JPH05295262A - Aromatic polysulfone film - Google Patents

Abstract

PURPOSE:To obtain the subject film useful for a flexible printed laminate, etc., having specific reduced viscosity, excellent heat resistance, chemical resistance and transparency, comprising a specific aromatic polyether sulfone having diphenyl structure, etc., and a polyether ketone. CONSTITUTION:A resin containing 51-100wt.% aromatic polysulfone having a diphenyl structure composed of a repeating unit of formula I or aromatic polysulfone containing 50-99mol% repeating unit of formula I and 50-1mol% at least one of repeating units of formula II, formula III, etc., having 0.35-0.6dl/g reduced viscosity in dimethylformamide at 1g/dl concentration at 30 deg.C and 49-0wt.% polyether imide or polyether ketone, is melted and extruded from an extruder at 400 deg.C die temperature, quenched by a rotary drum having 220 deg.C surface temperature, made into a film and wound to give the objective polysulfone film.

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 which is mainly composed of a resin containing an aromatic polysulfone having excellent heat resistance and chemical resistance and excellent transparency.

[0002]

2. Description of the Related Art Aromatic polysulfone resins are known as resins having excellent heat resistance, mechanical properties, and electrical properties and a very well-balanced physical property.
Widely used in fields such as the aircraft industry and the electrical 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 distortion temperatures of 203 ° C. and 174 ° C., respectively, and are excellent in heat resistance, and are also excellent in mechanical properties such as bending properties and tensile properties. However, in the electric / electronic materials and aircraft related industries in recent years, more advanced properties are required, and the applications where the properties of both resins are not sufficient are increasing. For example, a film for a flexible printed laminate 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, the chemical resistance of the aromatic polysulfone resin also has a drawback that the application of the film using the resin is limited because it has no resistance to a general-purpose solvent.

In order to meet this demand, a method for producing a multilayer film by extruding an aromatic polysulfone resin together with a polyetherketone and a polyphenylene sulfide resin is disclosed in JP-A-62-238737 and JP-A-62-237737. According to this method, although the heat resistance and chemical resistance of the obtained film are improved, there are drawbacks such as peeling phenomenon of the adhesive interface and deterioration of transparency. Yes, F
The heat resistance required for PC film etc. is not sufficient,
Not practically satisfactory.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made by paying attention to the above circumstances, and is superior in heat resistance and chemical resistance to a conventional aromatic polysulfone resin film and is transparent. An object is to obtain an aromatic polysulfone film having

[0005]

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

The aromatic polysulfone film of the present invention is
Aromatic polysulfone comprising a repeating unit represented by the following general formula (I), or 50 to 99 mol% of the repeating unit represented by the following general formula (I), and represented by the following general formulas (II) to (XVI) An aromatic polysulfone containing 50 to 1 mol% of any one of repeating units, having a reduced viscosity of 0.35 dl / in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C.
It is characterized by comprising a resin containing 51 to 100% by weight of aromatic polysulfone having a content of g or more and 0.6 dl / g or less and containing 49 to 0% by weight of polyetherketone or polyetherimide.

[0007]

[Chemical 3]

[0008]

[Chemical 4]

A preferred method for producing the aromatic polysulfone used in the present invention is a nucleophilic substitution polycondensation method in which a monomer having a hydroxyl group and a halogen group at the terminals is polymerized in the presence of an alkali metal salt in a polar solvent. Is used, and examples thereof include a method of polymerizing in an aprotic polar solvent in the presence of an alkali metal carbonate.

The alkali metal carbonate reacts with a monomer having a hydroxyl group among the monomers for forming the repeating units represented by the general formula (I) or (I) and (II) to (XVI). It is possible to form an alkali metal salt by way of example, and specific examples thereof include sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate, but sodium carbonate or potassium carbonate is particularly preferable. The amount of the alkali metal carbonate used is preferably an excessive molar amount with respect to the total molar amount of the monomers having a hydroxyl group in order to obtain a polymer and to increase the polymerization reaction rate. When the amount of the alkali metal carbonate used is small, a large amount of free hydroxyl groups are present and only a low molecular weight product is obtained, which is not preferable.

As the polar solvent, sulfone-based solvents such as sulfolane, diphenyl sulfone and dimethyl sulfoxide, or amide-based solvents such as dimethylacetamide and dimethylimidazoline are preferably used.

The polymerization temperature is usually in the range of 80 to 400 ° C, preferably 100 to 350 ° C.
When the reaction rate is lower than the above temperature range, the intended polymerization reaction does not proceed at a practically practical rate, and it is difficult to obtain a polymer having a required molecular weight. On the other hand, when the reaction rate is higher than the above range, side reactions other than the intended polymerization reaction cannot be ignored, and the resulting polymer is significantly colored. The time required for the polymerization reaction varies depending on the type of raw material components of the reaction, the type of polymerization reaction, etc.
The time is from minutes to 100 hours, and preferably from 1 hour to 24 hours.

