of Examples 1 to 4.

[Comparative Example 2, Comparative Example 16] Table 1 shows the composition ratios and results when only the polyetherimide resin was used in Examples 1 to 4. Comparative Example 2 was inferior in fluidity to Examples 1-4 and was not preferred.

[Comparative Examples 3 to 5] In Examples 1 to 4,
Table 1 shows the results when the acid compound was used at a composition ratio outside the range of the present invention. Comparative Examples 3 and 5 are inferior in thermal stability,
Not preferred. Comparative Example 4 was inferior in heat resistance and was not preferred.

[Examples 5 to 6] Polyetherketone resin PEK P22 as an aromatic polyetherketone resin
(Victrex), Ultem 1000 (GE Plastics) as a polyetherimide resin, and phthalic anhydride as an acid compound in the proportions shown in Table 2 and mixing, followed by thorough mixing with a tumbler mixer. Then, using a twin screw extruder having a screw diameter of 37 mm and L / D = 32, the mixture was melt-mixed and extruded at a cylinder temperature of 380 to 400 ° C. and a screw rotation speed of 100 rpm to obtain a pellet-shaped molding material composition. The composition obtained by the above method was molded into a test piece by an injection molding machine set at 380 to 400 ° C., and each physical property was measured. Using the composition obtained by the above method, a retention spiral flow test was performed under the conditions described above. Table 2 shows the results. All of the resin compositions of Examples 5 to 6 showed good mechanical properties, heat resistance and thermal stability.

[Comparative Examples 6 and 17] Tables 2 and 3 show the composition ratios and results when only the polyetherketone resin was used in Examples 5 to 6. Comparative Example 6 was not preferable because heat resistance was lower than Examples 5 to 6.

[Comparative Examples 7 and 8] In Examples 5 and 6,
Table 2 shows the results when the composition ratio of the acid compound [component (C)] was set to a numerical value different from that in the examples. Comparative Example 7 was inferior in thermal stability and was not preferred. Comparative Example 8 was inferior in heat resistance and was not preferred.

Example 7 As an aromatic polyetherketone resin, a polyetheretherketone resin PEEK was used.
450P (Victrex), Ultem 1000 (GE Plastics) as a polyetherimide resin, phthalic anhydride as an acid compound, and polyacrylonitrile-based carbon fiber HTA-C6- as a carbon fiber
After mixing and mixing TX (manufactured by Toho Rayon Co., Ltd.) in the proportions shown in Table 4, the mixture was sufficiently mixed with a tumbler mixer, and the cylinder was adjusted with a twin-screw extruder having a screw diameter of 37 mm and L / D = 32. Melt mixing and extrusion were performed at a temperature of 360 to 380 ° C and a screw rotation speed of 100 rpm to obtain a pellet-shaped molding material composition. The composition obtained by the above method was molded into a test piece by an injection molding machine set at 380 to 400 ° C., and each physical property was measured. Using the composition obtained by the above method, a retention spiral flow test was performed under the conditions described above. The results are shown in Table-4. The resin composition of Example 7 showed good mechanical properties, heat resistance, and thermal stability.

[Comparative Example 9] Table 4 shows the results when the composition ratio of the acid compound [component (C)] in Example 7 was changed to a numerical value different from that in Example. Comparative Example 9 was inferior in thermal stability and was not preferred.

Example 8 Polyetherketone resin PEK P22 (Victrex) as an aromatic polyetherketone resin, Ultem 1000 (GE Plastics) as a polyetherimide resin, phthalic anhydride as an acid compound, After blending and mixing polyacrylonitrile-based carbon fiber HTA-C6-TX (manufactured by Toho Rayon Co., Ltd.) as the carbon fiber at the ratio shown in Table-5,
Mix well with a tumbler mixer, and use a twin-screw extruder with a screw diameter of 37 mm and L / D = 32, a cylinder temperature of 380 to 400 ° C., and a screw rotation speed of 100 rpm.
To obtain a pellet-shaped molding material composition. The composition obtained by the above method was molded into test pieces using an injection molding machine set at 400 to 420 ° C., and the physical properties of each were measured. Further, a retention spiral flow test was performed under the conditions described above. The results are shown in Table-5. Example 8
The resin composition of (1) showed good mechanical properties, heat resistance, and thermal stability.

