JP2009173847A - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent heat resistance, melt molding workability and transparency and a molded article. <P>SOLUTION: The thermoplastic resin composition is obtained by mixing (A) 1-99 pts.wt. polyether imide and (B) 99-1 pts.wt. aromatic polyimide having ≤10% crystallinity per 100 pts.wt. in total of (A) and (B), wherein a 0.1 mm thick film formed from the thermoplastic resin composition has ≥70% total light transmittance and ≥1.5 GPa storage elastic modulus (E') at 200°C. In the thermoplastic resin composition, the (A) polyether imide and (B) aromatic polyimide form a both phase continuous structure having 0.001-1.0 μm structural period or a dispersion structure having 0.001-1.0 μm interparticle distance. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition excellent in heat resistance, melt molding processability and transparency. More specifically, heat resistance, chemical resistance, mechanical strength, aromatic polyimide, and heat resistance, melt molding processability and transparency are mixed with polyetherimide, which is excellent in heat resistance and melt molding processability. The present invention relates to an excellent thermoplastic resin composition.

  Polyetherimide is well known as an engineering plastic having relatively good heat resistance. Polyetherimide is an excellent resin that has a heat distortion temperature of around 200 ° C. and has fluidity at a temperature of 350 ° C. or higher, and can be melt-molded, and can be injection-molded and extruded. Here, if the heat distortion temperature of the polyetherimide can be increased, it can be developed for more applications where heat resistance requirements are severe.

  Patent Documents 1 and 2 disclose a polyetherimide resin composition composed of polyetherimide and a specific thermoplastic polyimide as a method for improving heat resistance in addition to the processability inherent in polyetherimide. However, the thermoplastic polyimides described in these documents have high crystallinity, and as a result of testing and verification by us, improvement in heat resistance was observed, but transparency was lost.

Patent Document 3 discloses a thermoplastic resin composition obtained by mixing liquid crystalline aromatic polyimide with a thermoplastic resin as a method for improving the melt molding processability of the thermoplastic resin. However, as a result of experimentation and verification by us, although improvement in melt molding processability is recognized, the improvement in heat resistance aimed at by the present invention has not been observed, and since it has liquid crystallinity, transparency is lost. It was to be.
JP-A 63-289067 Japanese Patent Laid-Open No. 1-313561 JP-A-6-179816

  An object of the present invention is to obtain a thermoplastic resin composition having improved heat resistance and transparency in addition to the excellent processability inherent in polyetherimide.

  As a result of intensive studies to solve the above problems, the present inventors have blended an aromatic polyimide having a crystallinity of 10% or less with polyetherimide, so that processability, heat resistance, and transparency are improved. It has been found that an improved thermoplastic resin composition can be obtained. A film having a thickness of 0.1 mm produced from such a thermoplastic resin composition has a total light transmittance of 70% or more, and a storage elastic modulus (E ′) at 200 ° C. of 1.5 GPa. The above can be obtained. Furthermore, by blending an aromatic polyimide having a crystallinity of 10% or less, a specific biphasic continuous structure or dispersed structure is formed in a thermoplastic resin composition composed of polyetherimide and aromatic polyimide. It was found that the composition having such a structure is particularly effective for the above purpose, and the present invention has been completed.

That is, the present invention provides: The total of (A) and (B) is 100 parts by weight, and (A) 1 to 99 parts by weight of polyetherimide and (B) 99 to 1 part by weight of aromatic polyimide having a crystallinity of 10% or less are blended. Thermoplastic resin composition.
2. 2. The thermoplastic resin composition according to 1, wherein a total light transmittance of a film having a thickness of 0.1 mm produced from the thermoplastic resin composition is 70% or more.
3. 3. The thermoplastic resin composition according to 1 or 2, wherein a molded article made of the thermoplastic resin composition has a storage elastic modulus (E ′) at 200 ° C. of 1.5 GPa or more.
4). In the thermoplastic resin composition, (A) polyetherimide and (B) aromatic polyimide having a crystallinity of 10% or less are a two-phase continuous structure having a structural period of 0.001 to 1 μm, or an interparticle distance of 0.001 to 0.001. 4. The thermoplastic resin composition according to any one of 1 to 3, which has a dispersion structure of 1 μm.
5. 5. The thermoplastic resin composition according to 4, wherein the two-phase continuous structure or the dispersed structure in the thermoplastic resin composition is formed by phase separation by spinodal decomposition.
6). 6. The thermoplastic resin composition according to 5, wherein the thermoplastic resin composition is obtained through melt-kneading.
7). 7. The thermoplastic resin according to 6, wherein the thermoplastic resin composition is obtained by compatibilization under shear during melt kneading and then phase separation under non-shear after discharge. Composition.
8). The total of (A) and (B) is 100 parts by weight, and (A) 50 to 99 parts by weight of polyetherimide and (B) 50 to 1 part by weight of aromatic polyimide having a crystallinity of 10% or less. The thermoplastic resin composition according to any one of 1 to 7.
9. (A) 1 to 99 parts by weight of polyetherimide and (B) 99 to 1 part by weight of aromatic polyimide having a crystallinity of 10% or less are melt-kneaded, with the total of (A) and (B) being 100 parts by weight. The method for producing a thermoplastic resin composition according to any one of 1 to 8, wherein the thermoplastic resin composition is subjected to compatibilization under shearing of time and then phase-separated under non-shearing after discharge.
10. A molded article comprising the thermoplastic resin composition according to any one of 10.1 to 8.
It is.

  According to the present invention, a thermoplastic resin composition and a molded product excellent in heat resistance, melt molding processability and transparency can be obtained as described below.

  Hereinafter, the present invention will be described in more detail.

  Examples of the (A) polyetherimide used in the thermoplastic resin composition of the present invention are described in U.S. Pat. Nos. 3,803,085, 3,380,097, 3,843,867, 3,905,942 and 4,107,147. And polyetherimides well known in the art. The polyetherimide resin contains two or more structural units of the formula (1), preferably 10 to 1000, more preferably 10 to 500.

Wherein T and R ¹ are independently selected from substituted and unsubstituted divalent aromatic groups. In one embodiment, T is —O— or a group of formula —O—Z—O—, and the divalent bond of the —O— or OZ—O— group is in the 3,3 ′ position, the 3,4 ′ position. , 4, 3′-position, or 4,4′-position, and Z includes a divalent group of the following formula (2), but is not limited thereto.

