JP3126213B2 - Aromatic polysulfone film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polysulfone film mainly comprising a resin containing an aromatic polysulfone copolymer, having excellent heat resistance and chemical resistance and having transparency.

[0002]

2. Description of the Related Art Aromatic polysulfone resins are known as resins having very well-balanced physical properties having excellent heat resistance, mechanical properties and electrical properties.
It is widely used in fields such as the aircraft industry and the electric and electronic industries. Representative examples of the aromatic polysulfone resin include Victrex PES (manufactured by ICI) and Udel Polysulfone (manufactured by Union Carbide). These aromatic polysulfone resins have heat deformation temperatures of 203 ° C. and 174 ° C., respectively, and are excellent in heat resistance and also in mechanical properties such as bending properties and tensile properties. However, in the electric / electronic material and aircraft related industries in recent years, higher properties have been required, and applications in which the properties of both resins are not sufficient are increasing. For example, a film for a flexible printed circuit board is required to have physical properties that can withstand a solder heat resistance test, but the heat resistance of a film using both resins is not sufficient and cannot be applied. Further, in the chemical resistance of the aromatic polysulfone resin, since there is no resistance to a general-purpose solvent, there is a disadvantage that the application use of a film using the resin is limited.

In order to meet this demand, a method of manufacturing a multilayer film by extruding an aromatic polysulfone resin together with a polyether ketone or a polyphenylene sulfide resin is disclosed in JP-A-62-238737.
According to this method, although the resulting film has improved heat resistance and chemical resistance, a peeling phenomenon at an adhesive interface occurs and transparency is impaired. It is not sufficient for heat resistance required for FPC films and the like, and is not satisfactory for practical use.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has excellent heat resistance and chemical resistance as well as transparency as compared with conventional aromatic polysulfone resin films. It is an object of the present invention to provide an aromatic polysulfone film having:

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, a film mainly composed of an aromatic polysulfone having a specific structure has been found to have transparency, heat resistance and resistance to heat. They have found that they have excellent chemical properties, and have completed the present invention.

The first aromatic polysulfone film in the present invention is obtained by polymerizing monomer units represented by the following general formulas (I), (II) and (III).
5 to 30 mol% of the monomer unit represented by
70 mol% is a monomer unit represented by the following general formulas (II) and (III), and has a concentration of 1 in dimethylformamide.
g / dl, reduced viscosity measured at a temperature of 30 ° C. is 0.35 d
1 / g to 0.6 dl / g aromatic polysulfone copolymer in a range of 51% by weight or more and less than 100% by weight
And a resin containing polyetherimide or polyether ketone in a range of 49% by weight or more and more than 0% by weight , thereby achieving the above object.

[0007]

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(However, in the above general formula, n is 3 or 4
Indicates an integer. R ¹ and R ² represent a hydrogen atom, a methyl group or a halogen atom, and may be the same or different. a and b are each an integer of 1 to 4,
They may be the same or different. X and Y each represent a halogen atom).

The second aromatic polysulfone film of the present invention is obtained by polymerizing the monomer units represented by the following general formulas (IV), (V) and (VI).
5) to 30 mol% of a monomer unit represented by V), the balance being 9
5-70 mol% is a monomer unit represented by the following general formulas (V) and (VI), and has a reduced viscosity of 0.35 in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C.
containing 50 to 100% by weight of an aromatic polysulfone copolymer of dl / g or more and 0.6 dl / g or less, and 49 to 0% by weight of polyetherimide or polyether ketone;
The above purpose is achieved.

[0010]

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(Where m is 3 or 4 in the above general formula)
Indicates an integer. R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom,
It represents a methyl group or a halogen atom, and may be the same or different from each other. c to f are integers of 1 to 4 and may be the same or different. Z represents a halogen atom).

The aromatic polysulfone copolymer, which is a component of the first aromatic polysulfone film of the present invention, comprises:
Obtained by polymerizing the monomer units represented by the above general formulas (I), (II) and (III),
And (III), except that OH, X and Y are excluded, and the repeating units are linearly linked via an ether bond.

