JP2002249660A - Resin composition containing polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide-containing resin composition which is low in the content of a low molecular weight compound, exhibits little deterioration of mechanical and electrical properties and imparts little influence to a work environment for an extrusion molding. SOLUTION: This resin composition contains polyimide (A) and 0.01-200 ppm of a low molecular weight compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition having excellent mechanical and electrical properties. For more information,
Low emission gas at high temperature, less impact on working environment of resin processing process, less impact on human body under high temperature usage environment, for example, resin molding material, electronic base material, automotive application, magnetic recording The present invention relates to a resin composition suitable for use in a wide range of fields requiring a resin processing step, such as a film for a medium, a film for electric and electronic parts, and a film for a packaging material.

[0002]

2. Description of the Related Art Resin compositions containing polyetherimide (PEI) and polyimide are excellent in properties such as heat resistance, flame retardancy, electric properties, rigidity and chemical resistance.
It is attracting attention as engineering plastics. As the polyetherimide, trade name Ultem
(Manufactured by GE Plastics) is known, and has been used as a thermoplastic polyimide which can be injection-molded in various fields such as electronic parts and automobile parts.

[0003] In recent years, the environment in which electronic parts and automobile parts using the resin composition containing the above polyetherimide or polyimide are used has been increasingly heated.
However, this resin composition, when the use environment becomes high temperature,
It has become clear that low-molecular-weight compounds are generated in the resin at a concentration of several ppm or more, and that there is a concern that there is a risk of adverse effects on the human body, and that mechanical and electrical properties are degraded. Further, in the processing step, there has been a problem that a low molecular weight compound is generated at the time of the melt extrusion and a worker at a manufacturing site sucks the compound.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to provide a polyimide-containing resin composition having a low content of a low-molecular-weight compound, excellent mechanical properties and electrical properties, and the like. An object of the present invention is to provide a molded article and a film made of a product.

[0005]

The present invention contains a polyimide (A) and has a low molecular weight compound content of 0.01 to 0.01.
The main feature is a resin composition of 200 ppm.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Polyimide (A) used in the present invention
Is a polymer containing, but not limited to, a cyclic imide group as a repeating unit. Among them, it is preferable that the polymer further has a melt moldability, for example,
U.S. Pat. No. 4,141,927, Patent No. 26226
No. 78, Patent No. 2606912, Patent No. 26
Japanese Patent No. 06914, Japanese Patent No. 2596565, Japanese Patent No. 2596566, Japanese Patent No. 2598478, and the like.
6, Japanese Patent No. 2599171, Japanese Patent Application Laid-Open No. 9-4
No. 8852, Japanese Patent No. 2,565,556, Japanese Patent No. 2,564,636, Japanese Patent No. 2,564,637,
Japanese Patent No. 25653548, Japanese Patent No. 25663547, Japanese Patent No. 2558341, Japanese Patent No. 25583
No. 39, Japanese Patent No. 2,834,580, and the like. As long as the effects of the present invention are not impaired, structural units other than cyclic imide groups, for example, ether units, aromatic, aliphatic, alicyclic ester units, oxycarbonyl It goes without saying that a unit or the like may be contained.

As the polyimide (A), for example,
Those containing a structural unit represented by the following general formula are preferred.

[0008]

Embedded image Ar in the above formula is an aromatic group having 6 to 42 carbon atoms, R is a divalent aromatic group having 6 to 30 carbon atoms, and a fat having 2 to 30 carbon atoms. Group 4,
A divalent organic group selected from the group consisting of alicyclic groups having up to 30 carbon atoms.

In the above general formula, Ar is, for example,

[0010]

Embedded image

[0011]

Embedded image Can be mentioned. As R, for example,

[0012]

Embedded image

[0013]

Embedded image Can be mentioned.

These may be present alone or in combination of two or more in the polymer chain, as long as the effects of the present invention are not impaired.

The polyimide (A) used in the present invention is not particularly limited, but is preferably a mixture of a thermoplastic resin (B) such as polyester and the like in view of melt moldability and handleability. As shown by the following general formula, polyetherimide, which is a polymer that is a structural unit containing an ether bond in a polyimide component, can be mentioned.