[Comparative Example 10] Table 5 shows the results when the composition ratio of the acid compound [component (C)] in Example 8 was changed to a numerical value different from that in the example. Comparative Example 10 was inferior in thermal stability and was not preferred.

Example 9 and Comparative Example 11 The results obtained in Example 1 and Comparative Example 3 when maleic anhydride was used as the acid compound are shown in Table-6. The resin composition of Example 9 exhibited good mechanical properties, heat resistance, fluidity, and thermal stability. Comparative Example 11 was inferior in heat resistance and was not preferred.

Example 10 / Comparative Example 12 The results obtained in Example 1 and Comparative Example 3 when itaconic anhydride was used as the acid compound are shown in Table-7. The resin composition of Example 10 shows good mechanical properties, heat resistance, fluidity, and thermal stability. Comparative Example 12 was inferior in heat resistance and was not preferred.

[Examples 11 to 13]
Table 8 shows the results when the amount of the phthalic anhydride as the acid compound was changed. The resin compositions of Examples 11 to 13 are:
Excellent mechanical properties, heat resistance, and thermal stability were exhibited.

Example 14 Polyetheretherketone resin PEEK was used as the aromatic polyetherketone resin.
450P (manufactured by Victorex), Ultem 1000 (manufactured by GE Plastics) as a polyetherimide resin, and phthalic anhydride as an acid compound at the same ratio as in Example 1 and mixing, and then thoroughly mixed with a tumbler mixer. Then, screw diameter 25 mm, L / D = 16,
Using a film extruder set at a lip of 0.1 mm and a roll temperature of 150 ° C., melt-mix at a cylinder temperature of 340 to 360 ° C. and a screw rotation speed of 30 rpm, and extrude about 50 μm.
m was obtained. The molded product obtained by the above method was pulverized and charged from the hopper of the film extruder to obtain an extruded film-like molded product under the same conditions.
This operation was repeated, and the same material was used. The number of times the film could be formed was confirmed. As a result, it was confirmed that the film could be formed ten times.

Here, the state in which a film can be formed means that a film having a uniform appearance and good appearance can be obtained, and a film can be stably formed under the same extrusion conditions. The state in which the film cannot be formed is a state in which the melt viscosity of the resin composition is remarkably increased and the film cannot be formed under the same extrusion conditions, or the appearance of the film due to an increase in the resinous gel material on the film. Refers to a state in which is significantly deteriorated.

The resin composition of Example 14 can withstand a thermal history up to 10 times to obtain a good film-shaped molded product, and thus clearly has good thermal stability. .

Comparative Example 13 The same procedure as in Example 14 was carried out except that no acid compound was added, and the number of times the film could be formed was confirmed. As a result, it was confirmed that the film could be formed only three times. When the film formation is performed three or more times, the melt viscosity of the resin composition increases remarkably, and at the same time, the amount of gel-like substance increases on the film, so that a uniform film cannot be obtained. Comparative Example 13 was not preferable because it was inferior to Example 14 in thermal stability.

[Examples 15 and 16, Comparative Examples 18 and 21]
As an aromatic polyetherketone resin, PEKEKK resin Ultrapek A1000 (PEKEKK, BA
SF), Ultem as polyetherimide resin
1000 (manufactured by GE Plastics) and phthalic anhydride as an acid compound in the proportions shown in Table 3 and mixing. With a twin screw extruder, cylinder temperature 380-400 ° C, screw rotation speed 100r
The mixture was melt-mixed at pm and extruded to obtain a pellet-shaped molding material composition. 380-400 of the composition obtained by the above method
Test pieces were molded with an injection molding machine set at ° C., and the physical properties of each were measured. Using the composition obtained by the above method, a retention spiral flow test was conducted under the above-mentioned conditions. Table 3 shows the composition ratio and the results. Example 15-
All 16 resin compositions exhibited good mechanical properties, heat resistance and thermal stability. Table 3 shows Comparative Examples 18 to 21 in which the composition ratio of the components (A), (B) and (C) was changed from Examples 15 to 16. Comparative Examples 18 to 21
Neither of them reached Examples 15 to 16 and was not preferred.