The mole fraction of the monomer unit (I) in the copolymer is 5 to 30 mol%, preferably 10 to 2 mol%.
5 mol%. If the molar fraction is less than 5 mol%, the effect of improving heat resistance when formed into a film is not sufficient, and if it exceeds 30 mol%, the melt viscosity of the aromatic polysulfone copolymer is extremely increased. Impaired, not practical.

The above-mentioned aromatic polysulfone copolymer has a molecular weight of 1 g / dl in dimethylformamide at a temperature of 3 g / dl.
It can be represented by the reduced viscosity measured at 0 ° C. In this case, it is necessary that the viscosity is 0.35 dl / g or more and 0.6 dl / g or less. When the reduced viscosity is less than 0.35 dl / g, the mechanical properties when the aromatic polysulfone copolymer is formed into a film are reduced. When the reduced viscosity exceeds 0.6 dl / g, the film processability is reduced, and both are not preferred. .

The dihydroxy compound represented by the above general formula (I) used in the present invention is, for example, 4,4 ″-
Dihydroxy-p-terphenyl and 4,4 ″ ′-dihydroxy-p-quarterphenyl are preferably used. Note that 4,
4 '''-dihydroxy-p-quarterphenyl is, for example, J
It can be synthesized according to the method described in ournal of Chemical Society 1379-85 (1940).

The above general formula (I) used in the present invention
As the monohalogenomonohydroxysulfone compound represented by I), a compound represented by the following formula is suitably used.

[0017]

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In the compound represented by the above formula (III) used in the present invention, examples of the halogen atom represented by Y include fluorine, chlorine and iodine, and fluorine and chlorine are particularly preferred. R ¹ and R ² include a hydrogen atom, a methyl group and a halogen atom, and preferred halogen atoms are chlorine and bromine. Preferably, a compound represented by the following formula can be exemplified.

[0019]

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The aromatic polysulfone copolymer, which is a component of the second aromatic polysulfone film of the present invention, comprises:
Obtained by polymerizing the monomer units represented by the above general formulas (IV), (V) and (VI),
And (VI) except that OH and Z are excluded from each other in a straight chain via an ether bond.

The mole fraction of the monomer units (IV) in the copolymer is 5 to 30 mol%, preferably 10 to 2 mol%.
5 mol%. If the molar fraction is less than 5 mol%, the effect of improving heat resistance when formed into a film is not sufficient, and if it exceeds 30 mol%, the melt viscosity of the aromatic polysulfone copolymer is extremely increased. Impaired, not practical.

The aromatic polysulfone copolymer has a molecular weight of 1 g / dl in dimethylformamide at a temperature of 3 g / dl.
It can be represented by the reduced viscosity measured at 0 ° C. In this case, it is necessary that the viscosity is 0.35 dl / g or more and 0.6 dl / g or less. When the reduced viscosity is less than 0.35 dl / g, the mechanical properties when the aromatic polysulfone copolymer is formed into a film are reduced. When the reduced viscosity exceeds 0.6 dl / g, the film processability is reduced, and both are not preferred. .

The dihydroxy compound represented by the above general formula (IV) used in the present invention is, for example, 4,4 ″-
Dihydroxy-p-terphenyl and 4,4 ″ ′-dihydroxy-p-quarterphenyl are preferably used. Note that 4,
4 '''-dihydroxy-p-quarterphenyl is, for example, J
It can be synthesized according to the method described in ournal of Chemical Society 1379-85 (1940).

In the dihydroxy compound represented by the above general formula (V) used in the present invention, R ³ and R ⁴ are a hydrogen atom, a methyl group or a halogen atom. As the halogen atom, chlorine and bromine are preferred. Suitable compounds include those represented by the following formula.

[0025]

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In the compound represented by formula (VI) used in the present invention, examples of the halogen atom represented by Z include fluorine, chlorine and iodine, and fluorine and chlorine are particularly preferred. R ⁵ and R ⁶ include a hydrogen atom, a methyl group and a halogen atom, and preferred halogen atoms are chlorine and bromine. Suitable compounds include those represented by the following formula.