[0016]

Embedded image However, in the above formula, R ₁ is 2 to 30 divalent aromatic or aliphatic group, a divalent organic radical selected from the group consisting of cycloaliphatic radicals having carbon atoms, R ₂ Is the same divalent organic group as R described above.

R ₁ and R ₂ are, for example, aromatic groups represented by the following formula groups:

[0018]

Embedded image Can be mentioned.

In the present invention, when a polyetherimide having a glass transition temperature of 350 ° C. or lower, more preferably 250 ° C. or lower is used, the effects of the present invention can be easily obtained, and the compatibility with the polyester (A) and the melt moldability can be improved. From the viewpoint, 2,2-bis [4- (2,2) having a structural unit represented by the following formula:
3-dicarboxyphenoxy) phenyl] propane dianhydride and m-phenylenediamine, or a condensate of p-phenylenediamine is preferred.

[0020]

Embedded image This polyetherimide is called "Ultem" (registered trademark).
It is available from GE Plastics under the trademark name.

Examples of low molecular weight compounds contained in the composition together with the polyimide (A) include, for example, 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,3-dichlorobenzene, chlorobenzene, benzene, toluene, phthalate Acid anhydride, phthalimide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, dimethylmethoxyacetamide, N-methylcaprolactam, dimethylsulfone, One or two or more of tetramethylsulfone and N-acetyl-2-pyrrolidone are exemplified. These are often residues such as solvents and catalysts used during polyimide polymerization. In the case of polyetherimide, dichlorobenzene is contained as a low molecular weight compound,
In the case of other polyimides, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, dimethylmethoxyacetamide, N-methylcaprolactam, dimethyl Sulfone,
One or more of tetramethylsulfone and N-acetyl-2-pyrrolidone are often included as low molecular weight compounds.

In the present invention, the content of the low molecular weight compound in the resin composition needs to be 0.01 to 200 ppm.
When the content of the low molecular weight compound exceeds 200 ppm, the tensile modulus and the dielectric constant of a molded article or a film made of the resin composition are significantly reduced as compared with the case of the resin composition of the present invention. When the content of the low-molecular-weight compound exceeds 200 ppm, the amount of low-molecular-weight gas generated during molding processing increases rapidly, and the concentration of the low-molecular-weight gas in the working environment exceeds the allowable range. A more preferred range for the low molecular weight compound content is 0.01 to 150 ppm, a still more preferred range is 0.01 to 100, and a most preferred range is 0.01 to 5 ppm.
It is 0 ppm.

In the present invention, gas chromatography (GC) analysis is preferably used for measuring the content of the low molecular weight compound. In the GC measurement, a low molecular weight compound in the resin can be detected at a content of 95% or more under the condition of 300 ° C. × 30 minutes. In the present invention, the measurement conditions: 30
The amount generated in a nitrogen atmosphere at 0 ° C. for 30 minutes is defined as the content.

On the other hand, other thermoplastic resins (B) that can be contained in the resin composition include polyester,
Preferred are polyether ether ketone, polycarbonate, polyether sulfone, polyphenylene sulfide, polyamide imide, polyarylate, polyimide, polyethylene and the like. Above all, a resin having excellent compatibility with the polyimide (A) is more preferable, and particularly preferably,
Polyester and polyetheretherketone.

Preferred polyesters include polyalkylene terephthalate (polyethylene terephthalate,
Polynaphthalene terephthalate, polycyclohexane terephthalate, polypropylene terephthalate, polyethylene terephthalate / isophthalate copolymer, etc.),
Examples thereof include wholly aromatic polyester and liquid crystalline polyester.

The resin composition of the present invention contains a plasticizer, a weathering agent and a plasticizer as long as the effects of the present invention are not impaired.
Compounds such as antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, coloring agents, and conductive agents, inorganic particles, organic particles, and other kinds of polymers may be added.