Further, in the polymerization, the monomers are mixed such that all the halogen groups are 90% of the total hydroxyl groups of the monomers.
It is preferably used within the range of 110 mol%. 95 to 1 to obtain higher molecular weight aromatic polysulfone
It is preferably used within the range of 05 mol%.

The aromatic polysulfone film used in the present invention contains the above-mentioned aromatic polysulfone alone or in a resin having a majority, ie, 51 to 100% by weight, and contains 49 to 100% of polyetherimide or polyetherketone.
It is formed from a resin containing 0% by weight. In this case, the aromatic polysulfone is more preferably 60 to 100% by weight, and the polyetherimide or polyether ketone is 40 to 0%.
It is formed from a resin that is weight percent. When the amount of aromatic polysulfone is less than 51% by weight, heat resistance is lowered and, for example, physical properties required as a film for electronic materials are not satisfied, which is not preferable.

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

[0016]

[Chemical 5]

(In the above general formula, a is an integer of 1 or more, preferably 10 to 10,000, and the group -OR
¹ <is

[0018]

[Chemical 6]

Is selected from Here, R ⁴ is hydrogen, a lower alkyl group or a lower alkoxy group, preferably polyetherimide is represented by the following formula (XVII ′)

[0020]

[Chemical 7]

And a third —O—R ¹ <where R ⁴ is hydrogen. The divalent bond of —O—R ² —O— is the same as the two phenyl groups in the above formula (XVII ′),
3,3 ';3,4'; 4,3 'or 4,4', and R ² is a divalent organic group, group (1)

[0022]

[Chemical 8]

And group (2)

[0024]

[Chemical 9]

Is selected from In group (2), R ⁵
Is the following group

[0026]

[Chemical 10]

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

[0028]

[Chemical 11]

And R ⁶ is

[0030]

[Chemical 12]

2 selected from and d is an integer from 1 to 5
A valent organic group;).

For the purposes of the present invention, particularly preferred polyetherimides are --O--R ¹ <and R ² respectively.

[0033]

[Chemical 13]

And R ³ is

[0035]

[Chemical 14]

Is a polyetherimide selected from Most preferred are polyetherimides where R ³ is metaphenylene.

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

[0038]

[Chemical 15]

The repeating unit represented by, and other repeating units shown below

[0040]

[Chemical 16]

Examples of the structure include
A polyetherketone containing solely the repeating unit of the above formula (XVIII) is preferably used.

In order to produce the aromatic polysulfone film of the present invention, a resin solution dissolved in an organic solvent, which is heated and melted by an ordinary extruder, is cast into a film by casting the resin solution. A method of volatilizing the organic solvent may be used. However, in the production of a film composed of aromatic polysulfone and polyether ketone, a film cannot be formed by a casting method because there is no solvent that dissolves the polyether ketone.

In forming a resin containing an aromatic polysulfone into a film by an extrusion method, the barrel temperature of the extruder is usually set to 280 to 420 ° C., preferably 300 to 400 ° C., and the die temperature is usually 300 to 400 ° C. The temperature is set to 450 ° C, preferably 320 ° C to 400 ° C. At a high temperature of 400 ° C. or higher, decomposition of the aromatic polysulfone occurs, so it is preferable to form the film at 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 the moving surface of a rotating drum or the like, and sent to a winding device to obtain a film. The winding speed of the winding device depends on the capacity of the manufacturing device, but in order to obtain a film having excellent thickness accuracy and good surface property,
The speed is preferably 50 m / min or less, more preferably 20 m / min or less.

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

In the aromatic polysulfone-polyetheramide mixed system, the extruder barrel temperature is usually 260.
~ 420 ° C, preferably 280-400 ° C,
The die temperature is usually 300 to 420 ° C., preferably 320.
Set to ~ 400 ° C. After that, it is supplied to the moving surface such as a rotating drum set in the range of 100 to 220 ° C.,
It is rapidly cooled to form a film.

In the aromatic polysulfone-polyether ketone mixed system, the barrel temperature of the extruder is usually 330.
~ 420 ° C, preferably set to 350-400 ° C,
The die temperature is usually 340 to 420 ° C., preferably 350
Set to ~ 400 ° C. After that, it is supplied to a moving surface such as a rotating drum set in the range of 100 to 260 ° C,
It is rapidly cooled to form a film.