[0027]

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The production method of the aromatic polysulfone copolymer, which is a component of the first and second aromatic polysulfone films in the present invention, is not particularly limited.
Preferably, a nucleophilic substitution polycondensation method in which a monomer as a raw material is polymerized in a polar solvent in the presence of an alkali metal salt is used. As the alkali metal salt, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate and the like are preferable, and sodium carbonate or potassium carbonate is particularly preferable. As the polar solvent, a sulfone-based solvent such as sulfolane, diphenylsulfone, and diphenylsulfoxide, or an amide-based solvent such as dimethylacetamide and dimethylimidazoline is preferably used.
The polymerization temperature is usually in the range of 80 to 400 ° C, preferably in the range of 100 to 350 ° C. The mixing ratio of the monomer to be polymerized is preferably such that all the halogen groups are in the range of 90 to 110 mol% with respect to all the hydroxyl groups of the monomer, in order to obtain a higher molecular weight aromatic polysulfone copolymer. Is preferably in the range of 95 to 105 mol%.

The first and second aromatic polysulfone films of the present invention contain a resin having the polysulfone copolymer alone or a majority, that is, containing 51 to 100% by weight of the aromatic polysulfone copolymer, and containing polyetherimide or 49 to 0% by weight of polyether ketone
It is formed from the contained resin. In this case, more preferably, the aromatic polysulfone copolymer is 60 to 100% by weight.
And is formed from a resin containing 40 to 0% by weight of polyetherimide or polyetherketone. When the content of the aromatic polysulfone copolymer is less than 51% by weight, heat resistance is lowered, and physical properties required as a film for electronic materials, for example, are not satisfied, which is not preferable.

As the polyetherimide optionally contained in the above resin, those represented by the following general formula (VII) can be used.

[0031]

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(In the above formula, g is an integer of 1 or more, preferably 10 to 10,000, and the group -OT <
Is

[0033]

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Is selected from Here, R ⁹ is hydrogen, a lower alkyl group or a lower alkoxy group, and the polyetherimide is preferably represented by the following formula (VII ′)

[0035]

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And a third -OT <, wherein R ⁹ is hydrogen. The divalent bond of —O—R ⁷ —O— is formed with respect to two phenyl groups in the above formula (VII ′),
(1) group located at the 3 ';3,4'; 4,3 'or 4,4' position, and R ⁷ is a divalent organic group;

[0037]

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And (2) group

[0039]

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Is selected from (2) In the group, V is the following group

[0041]

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Wherein q is 0 or 1,
y is an integer of 1 to 5. R ⁸ represents (a) 6 carbon atoms
Aromatic hydrocarbon groups having from 20 to 20 and halogenated derivatives thereof; (b) alkylene groups and cycloalkylene groups having from 6 to 20 carbon atoms, (c) having 2 carbon atoms
A polydiorganosiloxane in which an alkylene group having 1 to 3 is located at a terminal; and (c) a compound represented by the following formula:

[0043]

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Wherein Q is the following group

[0045]

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2 wherein x is an integer of 1 to 5
Is a valence organic group .

For the purposes of the present invention, particularly preferred polyetherimides are those wherein -OT <and R ⁷ are each

[0048]

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And R ⁸ is

[0050]

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Is a polyetherimide selected from Most preferred are polyetherimides wherein R ⁸ is metaphenylene.

The polyether ketone optionally contained in the above resin is represented by the following formula (VIII)

[0053]

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And a repeating unit represented by the formula:
Other repeating units shown below

[0055]

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The structure including
A polyether ketone containing the repeating unit of the above formula (VIII) alone is preferably used.

In order to produce the first and second aromatic polysulfone films of the present invention, a film is formed by a T-die extrusion method in which a conventional extruder is heated and melted, or a resin solution dissolved in an organic solvent is cast. Then, a method of volatilizing the organic solvent may be used. However, in the production of a resin film containing an aromatic polysulfone copolymer and polyether ketone, a film cannot be formed by a casting method because there is no solvent that dissolves polyether ketone.