The intrinsic viscosity of the resin composition is preferably from 0.5 to 0.8 dl / g, more preferably from 0.55 to 0.77 dl / g, most preferably from the viewpoint of the extrudability of the resin composition. 0.57 to 0.75 dl / g.

The content of the metal contained in the resin composition is preferably 5 to 500 ppm. When the metal content is within this range, low molecular weight compounds can be effectively removed. More preferably 10 to 400 pp
m, more preferably 50 to 300 ppm.

As a method for incorporating a metal atom into the resin composition, there are a compound containing an alkali metal such as lithium, sodium and potassium, an alkaline earth metal such as magnesium and calcium, and a metal atom such as zinc and manganese; Compounds consisting of germanium, antimony, and titanium, specifically, lithium acetate, calcium acetate, magnesium acetate, manganese acetate, lithium chloride,
A method of charging the extruder together with pellets containing a large amount of manganese chloride or the like is preferably used.

Examples of the germanium compound include germanium dioxide and germanium oxide and hydroxide such as germanium hydroxide containing crystal water, and germanium alkoxide compounds such as germanium tetramethoxide and germanium ethyleneglycoxide and phosphorus containing germanium phosphate and the like. Germanium compounds, germanium acetate, and the like can be given.

Examples of the antimony compound include antimony trioxide and antimony acetate.

Examples of the titanium compound include oxides such as titanium dioxide, hydroxides such as titanium hydroxide, alkoxide compounds such as tetramethoxytitanate, tetraethoxytitanate and tetrabutoxytitanate, and glycooxide compounds such as tetrahydroxyethyltitanate. ,
Compounds such as phenoxide compounds and acetates can be mentioned.

Further, the content of the polyimide (A) (ratio to the whole resin composition) is preferably from 5 to 95% by weight from the viewpoint of heat resistance and moldability. More preferably, 8 to 8
0% by weight, more preferably 10 to 50% by weight, most preferably 10 to 30% by weight.

As a method for measuring the ratio between the polyimide (A) and the thermoplastic resin (B) in the resin composition, the following method is preferably used. The resin composition is dissolved in a suitable solvent such as hexafluoroisopropanol / chloroform that dissolves both, and the NMR spectrum of the 1H nucleus is measured. In the obtained spectrum, the absorption (7.0) corresponding to the aromatic proton of bisphenol A of polyimide (A) was obtained.
ppm) and the peak area intensity of the absorption corresponding to the protons of the thermoplastic resin (B), and the molar ratio of the blend is calculated from the ratio and the number of protons. Further, the weight ratio is calculated from the formula weight corresponding to the unit unit of the polymer.

The amount of the carboxyl terminal group of the resin composition of the present invention is from 5 to 5 from the viewpoints of extrusion moldability, thermal decomposition and productivity.
50 equivalents / ton is preferred. More preferably 10-4
2 equivalents / ton, most preferably 20-35 equivalents / ton
n.

The amount of the amino terminal group of the resin composition of the present invention is from 0.1 to 0.5 from the viewpoints of extrusion moldability, thermal decomposition and productivity.
2-20 equivalents / ton is preferred. More preferably, 0.
It is 3 to 10 equivalents / ton, most preferably 0.4 to 5 equivalents / ton.

Further, the resin composition of the present invention preferably has a single glass transition temperature (Tg). The glass transition temperature in the present invention can be determined from the heat flux gap at the time of temperature rise in the differential scanning calorimetry according to JIS K7121. When it is difficult to make a determination only by a method using differential scanning calorimetry, a morphological method such as dynamic viscoelasticity measurement or microscopic observation may be used in combination. When determining the glass transition temperature by differential scanning calorimetry, it is also effective to use a temperature modulation method or a high sensitivity method.

Next, the method for producing the resin composition of the present invention will be described, but it is needless to say that the present invention is not limited to the following production method.