Wherein, as the Q, but are not limited to, -O -, - S -, - C (O) -, - SO 2 -, - SO -, - C y H 2y - (y is an integer of from 1 to 5 And divalent groups selected from the group consisting of halogenated derivatives thereof (such as, but not limited to, perfluoroalkylene groups), or groups of the formula —O—Z—O—, wherein —O— or The divalent bond of the —O—Z—O— group is located at the 3,3′-position, the 3,4′-position, the 4,3′-position or the 4,4′-position, and Z is not particularly limited. 2) is a divalent group.

R ^{1 in the} formula (1) is not particularly limited, but is an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, a linear or branched alkylene group having 2 to 20 carbon atoms, a carbon atom There are substituted or unsubstituted divalent organic groups such as a cycloalkylene group of 3 to 20 or a divalent group of the following general formula (3).

Wherein, as the Q, but are not limited to, -O -, - S -, - C (O) -, - SO 2 -, - SO -, - C y H 2y - (y is an integer of from 1 to 5 And divalent groups selected from the group consisting of halogenated derivatives thereof (such as, but not limited to, perfluoroalkylene groups), or groups of the formula —O—Z—O—, wherein —O— or The divalent bond of the —O—Z—O— group is located at the 3,3′-position, the 3,4′-position, the 4,3′-position or the 4,4′-position, and Z is not particularly limited. 2) is a divalent group.
Polyetherimide can be produced by various methods known to those skilled in the art including reaction of the following aromatic bis (ether anhydride) of formula (4) with an organic diamine of formula (5).

^{_{H 2 N-R 1 -NH 2}} (5)
In the formula, T and R ¹ are as defined in formulas (1) and (2), respectively. The polyetherimide containing the structural unit of the formula (1) may be copolymerized with other polymers such as polyester, polycarbonate, polyacrylate, and fluoropolymer.

  (A) Specific examples of aromatic bis (ether anhydride) and organic diamine which are raw materials for polyetherimide are disclosed in, for example, US Pat. Nos. 3,972,902 and 4,455,410. Specific examples of the aromatic bis (ether anhydride) of the formula (4) include 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenyl ether dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) benzophenone Dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride, 4 , 4′-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride, 4,4′-bis (2,3-dicarboxyphenoxy) diphenyl sulfide 4,4′-bis (2,3-dicarboxyphenoxy) benzophenone dianhydride, 4,4′-bis (2,3-dicarboxyphenoxy) diphenylsulfone dianhydride, 4- (2,3- Dicarboxyphenoxy) -4 '-(3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride, 4- (2,3-dicarboxyphenoxy) -4'-(3,4-dicarboxy Phenoxy) diphenyl ether dianhydride, 4- (2,3-dicarboxyphenoxy) -4 ′-(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4- (2,3-dicarboxyphenoxy) -4 '-(3,4-dicarboxyphenoxy) benzophenone dianhydride and 4- (2,3-dicarboxyphenoxy) -4'-(3,4-dicarboxyl Phenoxy) diphenyl sulfone dianhydride, and mixtures comprising two or more thereof.

  Aromatic bis (ether anhydride) must be produced by hydrolysis of the reaction product of nitro-substituted phenyldinitrile with a metal salt of a dihydric phenol compound in the presence of a dipolar aprotic solvent and subsequent dehydration reaction. Can do. The preferred aromatic bis (ether anhydride) belonging to the formula (4) is not particularly limited, but T is represented by the following formula (6), and the ether bond is, for example, 3, 3′-position, 3,4′-position. , A compound in the 4,3′-position or the 4,4′-position, or a mixture containing one or more thereof.

  Where Q is as defined above.

  Specific examples of the organic diamine of formula (5) include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1, 12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1,2- Sus (3-aminopropoxy) ethane, bis (3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis- (4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine, 2,4-diamino Toluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine, 5-methyl-4,6-diethyl-1 , 3-phenylene-diamine, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 1,5-diaminonaphthalene, bis (4-aminophenyl) methane, bis (2-chloro-4-amino) -3,5-diethylphenyl) methane, bis (4-aminophenyl) propane, 2,4-bis ( -Amino-t-butyl) toluene, bis (p-b-amino-t-butylphenyl) ether, bis (p-b-methyl-o-aminophenyl) benzene, bis (p-b-methyl-o-amino) Pentyl) benzene, 1,3-diamino-4-isopropylbenzene, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfone and bis (4-aminophenyl) ether. Mixtures containing one or more of these compounds may be present. Specifically, the diamino compound can be an aromatic diamine. More specifically, the diamino compounds are in particular m-phenylenediamine, p-phenylenediamine and mixtures thereof.

  The (A) polyetherimide used in the present invention preferably has a melt index of 0.1 to 10 grams per minute (g / min) as measured in accordance with American Society for Testing and Materials (ASTM) D1238. The polyetherimide preferably has a weight average molecular weight (Mw) of 5,000 to 500,000, more specifically 10,000 to 8,000, as measured by gel permeation chromatography using a polystyrene standard. Such polyetherimide resins have an intrinsic viscosity of more than 0.2 deciliter per gram (dl / g), preferably 0.35 to 0.7 dl / g, measured in m-cresol at 25 ° C. Have. Some specific examples of such polyetherimide are ULTEM (registered trademark) 1000 (number average molecular weight (Mn) 21000, Mw 54000, polydispersity 2.5), ULTEM (registered trademark) 1010 (Mn 19000, Mw 47000, many Dispersity 2.5), ULTEM (registered trademark) 1040 (Mn 12000, Mw 34,000 to 35000, polydispersity 2.9), ULTEM (registered trademark) XH6050 (Mn 23,000 to 26000, Mw 52000 to 58000, polydispersity 2.2) (All available from GE Plastics) or a mixture containing one or more of these, but is not limited to these.

  The polyetherimide used in the thermoplastic resin composition of the present invention is not particularly limited, but ULTEM (registered trademark) 1000 and ULTEM (registered trademark) 1010 are preferable from the viewpoint of molding processability and transparency, Among them, ULTEM (registered trademark) 1010 is more preferable.

  As the aromatic polyimide having a crystallinity of 10% or less for the component (B) used in the present invention, an aromatic polyimide resin containing an organic diamine of formula (7) and tetracarboxylic dianhydride as constituent components is used. It is preferable. That is, a diamine of the following formula (7) and a tetracarboxylic dianhydride of the following formula (10) are reacted in the presence or absence of an organic solvent, and the resulting polyamic acid is chemically or thermally reacted. Can be produced by imidization. The reaction temperature is usually 250 ° C. or lower, and the reaction pressure is not particularly limited, and can be sufficiently carried out at normal pressure. The reaction time varies depending on the tetracarboxylic dianhydride used, the type of solvent, and the reaction temperature, and the reaction is usually carried out for a time sufficient to complete the production of polyamic acid, which is an intermediate product. The reaction time is 24 hours, and in some cases within 1 hour is sufficient.