In forming a film comprising a resin containing an aromatic polysulfone copolymer by an extrusion method, the barrel temperature is usually 280 to 420 ° C., preferably 300 to 420 ° C.
400 ° C. and the die temperature is typically 300-4
The temperature is set to 50 ° C, preferably 320 to 400 ° C. 4
At a high temperature of 00 ° C. or higher, the decomposition of the aromatic polysulfone copolymer occurs. Therefore, the film is preferably formed at a temperature of 400 ° C. or lower. The high-temperature film extruded from the extruder is rapidly cooled to a temperature in the range of 100 to 260 ° C. on a moving surface such as a rotating drum, and sent to a winding device to obtain a film. The winding speed of the winding device is preferably 50 m / min or less, more preferably 20 m / min, in order to obtain a film having excellent accuracy due to thickness and good surface properties, although it depends on the capacity of the manufacturing device. min or less.

In forming a film containing an aromatic polysulfone copolymer and a resin containing polyetherimide or polyetherketone by an extrusion method, the aromatic polysulfone copolymer and the polyetherimide or polyetherketone are separately prepared. It is possible to supply the mixture to an extruder or to mix them with a melt mixer in advance and then supply the mixture to the extruder.

The barrel temperature of the extruder in the aromatic polysulfone copolymer-polyetherimide mixed system is usually
The temperature is set at 260 to 420 ° C, preferably 280 to 400 ° C, and the die temperature is usually set at 300 to 420 ° C, preferably 320 to 400 ° C. Then, 100-22
It is supplied to a moving surface of a rotating drum or the like set at a temperature of 0 ° C. and rapidly cooled to form a film.

The barrel temperature of the extruder in the aromatic polysulfone copolymer-polyether ketone mixed system is usually
The temperature is set at 330-420 ° C, preferably 350-400 ° C, and the die temperature is usually set at 340-420 ° C, preferably 350-400 ° C. Then 100-26
It is supplied to a moving surface of a rotating drum or the like set at a temperature of 0 ° C. and rapidly cooled to form a film.

When a resin containing an aromatic polysulfone copolymer is formed into a film by a casting method, a halogen-based solvent such as chloroform, methylene chloride and dichloroethane, dimethylformamide, dimethylacetamide and N-methylpyrrolidone are used as an organic solvent. Amide solvents such as dimethylformamide are preferred, and dimethylformamide is particularly preferred. In this case, the concentration of the resin dissolved in the organic solvent depends on the thickness of the target film, but is preferably 30% by weight or less in the resin solution. Considering the solubility of the resin and the workability of the solvent, the content is more preferably 20% by weight or less. The resin solution is cast on a commonly used drum coater and belt coater, dried and formed into a film. The drying temperature is preferably increased stepwise. Strictly speaking, by raising the drying temperature at a temperature not exceeding the glass transition temperature of the resin containing the residual organic solvent, the most efficient film formation becomes possible. Further, it is necessary to perform a process of drawing the film from a coater, blowing hot air on both sides of the film and drying the film to reduce the residual solvent to 1% by weight or less. In this case, the hot air temperature is determined by the glass transition temperature of the film. As described above, the temperature is preferably set to 260 to 280 ° C. If the residual solvent remains in an amount of 1% by weight or more, physical properties deteriorate, which is not preferable.

In the mixed system of aromatic polysulfone copolymer-polyetherimide, it is possible to form a film by the same method as the above-mentioned casting method, and as an organic solvent, trichloroethane, trichloromethane, tetrachloromethane or the like can be used. Amide-based solvents such as halogen-based solvents, dimethylformamide, dimethylacetamide, and N-methylpyrohydrin are preferably used, and dimethylacetamide is particularly preferred.

The obtained film can be stretched if necessary. In the extrusion method, a film stretched at an arbitrary magnification can be obtained by controlling the extrusion speed and the winding speed. Biaxial stretching using a commercially available biaxial stretching machine is also possible. Although the stretching ratio depends on the purpose and application, a stretching ratio of 5 times or less is preferable in consideration of workability, accuracy in thickness, and the like.