Pulverize polyimide (A) pellets using a crusher.
And pulverized into powder. The dispersion diameter at this time is 20 to 4
00 mesh is preferred, and more preferably 50-300.
Mesh, most preferably 100-250 mesh
You. The obtained powder is gradually reduced under reduced pressure (5 mmHg or less).
While maintaining the temperature at 140 to 180 ° C. under reduced pressure.
By continuing stirring for 0 to 300 minutes, a low molecular weight compound
The object is removed. The obtained powder was added to
To a vent-type twin-screw extruder heated to
Melt extrude and pelletize. The shear rate at this time is 50
~ 300 sec ^-1Is preferred, and more preferably 100 to
200 sec^-1And the residence time is preferably 0.5 to 10 minutes.
More preferably, the condition is 1 to 5 minutes. Also,
The degree of vacuum of the vent is between 0.1 mmHg and 5 mmHg.
Is preferred.

The resin composition of the present invention is molded by a known molding method such as extrusion molding, injection molding, compression molding, and transfer molding, and is put into practical use.

Next, the method for producing the resin molded article of the present invention will be described, but it goes without saying that the present invention is not limited to the following description. After vacuum drying the resin composition of the present invention at 180 ° C. for 3 hours or more, the resin composition is charged into an injection molding machine, and a cylinder temperature of 2
Extrude at 80-380 ° C, more preferably at 300-350 ° C. Molding is performed at a mold temperature of 50 to 100C, more preferably 70 to 90C. The resin composition of the present invention, which can be molded in this manner, has excellent elastic modulus and electrical properties, can be used for electronic base materials, automotive applications and the like, and is very useful.

The resin composition of the present invention is formed into a film by a known film forming method such as melt extrusion film forming and solution cast film forming, and is put into practical use. In the case of a film, it may be a non-oriented film or a uniaxially or biaxially oriented film.

Next, a specific example of the method for producing a biaxially oriented polyester film of the present invention will be described, but it goes without saying that the present invention is not limited to the following description.

The resin composition of the present invention (polyethylene terephthalate / polyimide = 40/60 to 60/40% by weight, intrinsic viscosity = 0.65 to 0.75 dl / l) and polyethylene terephthalate (PE) obtained by a usual method
The pellets of T) are mixed at a predetermined ratio,
After vacuum drying for more than an hour, throw it into an extruder and
After being melt-extruded at 20 ° C. and passed through a fiber-sintered stainless steel metal filter, it is discharged in a sheet form from a T-die. Further, the sheet is brought into close contact with a cooling drum having a surface temperature of 25 to 30 ° C. to be cooled and solidified to obtain a substantially non-oriented film.

Next, this unstretched film is biaxially stretched,
Biaxially oriented. As the stretching method, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used. In order to stretch under optimal conditions, it is preferable to stretch the unstretched film in the range of glass transition temperature (Tg) to Tg + 50 ° C.

Here, using a longitudinal stretching machine in which several rolls are arranged, stretching is performed in the longitudinal direction by utilizing the peripheral speed difference between the rolls (MD stretching), and then transverse stretching is performed by a stenter (TD). The stretching method will be described.

First, the unstretched film is made from (Tg) to (Tg).
+50) (° C), more preferably (Tg) to
(Tg + 30) (C), heated with a group of heating rolls in the range of 1.1 to 5.0 times, preferably 1.5 to 5.0 times in the longitudinal direction.
MD stretching is performed by a method of stretching 4.0 times, more preferably 2.0 to 3.5 times, and cooling with a group of cooling rolls at 20 to 50 ° C. Next, stretching in the width direction is performed using a stenter. The stretching ratio is 2.0 to 6.0 times, preferably 3.0 to 5.5 times, more preferably 4.0 to 5.5 times.
5.0 times, the temperature is in the range of (Tg) to (Tg + 50) (° C), and more preferably (Tg) to (Tg + 30) (° C).
(TD stretching). If necessary, while stretching this stretched film under tension or in the width direction,
The heat treatment is performed at 250 ° C, preferably 170 to 240 ° C, more preferably 160 to 220 ° C.

Then, after cooling to room temperature, the film edge is removed, and a biaxially stretched film can be obtained.