A polyamic acid is obtained by such a reaction, and then the polyamic acid is heated and dehydrated to 100 to 400 ° C. or chemically imidized using a commonly used imidizing agent to obtain an aromatic polyimide. Moreover, the production | generation of a polyamic acid and a thermal imidation reaction can be performed simultaneously, and an aromatic polyimide can also be obtained.
H ₂ N—R ² —NH ₂ (7)
In the formula, R ² represents an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, a linear or branched alkylene group having 2 to 20 carbon atoms, and a cycloalkylene group having 3 to 20 carbon atoms. Or a substituted or unsubstituted divalent organic group such as a divalent group of the following general formula (8).

Wherein, as the Q, but are not limited to, -O -, - S -, - C (O) -, - SO 2 -, - SO -, - C y H 2y - (y is an integer of from 1 to 5 And divalent groups selected from the group consisting of halogenated derivatives thereof (such as, but not limited to, perfluoroalkylene groups), or groups of the formula —O—Z—O—, wherein —O— or The divalent bond of the —O—Z—O— group is located at the 3,3′-position, the 3,4′-position, the 4,3′-position or the 4,4′-position, and Z is not particularly limited. 9) is a divalent group.

In the formula, R ³ has 4 to 27 carbon atoms, and an aliphatic group, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group and / or an aromatic group is directly or a cross-linking member It represents a tetravalent group which is a non-condensed polycyclic aromatic group connected to each other.

  Examples of the diamine of formula (7) used in this method include ether diamines of the following formula (11), diamines other than ether diamines of formula (11), such as m-aminobenzylamine, p-aminobenzylamine, 3, 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3 , 3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 1,3-bis (3-aminophenoxy Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- ( 4-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) phenyl] ketone, bis [4-aminophenoxy) phenyl] sulfide, And bis [4- (4-aminophenoxy) phenyl] sulfone.

In the formula, X represents at least one group selected from the group consisting of a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, sulfur, a carbonyl group, a thio group, a sulfonyl group, and an ether group; ¹ , Y ² , Y ³ and Y ⁴ are each a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a lower alkoxy group having 1 to 6 carbon atoms, a halogenated alkyl group, a halogenated alkoxy group, chlorine and / or bromine. Represents an atom.

  As the ether diamine of the formula (11), X in the formula is directly bonded, and 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) -3- Methylbiphenyl, 4,4′-bis (3-aminophenoxy) -3,3′-dimethylbiphenyl, 4,4′-bis (3-aminophenoxy) -3,5-dimethylbiphenyl, 4,4′-bis (3-Aminophenoxy) -3,3 ′, 5,5′-tetramethylbiphenyl, 4,4′-bis (3-aminophenoxy) -3,3′-dichlorobiphenyl, 4,4′-bis (3 -Aminophenoxy) -3,5-dichlorobiphenyl, 4,4'-bis (3-aminophenoxy) -3,3 ', 5,5'-tetrachlorobiphenyl, 4,4'-bis (3-aminophenoxy) ) − , 3′-Dibromobiphenyl, 4,4′-bis (3-aminophenoxy) -3,5-dibromobiphenyl, 4,4′-bis (3-aminophenoxy) -3,3 ′, 5,5′- Tetrabromobiphenyl, wherein X in the formula is a hydrocarbon group, [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1, 2-bis [4- (3-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2- [4- (3-aminophenoxy) phenyl] -2- [4- (3-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) -3-methylphenyl] propane, 2- [4- (3-aminophenoxy) ) Phenyl] -2- [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (3-aminophenoxy) -3,5-dimethylphenyl] propane, , 2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, In the formula, when X is sulfur, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) -3-methoxyphenyl] sulfide, [4- (3-aminophenoxy) ) Phenyl] [4- (3-aminophenoxy) 3,5-dimethoxyphenyl] sulfide, bis [4- (3-aminophenoxy) -3,5-dimethoxyphenyl] sulfi Wherein X in the formula is a carbonyl group, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] ketone, X in the formula Is sulfonyl group, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, and X in the formula is ether group Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, and X in the formula is 1,4-bis [4- (3- Aminophenoxy) phenoxy] benzene, 1,4-bis [4- (4-aminophenoxy) phenoxy] benzene, 1,4-bis [4- (3-aminophenoxy) Nzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone, and the like. Used in a mixture of more than one species.

  The diamine of the formula (7) used in the present invention is preferably an ether diamine of the formula (11). From the viewpoint of heat resistance and transparency of the resulting resin composition, in the ether diamine of the formula (11), X Is more preferably a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a direct bond.

  Moreover, diamines other than the above-mentioned ether diamine can be mixed and used within a range not impairing the melt fluidity of the aromatic polyimide. These diamines are usually used in a mixture of 30% by weight or less, preferably 5% by weight or less.

Moreover, as a specific example of the tetracarboxylic dianhydride which is one raw material used for manufacturing the aromatic polyimide, R ³ in the formula in the formula (10) is the following (a) to (e): It is defined as at least one selected from the group consisting of
(A) an aliphatic group having 4 to 9 carbon atoms (b) a cyclic aliphatic group having 4 to 9 carbon atoms (c) a monocyclic aromatic group represented by the following formula (12)

(D) A condensed polycyclic aromatic group represented by the following formula (13)

(E) A non-condensed polycyclic aromatic group in which aromatic groups represented by the following formula (14) are connected to each other directly or by a bridging member

Specifically ethylene tetracarboxylic acid dianhydride R ³ in the formula (10) is an aliphatic group, butane tetracarboxylic dianhydride, the R ³ in the formula (10) is a cycloaliphatic radical cyclopentane tetracarboxylic dianhydride as a thing, R ³ is pyromellitic dianhydride as a monocyclic aliphatic group in the formula, 1,2,3,4-benzene tetracarboxylic acid dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride in which R ³ in formula (10) is a condensed polycyclic aromatic group 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracar Boronic acid dianhydride, R ³ in formula (10) is otherwise bis (3,4-dicarboxy) (p-phenylenedioxy) dianhydride, X ^{1 in} formula (14) Is a —CO— group, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, X in formula (14) ¹ Is a direct bond 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, X ^{1 in} formula (14) Is an aliphatic group, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis ( 2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, X in formula (14) ¹ Bis (3,4-dicarboxyphenyl) ether dianhydride in which is —O— group, bis (3,4-dicarboxyphenyl) sulfone disilane in which X ¹ in formula (14) is —SO ₂ — group Such as anhydrides. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  Among the tetracarboxylic acids or dianhydrides thereof, from the viewpoints of transparency and heat resistance of the thermoplastic resin composition used in the present invention, the tetracarboxylic acid or dianhydride constituting the aromatic polyimide may be aromatic. Preferably, it is an aromatic tetracarboxylic acid or a dianhydride thereof, more preferably a phthalic anhydride or an aromatic tetracarboxylic acid represented by the following chemical formula (15) or a dianhydride thereof, More preferably, the acid is 40 to 95 mol%, and the aromatic tetracarboxylic acid represented by the formula (15) or its dianhydride is 5 to 60 mol%.