The thickness of the first and second aromatic polysulfone films in the present invention can be arbitrarily selected depending on the purpose and application. However, the limit of the thickness that can be controlled and processed depends on the film production method. In the film formation by the extrusion method, a film having an arbitrary thickness can be obtained by controlling the width of the opening of the T-die, the extrusion speed and the winding speed, but the accuracy and the surface property of the thickness are sufficiently controlled. In order to stably supply a good film with no defects and a defect, the film thickness is preferably 1 to 500 μm, more preferably 5 to 200 μm. When the film is formed by the casting method, when the film is too thin, when the film is peeled off from the top of the coater, the film tends to be damaged, and when the film is too thick, the residual solvent tends to remain. It is preferably 200 μm, more preferably 5 to 100 μm.

In order to improve the slipperiness of the film, inert inorganic particles such as alumina silicate, silicon oxide, kaolin, talc, calcium carbonate, lithium carbonate, barium carbonate, titanium oxide and magnesium oxide are previously added to the above resin. It is also possible to add it. The film of the present invention may be subjected to a surface coat and a surface treatment as necessary.

[0067]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto. The films obtained in the following Examples and Comparative Examples were evaluated for various properties based on the following methods.

[Evaluation of Film] Heat resistance The glass transition temperature of the film was measured using a differential scanning calorimeter (under a nitrogen stream, the temperature was raised at 20 ° C./min). Furthermore, a soldering iron at 260 ° C. was contacted for 30 minutes, and the shape change of the film was examined.

2. Chemical resistance test In a state where 1% strain was applied to the film, the films obtained in Examples and Comparative Examples were immersed in acetone, and a change in shape after 1 hour was examined.

Example 1 A 4-chloro-4 '-(p-hydroxyphenyl) diphenyl was placed in a 20 ml eggplant-shaped flask equipped with a stirrer, a gas inlet tube, a thermometer and a condenser having a receiver at the tip. 10.33 g of sulfone (30 mmo
l), 4,4 '''-dihydroxy-p-quarterphenyl
39 g (10 mmol), 2.88 g (10 mmol) of 4,4'-dichlorodiphenylsulfone, 3.41 g (25 mmol) of anhydrous potassium carbonate, 60 diphenylsulfone
g and toluene (25 ml) were charged and the atmosphere was replaced with nitrogen. Next, stirring and heating were started under a nitrogen atmosphere,
At 0 to 170 ° C, toluene was azeotropically distilled to remove water in the system. After confirming that the fraction stops after about 1 hour, 220 ° C. for 1 hour, 250 ° C. for 30 minutes, 280 ° C.
For 30 minutes and at 320 ° C. for 3 hours. After completion of the reaction, potassium chloride precipitated in the reaction solution was removed by filtration, and the filtrate was poured into a large amount of methanol to precipitate a polymer. The reduced viscosity of the obtained polymer is 0.40 dl.
/ G (in dimethylformamide, 30 ° C, 1g / dl)
Met.

The aromatic polysulfone copolymer was extruded by an extruder controlled at a barrel temperature of 380 ° C. and a die temperature of 400 ° C., and rapidly cooled by a rotating drum having a surface temperature set at 220 ° C. The film was fed to a winding device at a winding speed of 2 m / min to obtain a film having a thickness of 100 μm. Table 1 shows the results of the above evaluation of the obtained film.

(Examples 2, 3 and Comparative Examples 1 and 2) 4-chloro
-4 '-(p-hydroxyphenyl) diphenyl sulfone, 4,
An aromatic polysulfone copolymer was prepared in the same manner as in Example 1 except that the molar fractions of 4 '''-dihydroxy-p-quarterphenyl and 4,4'-dichlorodiphenylsulfone were changed as shown in Table 1. Prepared and filmed. Table 1 shows the results of the above evaluation of the obtained film.

Comparative Example 3 A film was formed in the same manner as in Example 1 except that Victrex PES (4100G, manufactured by ICI) was used as the aromatic polysulfone copolymer. Table 1 shows the results of the above evaluation of the obtained film.

[0074]

[Table 1]

In Table 1, A to C indicate the following matters.