(Method of Measuring Physical Properties and Method of Evaluating Effect) (1) Determination of Low Molecular Weight Compound A sample is weighed on an aluminum board and introduced into a heating tube. Attach a repair pipe (Carbotrap 400) to the heating pipe outlet. N ₂ in a stream,
Heat at 300 ° C. for 30 minutes. This heat treatment is performed by heating in an electric furnace as shown in the schematic diagram of FIG. 1, and the generated gas is trapped in a heating tube. The collection tube is connected to a thermal desorption device (TD
U), and perform GC and GC / MS measurements. 1. Equipment Gas chromatograph 5890series II 02 (Hewlett Packard) Integrator EZchrom Elite Client / Server (Scientific Software) Injection port Split / Splitless injection port (Hewlett Packard) Detector Flame Ionization Detector (Hewlett Packard) Column DB-5 (J & W) Serial Number (SN) ): 7393441 length 30m, inner diameter r 0.25mm, film thickness 0.25μm

[0050] 2. Measurement conditions 2-1. Injection equipment Themal Desorption Unit Model890 (TDU02, Supelco) Transfer temperature 280 ℃ Valve temperature 280 ℃ Desorption temperature 300 ℃ Desorption time 5 minutes Carrier gas Helium Injection mode Split (line flow 15.2ml / min, vent flow 13.8ml / min) 2- 2. Detector Detector temperature 320 ° C Gas Hydrogen 1.2kg / cm ² , Air 3.0kg / cm ² 2-3. Oven Column oven temperature Initial value 50 ° C (hold 5.0 minutes) End value 300 ° C (hold 10.0 minutes) Heating rate 10 ° C / min.linear gradient Standard solutions of low molecular weight compounds were prepared by appropriately diluting high concentration mother liquors. .

(2) Intrinsic viscosity (IV) The value calculated by the following equation from the solution viscosity measured in orthochlorophenol at 25 ° C. was used. ηsp / C = [η] + K [η] ² · C, where ηsp = (solution viscosity / solvent viscosity) −1,
C is the weight of the dissolved polymer per 100 ml of solvent (g / 1
00 ml, usually 1.2), and K is the Haggins constant (0.34
3). The solution viscosity and the solvent viscosity were measured using an Ostwald viscometer. The unit is indicated by [dl / g].

(3) Metal Content Germanium, antimony, titanium,
The strength of each magnesium element was quantified by comparison with a calibration curve obtained from each standard substance. (4) Carboxyl terminal group content The polymer was dissolved in orthochlorocresol / chloroform (weight ratio: 7/3) at 90 to 100 ° C, and the potential difference was determined by alkali.

(5) Amount of amino terminal group 1 g of the polymer is precisely weighed in a 100 ml beaker and dissolved in a mixed solvent of chloroform / methanol / phenol. Then, add a small amount of water and stir 0.1mo
Potentiometric titration was performed with 1-HCl to determine the amount. Automatic titrator: Model GT-05 manufactured by Mitsubishi Chemical Electrode used: glass electrode / reference electrode.

(6) Tensile Modulus of Resin Composition According to the test method ASTM-D638. (7) Dielectric constant A value at 1 kHz was measured according to the test method ASTM-D150.

(8) Young's modulus of film Measured using an Instron type tensile tester according to the method specified in ASTM-D882. The measurement was performed under the following conditions. Measuring device: Orientec Co., Ltd. automatic film strength and elongation measuring device "Tensilon" AMF / RTA-100 Sample size: width 10 mm x length 100 mm, pulling speed: 200 mm / min Measurement environment: temperature 23 ° C, humidity 65 % RH

[0056]

EXAMPLES The present invention will be described based on examples and comparative examples.

Example 1 Polyetherimide (manufactured by GE Plastics Co., Ltd.
(Registered trademark: Ultem 1010) with a twin-shaft crusher (MT
C-2038, manufactured by Miike Iron Works). The crushed diameter was 200 mesh. The obtained polyetherimide powder was put into a rotary vacuum dryer. The degree of vacuum is 2m
mHg and stirring at 180 ° C. for 300 minutes,
Removal of low molecular weight compounds was performed.