In the formula, R ⁴ is a non-condensed polycyclic aromatic group in which the aromatic groups represented by the formula (14) are connected to each other directly or by a bridging member.

  The aromatic polyimide used in the present invention is an aromatic dicarboxylic acid anhydride and / or an aromatic monoamine represented by the general formula (16) and / or the general formula (17) when the aromatic polyimide is produced. The aromatic polyimide which sealed the molecular terminal of the polymer obtained by making it react in coexistence is included.

V-NH ₂ (17)
In the formula, each of Z and V has 6 to 15 carbon atoms and is a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic aroma in which aromatic groups are connected to each other directly or by a cross-linking member. Represents at least one divalent and monovalent group selected from the group consisting of group groups.

  Examples of the carboxylic acid anhydride represented by the general formula (16) include phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride, and 2,3-dicarboxyphenyl phenyl. Ether anhydride, 3,4-dicarboxyphenyl phenyl ether anhydride, 2,3-biphenyl dicarboxylic acid anhydride, 3,4-biphenyl dicarboxylic acid anhydride, 2,3-dicarboxyphenyl phenyl sulfone anhydride, 3, 4-dicarboxyphenyl phenyl sulfone anhydride, 2,3-dicarboxyphenyl phenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalenedicarboxylic anhydride, 2,3-naphthalenedicarboxylic Acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 1, - anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, a dicarboxylic anhydride such as 1,9-anthracene dicarboxylic acid anhydride. These may be used alone or in combination of two or more.

  Among these carboxylic acid anhydrides, the aromatic polyimide from which phthalic anhydride is obtained is most preferable from the viewpoint of performance and practical use. When using carboxylic anhydride, the amount is 0.001-1.0 molar ratio per 1 mol of aromatic diamine represented by the general formula (7). If it is less than 0.001 mol, an increase in viscosity is observed at the time of high-temperature molding, which causes a decrease in molding processability. On the other hand, if it exceeds 1.0 mol, the mechanical properties are deteriorated. A preferred use amount is 0.01 to 0.5 mol.

  Examples of the aromatic monoamine represented by the general formula (17) include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,6-xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline O-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenidine, m-phenidine, p-phenidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzonitrile, m-aminobenz Zonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-aminobenzophenone, 3 -Aminobenzophenone, 4-aminobenzophenone, 2-aminophenyl phenyl sulfide, 3-aminophenyl phenyl sulfide, 4-aminophenyl phenyl sulfide, 2-aminophenyl phenyl sulfone, 3-aminophenyl phenyl sulfone, 4-aminophenyl phenyl sulfone , Α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 5 Amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol, 8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like. These aromatic monoamines may be substituted with a group that is not reactive with an amine or dicarboxylic anhydride, or may be used alone or in combination of two or more.

  When an aromatic monoamine is used, the amount is 0.001 to 1.0 mole ratio per mole of tetracarboxylic dianhydride represented by the general formula (10). If it is less than 0.001 mol, an increase in viscosity is observed at the time of high temperature molding, which causes a decrease in molding processability. On the other hand, when the molar ratio exceeds 1.0, the mechanical properties are deteriorated. A preferred amount is 0.01 to 0.5 mole.

  Furthermore, the aromatic polyimide used for the thermoplastic resin composition of the present invention has a crystallinity of 10% or less. Aromatic polyimide having a crystallinity of 5% or less is preferred, and it is more preferably completely amorphous. When the degree of crystallinity of the aromatic polyimide used exceeds 10%, the total light transmittance and the storage elastic modulus at 200 ° C. of the molded article made of the thermoplastic resin composition are lowered.

  The aromatic polyimide having a crystallinity of 10% or less for the component (B) used in the present invention is an aromatic polyimide having a repeating structural unit represented by the following general formulas (18) and (19). More preferably, it is an amorphous aromatic polyimide in which the repeating structural unit represented by the formula (18) is 40 mol% or more and the repeating structural unit represented by the formula (19) is 5 to 60 mol%. preferable. Specific examples of this aromatic polyimide include Mitsui Chemical Co., Ltd .; trade name Aurum PD450M.

In the formula, R ⁴ is R ³ defined in formula (10).

  Here, the crystallinity of the aromatic polyimide is a value measured by the following method.

After annealing for 10 minutes at 350 ° C. The aromatic polyimide performs DSC measurement in the range of 425 ° C. from 25 ° C. under measurement conditions of 20 ° C. / min, obtaining the melting energy [Delta] H _M. Next, DSC measurement is performed in the range of 25 ° C. to 425 ° C. under the measurement condition of 20 ° C./min using an aromatic polyimide that has not been annealed, and the crystallization energy (ΔH _cc ) and the melting energy (ΔH _m ) are obtained.

The crystallinity D _c1 of the aromatic polyimide is defined as in the following formula (20).
D _c1 = ((ΔH _m −ΔH _cc ) / ΔH _M ) × 100 (20)
In the thermoplastic resin composition of the present invention, the degree of crystallinity of the aromatic polyimide in the thermoplastic resin composition needs to be 10% or less, more preferably 1% or less, and most preferably 0%. When the degree of crystallinity exceeds 10%, the storage elastic modulus at 200 ° C. of the molded article made of the thermoplastic resin composition is lowered.

The crystallinity D _c2 of the aromatic polyimide in the thermoplastic resin composition is measured by the following method.

The thermoplastic resin pellet is heated and pressed at a predetermined temperature for 10 minutes and then rapidly cooled to produce a film having a thickness of 0.1 mm. Using this film, DSC measurement is performed in the range of 25 ° C. to 425 ° C. under measurement conditions of 20 ° C./min, and the crystallization energy (ΔH _cc ) and melting energy (ΔH _m ) are obtained.