A: molar fraction of 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone B: molar fraction of 4,4'''-dihydroxy-p-quarterphenyl C: 4,4'- Molar fraction of dichlorodiphenyl sulfone (Examples 4 to 6, Comparative Example 4) An aromatic polysulfone copolymer was prepared by the method described in Example 1, and a polyether ketone (Victrex PEEK, manufactured by ICI) was prepared. Were kneaded at a weight fraction shown in Table 2 using a Brabender graph extruder, and pelletized.

The obtained resin was extruded with an extruder controlled at a barrel temperature of 380 ° C. and a die temperature of 400 ° C.
It was quenched by a rotating drum whose surface temperature was set to 220 ° C.
The film was fed to a winding device at a winding speed of 2 m / min to obtain a film having a thickness of 100 μm. Table 2 shows the results of the above evaluation of the obtained film.

(Examples 7 to 9, Comparative Example 5) 4-chloro-4'-
(P-hydroxyphenyl) diphenyl sulfone, 4,4 '''
Aromatic polysulfone copolymer was prepared in the same manner as in Examples 4 to 6 and Comparative Example 4 except that the molar fractions of -dihydroxy-p-quarterphenyl and 4,4'-dichlorodiphenylsulfone were changed as shown in Table 2. A coalescence was prepared and formed into a film. Table 2 shows the results of the above evaluation of the obtained film.
Shown in

[0079]

[Table 2]

In Table 2, A to C and * indicate the following.

A: molar fraction of 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone B: molar fraction of 4,4'''-dihydroxy-p-quarterphenyl C: 4,4'- Molar fraction of dichlorodiphenyl sulfone *: weight ratio of aromatic polysulfone copolymer / polyether ketone (Examples 10 to 12, Comparative Example 6)
19.25 kg of N, N-dimethylacetamide (hereinafter abbreviated as DMAC) was charged, 5.75 kg of polyetherimide was gradually added at room temperature, and the mixture was stirred for 10 hours to completely dissolve the polyetherimide resin. A thick polyetherimide solution was obtained. Next, a part of this polyetherimide solution was divided into flasks each equipped with a stirrer at a rate of 200 g, and the aromatic polysulfone copolymer prepared by the method described in Example 1 was added to the polyetherimide in the ratio shown in Table 3. The mixture was stirred at room temperature for 5 hours and mixed. At this time, DMAC was added so that the solution concentration became 5% by weight. The mixture was cast on a glass plate with a doctor knife and dried in a hot air drier at 120 ° C. for 10 minutes.
This semi-dried film was fixed on a metal frame, and
To 180 ° C for 20 minutes and finally 260
Heat treatment was performed at 10 ° C. for 10 minutes to obtain a film having a thickness of 100 μm. Table 3 shows the results of the above evaluation of the obtained film.

(Examples 13 to 15, Comparative Example 7) 4-chloro
-4 '-(p-hydroxyphenyl) diphenyl sulfone, 4,
A film was prepared in the same manner as in Examples 10 to 12 and Comparative Example 6, except that the molar fractions of 4 '''-dihydroxy-p-quarterphenyl and 4,4'-dichlorodiphenylsulfone were changed as shown in Table 3. Was performed. Table 3 shows the results of the above evaluation of the obtained film.

[0083]

[Table 3]

In Table 3, A to C and * indicate the following.

A: mole fraction of 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone B: mole fraction of 4,4'''-dihydroxy-p-quarterphenyl C: 4,4'- Molar fraction of dichlorodiphenyl sulfone *: weight ratio of aromatic polysulfone copolymer / polyetherimide (Example 16) 20 ml eggplant equipped with a stirrer, a gas inlet tube, a thermometer and a condenser with a receiver at the tip In a mold flask, 3.39 g (10 mmol) of 4,4 ″ ′-dihydroxy-p-quarterphenyl, 5.76 g (20 mmol) of 4,4′-dichlorodiphenylsulfone, and 4,4′-dihydroxydiphenylsulfone. 51g (10mmo
l), 3.41 g (25 mmol) of anhydrous potassium carbonate,
60 g of diphenyl sulfone and 25 ml of toluene were charged, and the atmosphere was replaced with nitrogen. Next, stirring and heating were started under a nitrogen atmosphere, and azeotropic distillation of toluene was performed at 150 to 170 ° C. to remove water in the system. After about 1 hour, it was confirmed that the distillate had stopped.
30 minutes at 0 ° C., 30 minutes at 280 ° C., and 3 minutes at 320 ° C.
The reaction was performed for hours. After completion of the reaction, potassium chloride precipitated in the reaction solution was removed by filtration, and the filtrate was poured into a large amount of methanol to precipitate a polymer. The reduced viscosity of the obtained polymer was 0.45 dl / g (in dimethylformamide at 30 ° C., 1 g / dl).