The obtained polyetherimide powder was mixed with a co-rotating twin-screw extruder (TEM-produced by Toshiba Machine Co., Ltd.).
Using 35B), the extrusion temperature was 350 ° C., the degree of vent vacuum was 0.5 mmHg, the shear rate was 150 sec ⁻¹ , and the residence time was 3.5.
After melt-kneading under the conditions described above, the mixture was discharged, cooled with water, and then pelletized to obtain pellets of polyetherimide. 99% or more of the low molecular weight compound in this resin composition was dichlorobenzene (DCB), and the content was 40 ppm.

Using the pellets, a cylinder temperature of 350
C., a mold temperature of 210.degree. C. and an injection pressure of 155 MPa were used to mold various test pieces, and the tensile modulus (ASTM D-638) and the dielectric constant were measured. The amount of DCB in the test piece was 40 p.
pm.

Table 2 shows the evaluation results. Obtained resin composition (intrinsic viscosity = 0.67, carboxyl end group content = 5.
2 equivalents / ton, amount of amino terminal group = 0.5 equivalents / to
n, metal content = 55 ppm) had excellent properties with high tensile modulus and dielectric constant.

Example 2 A resin composition was prepared in the same manner as in Example 1 under the conditions shown in Table 1.

As shown in Table 2, since the obtained resin composition was within the range of the present invention, it had a high tensile modulus and a high dielectric constant and excellent properties.

Example 3 Polyetherimide (manufactured by GE Plastics Co., Ltd.
(Registered trademark: Ultem 1010) with a twin-shaft crusher (MT
C-2038, manufactured by Miike Iron Works). The crushed diameter was 200 mesh. The obtained polyetherimide powder was put into a rotary vacuum dryer. The degree of vacuum is 2m
mHg and stirring at 180 ° C. for 300 minutes,
Low molecular weight compounds (dichlorobenzene) were removed.

The obtained polyetherimide pellets (5
0 wt%) and a polyethylene terephthalate (PET) pellet having an intrinsic viscosity of 0.85 (50 wt%) are co-rotating twin-screw extruders (Toshiba Machine Co., Ltd. TEM-35).
Using B), an extrusion temperature of 300 ° C. and a degree of vent vacuum of 2.0
After melt-kneading under the conditions of mmHg, shear rate of 150 sec ^-1 and residence time of 3.5 minutes, the mixture was discharged, cooled with water and pelletized to obtain a resin composition containing 50% by weight of PEI.

Using the obtained pellets, various test pieces were molded at a cylinder temperature of 300 ° C., a mold temperature of 190 ° C., and an injection pressure of 125 MPa, and a tensile modulus (ASTM D-63) was obtained.
8) The dielectric constant was measured. Table 2 shows the results.

As shown in Table 2, the obtained resin composition had high tensile elastic modulus and high dielectric constant, and had excellent characteristics. The metals contained in the resin composition are magnesium and antimony, and the total metal content is 6%.
It was 0 ppm.

Examples 4 to 6 The ratio of the polyimide (A) to the thermoplastic resin (B) was changed and / or the type of the thermoplastic resin (B) was changed to polyether ether ketone (PEEK 150P: VICTR).
EX), pellets were obtained and various test pieces were formed in the same manner as in Example 3 under the conditions shown in Table 1 except that the test pieces were changed to EX. Table 2 shows the results.

Example 7 A resin composition containing 50% by weight of polyetherimide was prepared in the same manner as in Example 3. The pellet (20% by weight) and polyethylene terephthalate (intrinsic viscosity 0.6
Using the pellets of 2) (80% by weight), various test pieces were molded at a cylinder temperature of 300 ° C., a mold temperature of 190 ° C., and an injection pressure of 125 MPa, and a tensile strength (ASTMD-638),
The dielectric constant was measured. Table 2 shows the results.

As shown in Table 2, the obtained resin composition had a high tensile modulus and a high dielectric constant, and had excellent characteristics.

Example 8 The thermoplastic resin (B) was mixed with polyether ether ketone (P
A resin composition was prepared and molded in the same manner as in Example 7, except that the composition was changed to EEK 150P (manufactured by VICTREX). As shown in Table 2, the obtained resin composition had a high tensile modulus and a high dielectric constant, and had excellent properties.