The crystallinity D _c2 of the aromatic polyimide in the thermoplastic resin composition is defined as the following formula (21), where x is the weight fraction of the aromatic polyimide in the thermoplastic resin composition.
D _c2 = ((ΔH _m −ΔH _cc ) / ΔH _M ) / xx100 (21)
Incidentally, [Delta] H _M refers to the (20) aromatic polyimide single melting energy in the formula ([Delta] H _M).

  The thermoplastic resin composition of the present invention is adjusted so that the total of polyetherimide and aromatic polyimide is 100 parts by weight, and is in the range of 99 to 1 part by weight of aromatic polyimide with respect to 1 to 99 parts by weight of polyetherimide. Is done. 15 to 5 parts by weight of aromatic polyimide is preferable with respect to 85 to 95 parts by weight of polyetherimide, and 8 to 6 parts by weight of aromatic polyimide is more preferable with respect to 92 to 94 parts by weight of polyetherimide.

  In the thermoplastic resin composition of the present invention, the heat resistance improvement effect by the aromatic polyimide is recognized even in a small amount, and the lower limit of the composition ratio of the aromatic polyimide is 1 part by weight, preferably 5 parts by weight or more, more preferably Is 6 parts by weight or more.

  In the thermoplastic resin composition of the present invention, the effect of improving the melt processability by polyetherimide is recognized even in a small amount, and the lower limit of the composition ratio of the aromatic polyimide is 1 part by weight, preferably 85 parts by weight or more, More preferably, it is 92 parts by weight or more.

  In the thermoplastic resin composition of the present invention, the total light transmittance of a film having a thickness of 0.1 mm produced from the thermoplastic resin composition is 70% or more, more preferably 80% or more, and still more preferably 85%. That's it. By using an aromatic polyimide having a crystallinity of 10% or less, a film made of a thermoplastic resin composition having a total light transmittance of 70% or more can be obtained, and has excellent transparency. It can be said that.

  In the present invention, a film having a thickness of 0.1 mm is produced by heating and pressing the pellets (300 ° C. × 5 minutes), and the whole is obtained using a Nippon Denshoku haze meter (trade name “NDH-200”). The light transmittance is measured.

  The thermoplastic resin composition of the present invention has a storage elastic modulus (E ′) at 200 ° C. of 1.5 GPa or more. Preferably it is 2 GPa or more, More preferably, it is 2.5 GPa or more, Most preferably, it is 3.0 GPa or more. By using an aromatic polyimide having a crystallinity of 10% or less, it is possible to obtain a molded article made of a thermoplastic resin composition having a storage elastic modulus (E ′) at 200 ° C. of 1.5 GPa or more, It turns out that it has the outstanding heat resistance.

  The storage elastic modulus (E ′) was measured by preparing a test piece having a length of 50 mm and a width of 15 mm, and using a DMS6100 made by SII, in a tension mode, a frequency of 1 Hz, a distance between chucks of 20 mm, and a heating rate of 2 ° C./min. , Performed at 23 ° C to 300 ° C. Further, the storage elastic modulus (E ′) at 200 ° C. is read from the temperature-storage elastic modulus (E ′) curve.

  The thermoplastic resin composition of the present invention is a biphasic continuous structure having a structural period of 0.001 to 1 μm by blending (A) polyetherimide and (B) an aromatic polyimide having a crystallinity of 10% or less, Alternatively, it is possible to obtain a resin composition whose structure is controlled to a dispersed structure having a distance between particles of 0.001 to 1 μm.

  In order to obtain such a structure, it is preferable that (A) polyetherimide and (B) aromatic polyimide are once dissolved in phase and formed into a structure by spinodal decomposition described later. Furthermore, in order to realize this structure formation, polyetherimide and aromatic polyimide are a partial miscible system described later, a shear field-dependent phase dissolution / phase decomposition system, or a reaction-induced phase decomposition system. It is preferable.

  In general, polymer alloys composed of two-component resins are compatible with these compositions in a practical system where the glass transition temperature is higher than the thermal decomposition temperature or lower, and vice versa. There are incompatible systems that dissolve, and partially compatible systems that are compatible in one region and phase separated in another region. In this partially compatible system, phase separation is performed by spinodal decomposition depending on the conditions of the phase separated state. And phase separation by nucleation and growth.

  Furthermore, in the case of a polymer alloy composed of three or more components, a system in which all three or more components are compatible, a system in which all three or more components are incompatible, a compatible phase having two or more components, and the rest There is a system in which one or more phases are incompatible, two components are partially compatible, and the remaining components are distributed in a partially compatible system composed of these two components. The polymer alloy composed of 3 or more components preferred in the present invention is a system in which 2 components are partially compatible and the remaining components are distributed to the partially compatible system composed of 2 components. In this case, the structure of the polymer alloy is 2 Since it can be replaced by a partially compatible structure composed of components, the following description will be made on behalf of a polymer alloy composed of two-component resins.

  Phase separation by spinodal decomposition refers to phase separation that occurs in an unstable state inside the spinodal curve in phase diagrams for different two-component resin compositions and temperatures, and phase separation by nucleation and growth refers to the phase separation. In the figure, it refers to phase separation that occurs in the metastable state inside the binodal curve and outside the spinodal curve.

  The spinodal curve refers to the difference (ΔGmix) between the free energy when compatibilized and the sum of the free energies in two phases that are not compatible (ΔGmix) when two different resins are mixed with respect to the composition and temperature. φ) is a curve that is partially differentiated twice (∂2ΔGmix / ∂φ2), and is an unstable state of ∂2ΔGmix / ∂φ2 <0 inside the spinodal curve and ∂ on the outside 2ΔGmix / ∂φ2> 0.

  The binodal curve is a boundary curve between the region where the system is compatible and the region where the system is separated with respect to the composition and temperature.

  Here, the case of being compatible in the present invention is a state in which they are uniformly mixed at the molecular level. Specifically, both phases having different two-component resins as main components are 0.001 μm or more. The case where the phase structure is not formed is indicated, and the case where the phase is incompatible is the case where the phase is not in a compatible state, that is, the phases mainly composed of two different resin components are 0.001 μm or more. It refers to the state of forming a phase structure. Whether or not they are compatible is determined by, for example, an electron microscope, a differential scanning calorimeter (DSC), or other various methods as described in Polymer Alloys and Blends, Leszek A Utracki, hanser Publishers, Munich Viema New York, P64. Judgment can be made.

  According to detailed theory, in spinodal decomposition, once the temperature of a mixed system that has been uniformly mixed at the temperature of the compatible region is rapidly increased to the temperature of the unstable region, the system will rapidly phase-separate toward the coexisting composition. To start. At that time, the concentration is monochromatized at a constant wavelength, and a two-phase continuous structure is formed in which both separated phases are continuously intertwined regularly with a structure period (Λm). After the formation of the two-phase continuous structure, the process in which only the concentration difference between the two phases increases while keeping the structure period constant is called the initial process of spinodal decomposition.

