JPH10219110A - Resin composition, pipe-like article produced therefrom, and production of the article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. from which a pipe-like article excellent in heat resistance, mechanical properties, dimensional stability, flame retardance, abrasion resistance, water repellency, electrical properties, low water absorption, etc., can be produced by melt extrusion by compounding an esterimide and a fluororesin. SOLUTION: This compsn. is obtd. by mixing and melting a polymide having ester groups and a fluororesin. Pref. the polyimide having ester groups is one represented by formula I (wherein Ar1 and Ar2 are each a divalent org. group; Ar3 is a tetravalent org. group; n and p are each a positive integer of 1 or higher; m is 0 or a positive integer of 1 or higher). Pref. the fluororesin is at least one resin selected from among resins represented by formula II (wherein R is F, Cl, CF3 , or alkoxy). The content of the esterimide in the compsn. is pref. 5-99%. The compsn. is suitable for melt extrusion and can be molded into films, sheets, pipes, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition, a tubular article, and a method for producing the same, and more particularly, to a resin composition comprising a polyimide having an ester group and a fluororesin, a tubular article comprising the same, and a method for producing the same.

[0002]

2. Description of the Related Art In general, polyimide is widely used as a material particularly for electric and electronic equipment because it has excellent heat resistance, low temperature characteristics, chemical resistance, mechanical characteristics, electric characteristics and the like. In addition, the polyimide is used for various applications by utilizing its excellent properties. However, polyimides used for film applications generally have poor processability and have relatively high water absorption and friction coefficients.

[0003] On the other hand, fluororesins are widely used in lubricants and containers because of their excellent heat resistance, chemical resistance and low coefficient of friction. However, this fluororesin has the disadvantages of poor abrasion resistance and low elastic modulus, and has a problem that when it is used as a bearing for a bearing, the abrasion is severe and the durability is poor.

Further, when used for a fixing roller of a laser printer, it is necessary to increase the thickness of the film in order to maintain its shape, and there is a problem that thermal conductivity is poor. Further, the fluororesin has a melt viscosity of 10
There is a problem that the use is limited because extrusion molding is extremely high, about ¹¹ poises.

[0005]

In order to solve these problems, by adding a fluorine-based resin to a polyimide, or conversely, adding a polyimide to a fluorine-based resin, both of the advantages of the respective characteristics are obtained or the weak points are reinforced. Considerations have been made.

[0006] Of these, mechanical properties, friction and abrasion can be relatively easily improved, but workability and water absorption must be examined from the viewpoint of their molecular structure. No consideration was given.

[0007] Polyimides are thermoplastic and
Although classified into non-thermoplastics, those generally used are non-thermoplastic polyimides. This non-thermoplastic polyimide is generally formed by a casting method. However, the film formed by the casting method is poor in workability, and in order to form a tubular film by this, a process of manufacturing a tubular article by bonding the ends of the obtained film with an adhesive. And the cost was high due to low productivity due to limitations in the manufacturing process. In addition, the obtained tubular film has a problem that not only the joint remains but also causes inconvenience, and that when the bonding failure or the deterioration of the adhesive occurs, the joint is peeled off at the joint. In particular, when an adhesive is used, various properties such as heat resistance and chemical resistance of the tubular film are limited by the properties of the adhesive, and the properties of polyimide or fluorine-based resin cannot be sufficiently exhibited.

Therefore, the use of a thermoplastic polyimide which can be manufactured at a relatively low cost has been studied. However, the thermoplastic polyimide which has been conventionally used has a high melt viscosity, so that it can be used at a high temperature. It was necessary to use a suitable extruder.

[0009] In view of the above situation, the present inventors have
As a result of intensive studies, they have found that the above problems can be solved by using a polyimide having an ester group as the polyimide, and have completed the present invention.

[0010]

[Means for Solving the Problems]

The resin composition according to the present invention comprises at least
It consists of a polyimide having an ester group and a fluororesin.