Example 9 200 g of isophorone diisocyanate was added to 3000 ml of N-methyl-2-pyrrolidone (NMP) under a nitrogen atmosphere, followed by stirring. Next, 196 g of pyromellitic anhydride was added to this solution at room temperature, and the temperature was gradually raised. Thereafter, when heating was performed at 180 ° C. for 6 hours, the generation of carbon dioxide was terminated, so the heating was stopped. The polymer solution was developed in water and washed, and then the obtained polymer was dried to obtain a polyimide (a).

A resin composition was prepared, molded and evaluated in the same manner as in Example 7 except that the polyimide (a) was used as the polyimide (A).

Comparative Example 1 Polyetherimide (manufactured by GE Plastics Co., Ltd.
Registered trademark: Ultem 1010) pellet in the same direction
Rolling twin screw extruder (Toshiba Machine Co., Ltd. TEM-35
B) and an extrusion temperature of 350 ° C., as in Example 1.
Shear rate 150 seconds ^-1Kneading under the condition of residence time 3.5 minutes
After discharging, water cooling and then pelletizing to polyetherimide
A resin pellet was obtained. Dichlorobenzene in this resin composition
The content of benzene (DCB) is 320 ppm, which is within the range of the present invention.
Because it was outside, near the extrusion die (30 cm from the die)
The low molecular weight compound concentration was as high as 50 ppm.

Using the pellets, a cylinder temperature of 350
C., a mold temperature of 210.degree. C. and an injection pressure of 155 MPa were used to form various test pieces, and the tensile modulus (ASTM D-638) and the dielectric constant were measured. Table 2 shows the results. As a result, the tensile elastic modulus and the dielectric constant were low, and the characteristics were clearly inferior to those of Example 1.

Comparative Examples 2 and 3, except that the low molecular weight compound was not removed.
Pellets were prepared in the same manner as in Examples 3 and 5. As is evident from Table 2, only the melt extrusion with the twin screw extruder resulted in a large amount of DCB and out of the range of the present invention.
The dichlorobenzene concentration of m) was a high value.

Using the pellets, a cylinder temperature of 350
C., a mold temperature of 210.degree. C. and an injection pressure of 155 MPa were used to form various test pieces, and the tensile modulus (ASTM D-638) and the dielectric constant were measured. Table 2 shows the results. As a result, the tensile modulus and the dielectric constant were low, and the properties were clearly inferior to those of Examples 3 and 5.

Comparative Example 4 A pellet of polyetherimide (registered trademark: Ultem 1010, manufactured by GE Plastics Co., Ltd.) which had not been subjected to the removal treatment of a low molecular weight compound was subjected to a single screw extruder (φ = 90).
mm, L / D = 28), discharged, cooled with water and pelletized to obtain pellets of polyetherimide. The concentration of the low molecular weight compound in the obtained pellet was as high as 330 ppm, and the concentration of the low molecular weight compound in the vicinity was also as high as 70 ppm.

Using the pellets, a cylinder temperature of 350
C., a mold temperature of 210.degree. C. and an injection pressure of 155 MPa were used to form various test pieces, and the tensile modulus (ASTM D-638) and the dielectric constant were measured. Table 2 shows the results. As a result, the tensile modulus and the dielectric constant were low, and the properties were clearly inferior to those of Examples 1 and 2.

[0079]

[Table 1]

[0080]

[Table 2]

Example 10 In the same manner as in Example 3, a pellet containing 50% by weight of polyetherimide was prepared. The obtained pellet (2
0% by weight) and polyethylene terephthalate pellets (80% by weight) having an intrinsic viscosity of 0.62.
Dried at 80 ° C. for 3 hours. The mixed pellet was put into a single screw extruder (φ = 90 mm, L / D = 28) and passed through a fiber sintered stainless metal filter (1.2 μm cut) at a shear rate of 10 sec ⁻¹ , It was discharged in a sheet form from a T-die. The sheet was placed on a cooling drum having a surface temperature of 25 ° C. at a draft ratio of 10 m / m.
It was solidified and quenched at a speed of minutes to obtain a substantially non-oriented unstretched film. Dichlorobenzene (DCB) around 30 cm from the end of the T-die die was not detected.