Furthermore, the structural period (Λm) in the initial process of the above-mentioned spinodal decomposition has a thermodynamic relationship as shown in the following equation.
[Lambda] m to [| Ts-T | / Ts] -1/2
(Where Ts is the temperature on the spinodal curve)
Here, the two-phase continuous structure referred to in the present invention refers to a structure in which both components of the resin to be mixed each form a continuous phase and are entangled three-dimensionally. A schematic diagram of this two-phase continuous structure is described, for example, in “Polymer Alloy Fundamentals and Applications (Second Edition) (Chapter 10.1)” (edited by the Society of Polymer Science: Tokyo Kagaku Dojin).

  In spinodal decomposition, after going through such an initial process, it goes through a medium-term process in which an increase in wavelength and an increase in concentration difference occur simultaneously, and a later process in which an increase in wavelength occurs in a self-similar manner after the concentration difference reaches the coexisting composition. In order to obtain the structure defined in the present invention, the desired structural period before the final separation into the macroscopic two phases has been reached. What is necessary is just to fix a structure in a step.

  In addition, in the process of increasing the wavelength from the mid-stage process to the late-stage process, depending on the influence of the composition and the interfacial tension, the continuity of one phase may be interrupted and the above-described biphasic continuous structure may be changed to a dispersed structure. In this case, the structure may be fixed when the desired interparticle distance is reached.

  Here, the dispersion structure referred to in the present invention is a so-called sea-island structure in which particles mainly composed of the other resin component are interspersed in a matrix mainly composed of one resin component. Point.

  The thermoplastic resin composition of the present invention is structurally controlled to have a biphasic continuous structure with a structural period of 0.001 to 1 μm or a dispersed structure with a distance between particles of 0.001 to 1 μm. By controlling the structural period of the initial process within the range of 0.001 to 0.1 μm, even if the wavelength and concentration difference increase after the above-mentioned intermediate period, both phases continue in the range of the structural period of 0.001 to 1 μm. The structure can be controlled to a structure having a dispersed structure having a distance of 0.001 to 1 μm or a distance between particles. In order to obtain more excellent heat resistance and transparency, the structure is developed and then a two-phase continuous structure with a structural period in the range of 0.001 to 0.5 μm, or a distance between particles of 0.001 to 0.5 μm. It is preferable to control to a dispersive structure of, and further to control to a dispersive structure having a structure period in the range of 0.001 to 0.1 μm or a distance between particles of 0.001 to 0.1 μm. Is more preferable. The effect of the present invention can be obtained by controlling the range of the structural period and the range of the interparticle distance, but by further developing the concentration difference, a structure having more excellent transparency and heat resistance can be effectively used. Can get to.

  On the other hand, in the nucleation and growth, which is the phase separation in the metastable region described above, a dispersed structure that is a sea-island structure is formed from the initial stage, and it grows. It is difficult to form a biphasic continuous structure in the range of 0.01 to 1 μm or a dispersed structure in the range of a distance between particles of 0.01 to 1 μm.

Moreover, in order to confirm the biphasic continuous structure by these spinodal decompositions or a disperse structure, it is important to confirm a regular periodic structure. For example, in addition to confirming that a two-phase continuous structure is formed by observation with an optical microscope or a transmission electron microscope, the scattering maximum in a scattering measurement performed using a light scattering device or a small-angle X-ray scattering device Confirmation of appearing is necessary. Note that the light scattering device and the small-angle X-ray scattering device have different optimum measurement regions, so that they are appropriately selected according to the size of the structure period. The existence of the scattering maximum in this scattering measurement is a proof that there is a regular phase separation structure with a certain period, and its period Λm corresponds to the structure period in the case of the biphasic continuous structure, and the interparticle distance in the case of the dispersion structure. Correspond. The value can be calculated by the following equation using the wavelength λ of the scattered light in the scatterer and the scattering angle θm that gives the scattering maximum.
Λm = (λ / 2) / sin (θm / 2)
In order to realize the spinodal decomposition, it is necessary to bring the polyetherimide and the aromatic polyimide into a compatible state and then to an unstable state inside the spinodal curve.

  First, as a method of realizing a compatible state with a resin composed of two or more components, after dissolving in a common solvent, spray drying, freeze drying, coagulation in a non-solvent substance, film formation by solvent evaporation, etc. from this solution is used. Examples thereof include a solvent casting method and a melt-kneading method in which a partially compatible system is melt-kneaded under compatible conditions. Among these, compatibilization by melt kneading, which is a dry process that does not use a solvent, is preferably used in practice.

  For compatibilization by melt kneading, an ordinary extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing step of the injection molding machine. The temperature for compatibilization needs to be a condition in which the partially compatible resin is compatible.

  Next, when the resin composition made into a compatible state by the above melt kneading is in an unstable state inside the spinodal curve, the temperature for making the unstable state when the spinodal decomposition is performed, and other conditions vary depending on the combination of the resins. Although it cannot be generally stated, it can be set by performing a simple preliminary experiment based on the phase diagram. In the present invention, as described above, after the structural period of the initial process is controlled to a specific range, the structure is further developed after the intermediate process to obtain a specific biphasic continuous structure or a dispersed structure defined in the present invention. preferable.

  The method for controlling to a specific structural period in this initial process is not particularly limited, but it is not less than the lowest glass transition temperature of the individual resin components constituting the thermoplastic resin composition and the above-mentioned thermodynamics. It is preferable to perform heat treatment at such a temperature as to reduce the structural period specified in terms of the size. Here, the glass transition temperature can be obtained from an inflection point generated at the time of temperature increase from room temperature at a temperature increase rate of 20 ° C./min with a differential scanning calorimeter (DSC).

  The method for developing the structure from the initial process is not particularly limited, but a method of heat-treating at the lowest temperature or higher among the glass transition temperatures of the individual resin components constituting the thermoplastic resin composition is usually preferably used. Further, it is preferable that the heat treatment temperature is equal to or higher than the crystal melting temperature of the crystalline resin because the structural development by the heat treatment can be effectively obtained, and that the heat treatment temperature is within the crystal melting temperature ± 20 ° C. Is preferable in order to facilitate the control of the crystal, and more preferably, the crystal melting temperature is within ± 10 ° C.