In forming a film of a resin containing an aromatic polysulfone by a casting method, a halogen-based solvent such as chloroform, methylene chloride and dichloroethane, an amide-based solvent such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone are used as an organic solvent. A solvent is preferably used, but dimethylformamide is particularly preferable. In this case, the concentration of the resin dissolved in the organic solvent depends on the thickness of the target film, but is 3% in the resin solution.
It is preferably 0% by weight or less. Considering the solubility of the resin and the workability of the solvent, it 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. It is preferable to increase the drying temperature stepwise. Strictly speaking, the most efficient film formation is possible by increasing the drying temperature at a temperature not exceeding the glass transition temperature of the resin containing the residual organic solvent. Further, a step is required in which the film is drawn from a coater, hot air is blown to both sides of the film to dry the film, and the residual solvent is reduced to 1% by weight or less. As described above, the temperature is preferably 260 to 280 ° C. If the residual solvent remains at 1% by weight or more, the physical properties are deteriorated, which is not preferable.

Even in a mixed system of aromatic polysulfone-polyetherimide, a film can be formed by a method similar to the above casting method, and as the organic solvent, a halogen-based solvent such as trichloroethane, trichloromethane or tetrachloromethane is used. Amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrohydrin are preferably used, and dimethylacetamide is particularly preferable.

The obtained film can be stretched if necessary. In the extrusion method, a film stretched to an arbitrary ratio 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 stretch ratio depends on the purpose and application, a stretch ratio of 5 times or less is preferable in consideration of workability and accuracy in thickness.

The thickness of the aromatic polysulfone film in the present invention can be arbitrarily selected depending on the purpose and application.
The limit of thickness that can be controlled and processed depends on the film manufacturing method. In the film formation by the extrusion method, the width of the opening of the T-die, the extrusion speed and the winding speed are controlled,
Although a film having an arbitrary thickness can be obtained, in order to stably supply a good film in which accuracy and surface property in thickness are sufficiently controlled and there is no defect, 1 to
The film thickness is preferably 500 μm, more preferably 5 to 200 μm. In the film formation in the casting method, if the thickness is too thin, the film is easily broken when peeled off from the coater, and if it is too thick, the residual solvent is likely to remain, so that the film thickness is 1 to 200 μm. Is preferable, and 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 also be surface-coated and surface-treated if necessary.

[0052]

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

[Evaluation of Film] 1. Using a differential scanning calorimeter, the glass transition temperatures of the films obtained in Examples and Comparative Examples were measured (under a nitrogen stream,
Temperature rise 20 ° C / min). Further, a soldering iron at 260 ° C. was contacted for 30 minutes to examine the change in film shape.

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

(Example 1) 4-chloro-4 '-(p-hydroxyphenyl) diphenyl sulfone was placed in a polymerization reaction vessel equipped with a stirrer, a gas inlet tube, a thermometer and a condenser having a receiver at the tip. 100 parts by weight, anhydrous potassium carbonate 22.1 parts by weight, and sulfolane 290 parts by weight were charged, and nitrogen substitution was carried out. Then, stirring and temperature increase were started in a nitrogen atmosphere, and the reaction was carried out at 220 ° C. for 1 hour, 230 ° C. for 30 minutes, and 240 ° C. for 3 hours while maintaining the temperature in the reaction system.
After the reaction was completed, the reaction solution was cooled to room temperature, 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 0.4 dl / g (30 ° C., 1 g / dl in dimethylformamide).

Barrel temperature of 380 ° C. and die temperature of 40
The aromatic polysulfone was extruded into an extruder controlled at 0 ° C. and rapidly cooled by a rotary drum whose surface temperature was set at 220 ° C. The film was fed into a winding device at a winding speed of 2 m / min to obtain a film having a thickness of 100 μm.
The results of the above evaluation of the obtained film are shown in Table 1.

(Example 2) 4-chloro-4 '-(p-hydroxyphenyl) diphenyl sulfone was placed in a polymerization reaction vessel equipped with a stirrer, a gas inlet tube, a thermometer and a condenser having a receiver at the tip. 100 parts by weight, 4-chloro-4'-hydroxydiphenyl sulfone 77.9 parts by weight, anhydrous potassium carbonate 4
4.1 parts by weight and 290 parts by weight of sulfolane were charged, and the atmosphere was replaced with nitrogen. Then, under nitrogen atmosphere, stirring and heating are started, and 220 ° C. for 1 hour, 230 ° C. for 30 minutes, 240 ° C.
The reaction was carried out for 3 hours while maintaining the temperature in the reaction system. After the reaction was completed, the reaction solution was cooled to room temperature, 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 0.42 dl / g (30 ° C., 1 g / dl in dimethylformamide).

The resin thus obtained was formed into a film in the same manner as in Example 1. The results of the above evaluation of the obtained film are shown in Table 1.

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

[0060]

[Table 1]

In Table 1, A and B indicate the following matters.