Subsequently, the unstretched film is stretched 3.4 times (MD stretching) at a temperature of 105 ° C. using a longitudinal stretching machine composed of a plurality of heated rolls and utilizing the peripheral speed difference between the rolls. Subsequently, the film is stretched 3.65 times (TD stretching) at a temperature of 100 ° C. using a stenter, heat-treated at 190 ° C., and cooled to room temperature.
A 0 μm biaxially stretched film was obtained.

The resulting film had a low Young's modulus and a high dielectric constant because of the low content of the low molecular weight compound, and had excellent characteristics. Also, the film is
It had a single glass transition temperature.

Comparative Example 5 A pellet containing 50% by weight of polyetherimide was prepared in the same manner as in Comparative Example 2 without removing the low molecular weight compound.

The obtained pellets (20% by weight) and polyethylene terephthalate pellets having an intrinsic viscosity of 0.62 (8
0% by weight) and dried at 180 ° C. for 3 hours. The mixed pellet is fed to a single screw extruder (φ = 90 mm,
L / D = 28), passed through a fiber sintered stainless metal filter (1.2 μm cut) at a shear rate of 10 sec ⁻¹ , and discharged from a T-die in a sheet form. The sheet was closely adhered and solidified on a cooling drum having a surface temperature of 25 ° C. at a draft ratio of 10 at a speed of 20 m / min using an electrostatic application method, and was quenched to obtain a substantially non-oriented unstretched film. T
Dichlorobenzene (D
The CB) concentration was as high as 30 ppm.

Subsequently, the unstretched film is stretched 3.4 times (MD stretching) at a temperature of 105 ° C. using a longitudinal stretching machine composed of a plurality of heated rolls and utilizing the peripheral speed difference between the rolls. Subsequently, the film is stretched 3.65 times (TD stretching) at a temperature of 100 ° C. using a stenter, heat-treated at 190 ° C., and cooled to room temperature.
A 0 μm biaxially stretched film was obtained.

Since the obtained film had a large content of dichlorobenzene and was out of the range of the present invention, the film was clearly inferior in Young's modulus and dielectric constant as compared with Example 10.

[0088]

[Table 3]

[0089]

The resin composition of the present invention is a polyimide-containing resin composition having a low content of low-molecular-weight compounds, a low mechanical property and electrical properties, and a small effect on the working environment of extrusion molding. It can be widely used in the fields of molding materials, composite materials, electric / electronic parts and the like.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing a heat treatment apparatus for measuring the content of a low molecular weight compound in a resin composition.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA15 AA43 AA50 AA51 AA60 AA64 AC03 AC12 AC13 AC14 AF13 AF36 AH12 4J002 BB02X CF00X CF16X CG00X CH09X CM04W CM04X CN01X CN03X EB126 EP016 EU016 EU026 EV206 EW156

Claims (8)

[Claims] 1. A resin composition comprising a polyimide (A) and a content of a low molecular weight compound of 0.01 to 200 ppm. 2. A polyether ether ketone,
The resin composition according to claim 1, comprising at least one thermoplastic resin (B) selected from polyester, polycarbonate, polyether sulfone, polyphenylene sulfide, polyamide imide, polyarylate, polyimide, and polyethylene. 3. The resin composition according to claim 1, wherein the low molecular weight compound is dichlorobenzene. 4. The low molecular weight compound is N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric triamide, dimethylmethoxyacetamide, N-methylcaprolactam The resin composition according to claim 1, wherein the resin composition is one or more of dimethylsulfone, tetramethylsulfone, and N-acetyl-2-pyrrolidone. 5. The resin composition according to claim 1, wherein the polyimide (A) is a polyetherimide. 6. The resin composition according to claim 1, wherein the content of the polyimide (A) is 5 to 95% by weight based on the total amount of the resin composition. 7. A molded article using the resin composition according to claim 1. 8. A film comprising the resin composition according to claim 1.