  In addition, as a method of immobilizing the structure product by spinodal decomposition, the structure fixing of one or both components of the phase-separated phase in a short time by rapid cooling or the like, and when one is a thermosetting component, Structural fixation utilizing the fact that the phase cannot freely move due to the reaction, and structural fixing utilizing the fact that when the other is a crystalline resin, the crystalline resin phase cannot be freely moved by crystallization.

  In the present invention, the polyetherimide and the aromatic polyimide are phase-separated by the above spinodal decomposition to obtain the thermoplastic resin composition of the present invention. It is preferable to combine a resin that is a system for phase dissolution / phase decomposition or a system for reaction-induced phase decomposition.

  In general, partial compatible systems are known to have a low-temperature compatible phase diagram that is easy to be compatible on the low temperature side in the same composition, and a high temperature compatible phase diagram that is easy to be compatible on the high temperature side. It has been. The lowest temperature between the compatible and incompatible branching temperatures in this low-temperature compatible phase diagram is called the lower critical solution temperature (LCST for short). The highest temperature among the incompatible branching temperatures is called the upper critical solution temperature (UCST).

  In the case of a low-temperature compatible phase diagram, a resin of two or more components that have become compatible using a partially compatible system can be brought to a temperature higher than the LCST and a temperature inside the spinodal curve. In the case of the figure, spinodal decomposition can be performed by setting the temperature below UCST and the temperature inside the spinodal curve.

  In addition to spinodal decomposition by this partially compatible system, spinodal decomposition is also induced by melt kneading in non-compatible systems, for example, once compatible under shearing during melt kneading, etc., and then in an unstable state again under non-shearing. Phase separation by spinodal decomposition is also possible by so-called shear field-dependent phase dissolution / phase decomposition in which phase decomposition occurs, and in this case as well, in the same manner as in the case of a partially miscible system, decomposition proceeds in a spinodal decomposition mode and both phases are ordered. Has a continuous structure. Furthermore, this shear field-dependent phase dissolution / phase decomposition is the same as the method based on the temperature change of the partially miscible system in which the spinodal curve does not change because the spinodal curve changes due to the shear field and the unstable region expands. The substantial degree of supercooling (| Ts−T |) also increases in the temperature change range, and as a result, it is easy to reduce the structural period in the initial process of spinodal decomposition in the above relational expression, so that it is preferably used. It is done. In order to achieve compatibilization by shearing during such melt kneading, a normal extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing step of the injection molding machine. In this case, the temperature for compatibilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for developing the structure from the initial process, and other conditions differ depending on the combination of the resins, and cannot be generally stated. The conditions can be set by performing a simple preliminary experiment based on the phase diagram under the shear conditions. Also, as a method of reliably realizing the compatibilization in the plasticizing process of the injection molding machine, it is melt-kneaded with a twin-screw extruder in advance and compatibilized, and after discharging, it is rapidly cooled in ice water or the like to fix the structure in the compatibilized state. A preferred example is a method of injection molding using a paste.

  Furthermore, even in a compatible system, phase separation by spinodal decomposition is possible by so-called reaction-induced phase decomposition in which an unstable state is caused by a change in molecular weight accompanying a chemical reaction and the like, and phase decomposition occurs. For example, the precursor of the resin component that is finally contained, such as the resin component raw material, oligomer, or low molecular weight material constituting the polymer alloy, is compatible with the remaining resin component, and the above monomer, oligomer, or low molecular weight material is In the case where the degree of polymerization and the resin to be alloyed cause phase separation with other resin components, at least one precursor of the resin components constituting the polymer alloy is added in the presence of the remaining resin components. It is possible to induce spinodal decomposition by causing a chemical reaction. Also in this case, the decomposition proceeds in a spinodal decomposition manner as in the case of the partially compatible system, and a regular biphasic continuous structure is obtained. Furthermore, this reaction-induced phase decomposition has the same temperature change range as compared with the method based on the temperature change of the partially miscible system in which the spinodal curve does not change because the spinodal curve changes due to the molecular weight change and the unstable region expands. Is more preferably used since the substantial degree of supercooling (| Ts−T |) increases, and as a result, it becomes easy to reduce the structural period in the initial stage of the spinodal decomposition in the above relational expression. In this case, the glass transition temperature and the crystalline melting temperature in the case of a crystalline resin change with a change in molecular weight due to polymerization and crosslinking, and further, the change from phase dissolution to phase decomposition due to the change in molecular weight varies depending on the system. The temperature for solubilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for developing the structure from the initial process, and other conditions cannot be generally stated, but they are shown in the phase diagram in combination with various molecular weights. Based on this, conditions can be set by performing a simple preliminary experiment.

  In addition, the addition of a third component which is a copolymer such as a block copolymer, a graft copolymer or a random copolymer containing a component constituting a polymer alloy to the polyetherimide and aromatic polyimide constituting the present invention causes phase decomposition. In order to reduce the free energy of the interface between phases, it is preferably used in order to facilitate the control of the structural period in the two-phase continuous structure and the distance between dispersed particles in the dispersed structure. In this case, the third component such as the copolymer is usually distributed to each phase of the polymer alloy composed of the two-component resin except the copolymer, and thus can be handled in the same manner as the polymer alloy composed of the two-component resin.

In mixing and preparing the thermoplastic resin composition according to the present invention, the following methods are preferable methods.
(1) The polyetherimide powder and the aromatic polyimide powder are pre-kneaded using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill, a ribbon blender, etc. to obtain a powder.
(2) Aromatic polyimide powder is dissolved or suspended in an organic solvent in advance, and polyetherimide is added to this solution or suspension and dispersed or dissolved uniformly. Then, the solvent is removed to form powder. .
(3) After dissolving or suspending polyetherimide in an organic solvent solution of polyamic acid, which is a precursor of the aromatic polyimide of the present invention, heat treatment is performed at 100 to 400 ° C., or an imide usually used After chemical imidization using an agent, the solvent is removed to form powder.

  The thermoplastic resin composition thus obtained is used as it is for various molding applications, that is, injection molding, compression molding, transfer molding, extrusion molding and the like, but it is a more preferable method after melt blending. .

  In particular, when the composition is mixed and prepared, mixing and melting powders, pellets, or powder and pellets is also a simple and effective method.

  For melt blending, equipment used for melt blending ordinary rubbers or plastics, such as hot rolls, Banbury mixers, plastic benders, extruders, etc. can be used. The melting temperature is set to be equal to or higher than the temperature at which the blending system can be melted and below the temperature at which the blending system begins to thermally decompose, but the temperature is usually 250 to 400 ° C, preferably 280 to 350 ° C, more preferably 300 ° C. ~ 330 ° C.