A: Repeating unit

[0063]

[Chemical 17]

Molar fraction of B: Repeating unit

[0065]

[Chemical 18]

Molar Fraction (Examples 3 to 5, Comparative Example 2) N, N
-Dimethylacetamide (hereinafter abbreviated as DMAC)
After charging 19.25 kg, 5.75 kg of polyetherimide was gradually added at room temperature and stirred for 10 hours to completely dissolve the polyetherimide to obtain a polyetherimide solution. Next, a portion of this polyetherimide solution
The mixture was divided into flasks each equipped with a stirrer (00 g) and the aromatic polysulfone prepared by the method described in Example 1 was added to the polyetherimide in the proportions shown in Table 2, and the mixture was stirred at room temperature for 5
Stir and mix for hours. At this time, DMAC was added so that the solution concentration became 5% by weight.

This mixed solution was cast on a glass plate with a doctor knife and dried at 120 ° C. for 10 minutes in a hot air dryer. Fix this semi-dry film on a metal frame and
The temperature was raised from 20 ° C. to 180 ° C. in 20 minutes, and finally heat-treated at 260 ° C. for 10 minutes to obtain a film having a thickness of 100 μm. Table 2 shows the results of the above evaluations of the obtained film.

(Examples 6 to 8 and Comparative Example 3) Films were produced in the same manner as in Examples 3 to 5 and Comparative Example 2 except that the aromatic polysulfone prepared by the method described in Example 2 was used. did. Table 2 shows the results of the above evaluations of the obtained film.

(Comparative Example 4) A film was produced in the same manner as in Examples 3 to 5 and Comparative Example 2 except that Victrex PES (manufactured by ICI, 4100G) was used as the aromatic polysulfone. Table 2 shows the results of the above evaluations of the obtained film.

[0070]

[Table 2]

In Table 2, A, B and * indicate the following matters.

A: Repeating unit

[0073]

[Chemical 19]

Molar fraction of B: Repeating unit

[0075]

[Chemical 20]

Molar Fraction of *: Aromatic Polysulfone / Polyetherimide Weight Ratio (Examples 9 to 11, Comparative Example 5) Aromatic polysulfone and polyether ketone (ICI prepared by the method described in Example 1) Victrex PEEK (manufactured by the company) was kneaded at a ratio shown in Table 3 with a Brabender Plastograph extruder and pelletized. The composition obtained was adjusted to a barrel temperature of 3
The mixture was extruded into an extruder controlled at 80 ° C. and a die temperature of 400 ° C., and rapidly cooled by a rotary drum whose surface temperature was set at 220 ° C. The film was fed into a winding device at a winding speed of 2 m / min to obtain a film having a thickness of 100 μm. The results of the above evaluation of the obtained film are shown in Table 3.
Shown in.

(Examples 12 to 14, Comparative Example 6) Example 2
Films were produced in the same manner as in Examples 9 to 11 and Comparative Example 5, except that the aromatic polysulfone prepared by the method described in 1. was used. Table 3 shows the results of the above evaluations of the obtained film.

(Comparative Example 7) A film was produced in the same manner as in Examples 9 to 11 and Comparative Example 5, except that Victrex PES (manufactured by ICI, 4100G) was used as the aromatic polysulfone. Table 3 shows the results of the above evaluations of the obtained film.

[0079]

[Table 3]

In Table 3, A, B and * indicate the following matters.

A: Repeating unit

[0082]

[Chemical 21]

Molar fraction of B: Repeating unit

[0084]

[Chemical formula 22]

Molar Fraction of *: Aromatic Polysulfone / Polyetherimide Weight Ratio (Comparative Example 8) Examples 3 to 5 and Comparative Examples except that aromatic polysulfone was not used and only polyetherimide was used. A film was produced in the same manner as in 2. Table 4 shows the results of the above evaluations of the obtained film.

Comparative Example 9 Example 9 was repeated except that the aromatic polysulfone was not used and only the polyether ketone was used.
A film was produced in the same manner as in -11 and Comparative Example 5. The results of the above evaluation of the obtained film are shown in Table 4.
Shown in.

[0087]

[Table 4]

[0088]

As is clear from the above description, the aromatic polysulfone film obtained according to the present invention is superior in heat resistance and chemical resistance and transparent as compared with the conventional aromatic polysulfone film. It has sex. This film is industrially advantageous because it can be manufactured by a usual method.

Claims (1)

[Claims] 1. An aromatic polysulfone comprising a repeating unit represented by the following general formula (I), or 50 to 99 mol% of a repeating unit represented by the following general formula (I), and the following general formulas (II) to ( XVI) is an aromatic polysulfone containing any one of the repeating units represented by XVI) in an amount of 50 to 1 mol% and has a reduced viscosity measured in dimethylformamide at a concentration of 1 g / dl and a temperature of 30 ° C.
51 to 100% by weight of aromatic polysulfone of 0.35 dl / g or more and 0.6 dl / g or less, and 49 to 0% by weight of polyetherimide or polyetherketone
An aromatic polysulfone film comprising a resin contained therein. [Chemical 1] [Chemical 2]