The aromatic polysulfone copolymer was extruded with an extruder controlled at a barrel temperature of 380 ° C. and a die temperature of 400 ° C., and rapidly cooled with a rotating drum having a surface temperature set at 220 ° C. The film was fed to a winding device at a winding speed of 2 m / min to obtain a film having a thickness of 100 μm. Table 4 shows the results of the above evaluation of the obtained film.

(Examples 17 and 18, Comparative Examples 8 and 9)
Same as Example 16 except that the molar fraction of 4 '''-dihydroxy-p-quarterphenyl,4,4'-dichlorodiphenylsulfone and 4,4'-dihydroxydiphenylsulfone was changed as shown in Table 4 To prepare an aromatic polysulfone copolymer, and formed into a film. Table 4 shows the results of the above evaluation of the obtained film.

(Examples 19 to 21) 3,3 ', 5,5'-Tetramethyl 4,4'-dihydroxydiphenylsulfone was used in place of 4,4'-dihydroxydiphenylsulfone, and the moles shown in Table 4 were used. Example 16 except that the monomers were polymerized in fractions.
Prepare an aromatic polysulfone copolymer in the same manner as in
It was made into a film. Table 4 shows the results of the above evaluation of the obtained film.

Comparative Example 10 Victrex PES (4100G, manufactured by ICI) was added to an aromatic polysulfone copolymer.
A film was formed in the same manner as in Example 1 except for using. Table 4 shows the results of the above evaluation of the obtained film.

[0090]

[Table 4]

In Table 4, B to E indicate the following items.

B: Molar fraction of 4,4 '''-dihydroxy-p-quarterphenyl C: Molar fraction of 4,4'-dichlorodiphenylsulfone D: Molar fraction of 4,4'-dihydroxydiphenylsulfone E: molar fraction of 3,3 ′, 5,5′-tetramethyl 4,4′-dihydroxydiphenylsulfone (Examples 22 to 24, Comparative Example 11) Copolymerization of aromatic polysulfone by the method described in Example 16 A coalescence was prepared, and this was kneaded with a polyether ketone (Victrex PEEK, manufactured by ICI) at a weight fraction shown in Table 5 using a Brabender graph extruder to form pellets.

The obtained resin was extruded with an extruder controlled at a barrel temperature of 380 ° C. and a die temperature of 400 ° C.
It was quenched by a rotating drum whose surface temperature was set to 220 ° C.
The film was fed to a winding device at a winding speed of 2 m / min to obtain a film having a thickness of 100 μm. Table 5 shows the results of the above evaluation of the obtained film.

(Examples 25 to 27, Comparative Example 12) 4,4 '''-dihydroxy-p-quarterphenyl,4,4'-
An aromatic polysulfone copolymer was prepared in the same manner as in Examples 22 to 24 and Comparative Example 11 , except that the molar fractions of dichlorodiphenylsulfone and 4,4′-dihydroxydiphenylsulfone were changed as shown in Table 5. Into a film. Table 5 shows the results of the above evaluation of the obtained film.

[0095]

[Table 5]

In Table 5, B to D and * indicate the following.