  As the molding method of the thermoplastic resin composition of the present invention, extrusion molding or injection molding which is a highly productive molding method for forming a uniform melt blend is suitable, but other transfer molding, compression molding, Sintering molding, extrusion film molding, etc. may be applied.

  In the present invention, a filler may be used as necessary in order to improve strength and dimensional stability. The filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used. Examples of the filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal Fibrous fillers such as fibers, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate and other silicates, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, Rasubizu, ceramic beads, non-fibrous fillers such as boron nitride and silicon carbide and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, these fibrous and / or non-fibrous fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, It is preferable in terms of obtaining superior mechanical strength.

  In order to improve strength, dimensional stability and the like, when such a filler is used, the amount of the filler is not particularly limited, but is usually 1 to 400 parts by weight per 100 parts by weight of the thermoplastic resin composition.

  In addition, with respect to the thermoplastic resin composition of the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant aid, an antistatic agent, and a mold release agent within the range not impairing the object of the present invention. One or more usual additives such as lubricants and coloring agents can be added.

  These additives can be blended at any stage of producing the thermoplastic resin composition of the present invention. For example, a method of adding at the same time when blending at least two resins, Examples thereof include a method in which the component resins are added after melt kneading, and a method in which the resin is first added to one resin and melt kneaded, and then the remaining resin is blended.

  The thermoplastic resin composition of the present invention can be effectively used for products that require a higher use temperature than polyetherimide that has been available in the past. Such products are not particularly limited, and examples thereof include applications such as automobiles, office equipment, electrical / electronic equipment, automatic labor saving equipment, aviation, space equipment, and general industrial equipment.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.

In the following examples and comparative examples, the following resins were used.
Polyetherimide: ULTEM (registered trademark) 1010 (manufactured by GE Plastics)
Aromatic polyimide 1: AURUM (registered trademark) PD450 (manufactured by Mitsui Chemicals), softening temperature 390 ° C., crystallinity 12%
Aromatic polyimide 2: AURUM (registered trademark) PD450M (manufactured by Mitsui Chemicals), softening temperature 380 ° C., crystallinity 0%

[Total light transmittance]
Haze meter: NDH-200 (trade name) manufactured by Nippon Denshoku Co., Ltd.

[Storage modulus (E ')]
A test piece having a length of 50 mm and a width of 15 mm was cut out from a 0.1 mm-thick film, and using a DMS6100 manufactured by SII, in a bending mode, a frequency of 1 Hz, a distance between chucks of 20 mm, a heating rate of 2 ° C./min, and 23 ° C.- Measured at 300 ° C. Furthermore, the storage elastic modulus at 200 ° C. was read from the storage elastic modulus (E ′)-temperature curve.

Example 1
After mixing and mixing polyetherimide and aromatic polyimide in the proportions shown in Table 1, in a twin screw extruder (TEX30α manufactured by Nippon Steel Works, L / D = 45.5) set at an extrusion temperature of 320 ° C. The gut discharged from the die was immediately cooled into ice water and pelletized.

The produced pellet was formed into a sheet by a pressure press (320 ° C. × 3 minutes, press pressure: 5 MPa), and the total light transmittance was measured using the obtained sheet (thickness 0.1 mm).
Next, a sample of length × width × thickness = 50 mm × 15 mm × 0.1 mm was cut out and subjected to a viscoelasticity measuring apparatus, and the storage elastic modulus (E ′) at 200 ° C. is shown in Table 1.

  Furthermore, the sample from which the ultrathin slice was cut out was observed with a transmission electron microscope at a magnification of 100,000 times, the structural period and the state of the structure were observed, and the results are shown in Table 1.

Examples 2-5
Except that the blending and sheet preparation conditions were changed as shown in Table 1, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Examples 1-4
Except that the blending and sheet preparation conditions were changed as shown in Table 1, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 5
Evaluation was made in the same manner as in Example 3 except that the aromatic polyimide used was changed to the liquid crystalline polyimide of Synthesis Example 1 (crystallinity 40%) in JP-A-06-179816. It was described in.

  The thermoplastic resin compositions of Examples 1 to 5 are excellent in all of transparency, heat resistance and processability, whereas Comparative Examples 1 to 5 are inferior in transparency, heat resistance and processability. it is obvious.

  Since the resin compositions of these examples have the properties of polyetherimide and also have heat resistance, for example, for automobiles, office equipment, electrical / electronic equipment, automatic labor-saving equipment, aviation, space equipment The present invention can be said to be of great significance because it can be widely used as a material for parts in all industrial fields such as industrial use and general industrial equipment.

Claims (10)

The total of (A) and (B) is 100 parts by weight, and (A) 1 to 99 parts by weight of polyetherimide and (B) 99 to 1 part by weight of aromatic polyimide having a crystallinity of 10% or less are blended. Thermoplastic resin composition. The thermoplastic resin composition according to claim 1, wherein a total light transmittance of a film having a thickness of 0.1 mm produced from the thermoplastic resin composition is 70% or more. The thermoplastic resin composition according to claim 1 or 2, wherein the molded article made of the thermoplastic resin composition has a storage elastic modulus (E ') at 200 ° C of 1.5 GPa or more. In the thermoplastic resin composition, (A) polyetherimide and (B) aromatic polyimide having a crystallinity of 10% or less are a two-phase continuous structure having a structural period of 0.001 to 1 μm, or an interparticle distance of 0.001 to 0.001. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin composition has a dispersion structure of 1 µm. The thermoplastic resin composition according to claim 4, wherein the two-phase continuous structure or the dispersed structure in the thermoplastic resin composition is formed by phase separation by spinodal decomposition. 6. The thermoplastic resin composition according to claim 5, wherein the thermoplastic resin composition is obtained through melt-kneading. The heat according to claim 6, wherein the thermoplastic resin composition is obtained by compatibilization under shear during melt kneading and then phase separation under non-shear after discharge. Plastic resin composition. The total of (A) and (B) is 100 parts by weight, and (A) 50 to 99 parts by weight of polyetherimide and (B) 50 to 1 part by weight of aromatic polyimide having a crystallinity of 10% or less. The thermoplastic resin composition according to any one of claims 1 to 7. (A) 1 to 99 parts by weight of polyetherimide and (B) 99 to 1 part by weight of aromatic polyimide having a crystallinity of 10% or less are melt-kneaded, with the total of (A) and (B) being 100 parts by weight. The method for producing a thermoplastic resin composition according to any one of claims 1 to 8, wherein the phase is separated under non-shearing after discharge after compatibilizing under shearing. The molded article which consists of a thermoplastic resin composition of any one of Claims 1-8.