[0090]

[Table 1]

[0091]

[Table 2]

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

[0095]

[Table 6]

[0096]

[Table 7]

[0097]

[Table 8]

[0098]

According to the present invention, a resin composition comprising an aromatic polyetherketone resin and a polyetherimide resin is remarkably excellent in heat melting, which is extremely difficult according to the prior art. It has become possible to impart flow stability over time.

Since the resin composition according to the present invention has remarkably excellent flow stability over time during heating and melting and has remarkably improved molding processability, the resin composition according to the present invention is molded and processed. In addition to providing excellent mechanical strength, heat resistance, and flow characteristics, molded products that have precise and fine shapes (eg, structural members, machine parts, automotive parts, base materials for space aircraft, etc.) It has become possible to manufacture.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 79/08 C08L 79/08 B (72) Inventor Masaji Yoshimura 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals, Inc. F-term (reference) 4F071 AA51 AA60 AB03 AC09 AD01 AE05 AE17 AH07 AH17 BA01 BB05 BB06 BC01 BC03 4J002 BD123 CH00X CH09W CL063 CM05X DA017 DA027 DA067 DE127 DE147 DE187 DE237 DG027 DG047 DJ007 DJ017 DJ07 077 EL007 FD206 GM00 GN00

Claims (15)

[Claims] 1. A resin composition comprising (A) an aromatic polyetherketone resin and (B) a polyetherimide resin, comprising (C) an acid compound. 2. The resin composition according to claim 1, wherein the acid compound (C) is an acid and / or an acid anhydride. 3. The resin composition according to claim 1, wherein the acid compound (C) is an organic acid and / or an organic acid anhydride. 4. The resin composition according to claim 1, wherein the acid compound (C) is a carboxylic acid and / or a carboxylic anhydride. 5. The resin composition according to claim 4, wherein the carboxylic acid is at least one selected from the group consisting of maleic acid, propylmaleic acid, chloromaleic acid, and citraconic acid. 6. The method according to claim 6, wherein the carboxylic anhydride is maleic anhydride,
The resin composition according to claim 4, wherein the resin composition is at least one selected from the group consisting of propyl maleic anhydride, chloromaleic anhydride, and citraconic anhydride. 7. The resin according to claim 4, wherein the acid compound (C) is at least one selected from the group represented by the chemical formulas (1) to (3) to (3). In the composition (in the chemical formulas (1) and (2), R ₁
Is an alkyl group having 1 to 3 carbon atoms, 1 to 3 carbon atoms
An alkenyl group, hydrogen or a halogen group. In the chemical formula (3), R ₂ is an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 1 to 3 carbon atoms, and 6 carbon atoms.
To 96 aromatic hydrocarbon groups, hydrogen, halogen groups, or
A carboxyl group, and p is a number from 1 to 4. ). Embedded image 8. A polymer in which the aromatic polyetherketone resin (A) has a repeating unit represented by the chemical formula (4), and a repeating unit represented by the chemical formula (5): And at least one polymer selected from the group consisting of a polymer having a repeating unit represented by the chemical formula (6) [Chemical Formula 2]. The resin composition according to any one of the above. Embedded image 9. A method according to claim 1, wherein the aromatic polyether ketone resin (A) is a repeating unit represented by the chemical formula (4), a repeating unit represented by the chemical formula (5): 6) The resin composition according to any one of claims 1 to 7, wherein the resin composition comprises a polymer having at least one type of repeating unit selected from the group consisting of repeating units represented by Chemical Formula 3. object. Embedded image 10. The method according to claim 1, wherein the polyetherimide resin (B) comprises a resin having a repeating unit represented by the chemical formula (7) [Formula 4]. Resin composition. Embedded image 11. A resin composition comprising (A) 1 to 99 parts by weight of an aromatic polyether ketone resin and (B) 99 to 1 parts by weight of a polyetherimide resin, and (C) The resin composition according to any one of claims 1 to 10, wherein 0.1 to 10 parts by weight of an acid compound is added. 12. A resin composition comprising 5 to 100 parts by weight of a filler with respect to 100 parts by weight of the resin composition according to claim 1. 13. The filler according to claim 12, wherein the filler is carbon fiber.
The resin composition described in the above. 14. A molded article comprising the resin composition according to claim 1. 15. A film or sheet comprising the resin composition according to claim 1.