B: molar fraction of 4,4 ′ ″-dihydroxy-p-quarterphenyl C: molar fraction of 4,4′-dichlorodiphenylsulfone D: molar fraction of 4,4′-dihydroxydiphenylsulfone *: Weight ratio of aromatic polysulfone copolymer / polyether ketone (Examples 28 to 30, Comparative Example 13)
19.25 kg of N, N-dimethylacetamide (hereinafter abbreviated as DMAC) was charged, 5.75 kg of polyetherimide was gradually added at room temperature, and the mixture was stirred for 10 hours to completely dissolve the polyetherimide resin. A thick polyetherimide solution was obtained. Next, a part of this polyetherimide solution was divided into flasks each equipped with a stirrer by 200 g. The mixture was stirred at room temperature for 5 hours and mixed.
At this time, DMAC was added so that the solution concentration became 5% by weight. The mixture was cast on a glass plate with a doctor knife and dried in a hot air drier at 120 ° C. for 10 minutes. This semi-dried film was fixed to a metal frame, and 12
The temperature was raised from 0 ° C to 180 ° C for 20 minutes.
Heat treatment was performed at 60 ° C. for 10 minutes to obtain a film having a thickness of 100 μm. Table 6 shows the results of the evaluation of the obtained film.

(Examples 31 to 33, Comparative Example 14) 4,4 '''-dihydroxy-p-quarterphenyl,4,4'-
Films were formed in the same manner as in Examples 28 to 30 and Comparative Example 13 except that the molar fractions of dichlorodiphenylsulfone and 4,4'-dihydroxydiphenylsulfone were changed as shown in Table 1. Table 6 shows the results of the evaluation of the obtained film.

[0099]

[Table 6]

In Table 6, B to D and * indicate the following.

B: molar fraction of 4,4 '''-dihydroxy-p-quarterphenyl C: molar fraction of 4,4'-dichlorodiphenylsulfone D: molar fraction of 4,4'-dihydroxydiphenylsulfone *: Weight ratio of aromatic polysulfone copolymer / polyetherimide (Comparative Example 15) Only the polyether ketone was mixed with the aromatic polysulfone copolymer in the same manner as in Examples 4 to 6 and Comparative Example 4. Filmed. Table 7 shows the results of the above evaluation of the obtained film.

(Comparative Example 16) In Examples 10 to 10 without adding an aromatic polysulfone copolymer to a polyetherimide solution.
A film was formed in the same manner as in Example 12 and Comparative Example 6. Table 7 shows the results of the above evaluation of the obtained film.
Shown in

[0103]

[Table 7]

[0104]

As is apparent from the above description, the first and second aromatic polysulfone films obtained according to the present invention have higher heat resistance and resistance to heat than conventional films made of aromatic polysulfone resin. It has excellent chemical properties and transparency. This film can be manufactured by a usual method, and is industrially advantageous.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 79:08)

Claims (2)

(57) [Claims] 1. A polymer obtained by polymerizing monomer units represented by the following general formulas (I), (II) and (III):
5 to 30 mol% of the monomer unit represented by
70 mol% is a monomer unit represented by the following general formulas (II) and (III), and has a concentration of 1 in dimethylformamide.
g / dl, reduced viscosity measured at a temperature of 30 ° C. is 0.35 d
1 / g to 0.6 dl / g aromatic polysulfone copolymer in a range of 51% by weight or more and less than 100% by weight
An aromatic polysulfone film comprising a resin containing polyetherimide or polyether ketone in a range of 49% by weight or more and more than 0% by weight . Embedded image (In the above general formula, n represents an integer of 3 or 4. R ¹ and R ² represent a hydrogen atom, a methyl group or a halogen atom, and may be the same or different. A and b are respectively An integer of 1 to 4, which may be the same or different from each other, and X and Y each represent a halogen atom). 2. A polymer obtained by polymerizing monomer units represented by the following general formulas (IV), (V) and (VI):
5) to 30 mol% of a monomer unit represented by V), the balance being 9
5-70 mol% is a monomer unit represented by the following general formulas (V) and (VI), and has a reduced viscosity of 0.35 in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C.
containing 50 to 100% by weight of an aromatic polysulfone copolymer of dl / g or more and 0.6 dl / g or less, and 49 to 0% by weight of polyetherimide or polyether ketone;
An aromatic polysulfone film, comprising a resin to be contained. Embedded image (In the above general formula, m represents an integer of 3 or 4. R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, a methyl group or a halogen atom, and may be the same or different. And c to f are each an integer of 1 to 4,
They may be the same or different. Z represents a halogen atom).