Further, in the polyimide having an ester group, a compound represented by the general formula (1):

[0013]

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(Wherein, Ar ₁ and Ar ₂ are divalent organic groups,
Ar ₃ represents a tetravalent organic group. Further, n and p are positive integers of 1 or more, and m is 0 or a positive integer of 1 or more. ).

Further, in the polyimide having an ester group, Ar ₁ in the general formula (1) is

[0016]

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Is to be selected from the divalent organic groups represented by

In the polyimide having an ester group, Ar ₂ in the general formula (1) is

[0019]

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[0020]

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Is to be selected from the divalent organic groups represented by

Further, in the polyimide having an ester group, Ar ₃ in the general formula (1) is

[0023]

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[0024]

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Is to be selected from the tetravalent organic groups represented by

In the polyimide having an ester group, the fluorine-based resin may be represented by the following general formula (2):

[0027]

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(Wherein R is selected from F, Cl, CF ₃ and alkoxy groups).

Further, when the fluororesin is polytetrafluoroethylene, its melting point is 325 ° C. or more.

The gist of the method for molding a resin composition according to the present invention is to mix at least a polyimide having an ester group and a fluororesin, and to heat and melt the resin at a temperature not lower than the melting point of the resin. Extrusion molding.

The gist of the method for producing a tubular article according to the present invention is that at least a polyimide having an ester group and a fluororesin are mixed, heated to a temperature higher than the melting point of the resin, melted, and extruded. It is to form a film into a tube by molding.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an embodiment of a resin composition according to the present invention, a tubular article made of the same, and a method for producing the same will be described.

First, the resin composition according to the present invention is composed of a polyimide having at least an ester group (hereinafter referred to as ester imide) and a fluororesin. First, the ester imide used in the resin composition is used. An example of a manufacturing method will be described.

The ester imide having a specific structure, which is a component of the resin composition according to the present invention, is represented by the following general formula (3): H ₂ N—Ar ₂ —NH ₂ (3) (where Ar ₂ is Chemical formula 16

[0035]

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[0036]

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A divalent organic group selected from the group consisting of: And a diamine represented by the general formula (4)

[0038]

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(Wherein, Ar ₁ is

[0040]

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It represents a divalent organic group selected from more. And / or diester acid dianhydride represented by the general formula (5):

[0042]

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(Wherein, Ar ₃ is

[0044]

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[0045]

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A tetravalent organic group selected from the group consisting of: A polyamic acid solution is obtained from the tetracarboxylic dianhydride represented by the formula) by a known method.

The mixing ratio of the diester dianhydride and the tetracarboxylic dianhydride is preferably 20 to 100% of the total acid component of the diester dianhydride. Also,
The total amount of the acid components represented by the general formulas (4) and (5) and the total amount of the diamine components represented by the general formula (3) are preferably used in equimolar amounts.

The organic solvent used for the polyamic acid formation reaction includes sulfoxide solvents such as diethylsulfoxide, formamide solvents such as N, N-dimethylformamide, and acetamide solvents such as N, N-dimethylacetamide. And pyrrolidone solvents such as N-methyl-2-pyrrolidone, and phenol solvents such as phenol. These can be used with only one kind of solvent or a mixed solvent of two or more kinds. Further, a mixed solvent composed of these polar solvents and a non-solvent of polyamic acid can also be used.

Thereafter, thermal or chemical imidization is performed to obtain an ester imide. In the thermal imidization, a dehydrating agent having a stoichiometry or more is added, and the solution is left at the temperature of the solution with stirring. In the chemical imidization, a stoichiometric or more dehydrating agent and a catalytic amount of a tertiary amine are added to a solution of the polyamic acid polymer, and the mixture is stirred at room temperature for several hours. After dropping and appearing in a string or lump, drying and pulverization yields a desired polyimide powder.

Alternatively, if an appropriate amount of a poor solvent is added together with a dehydrating agent and a tertiary amine, and the mixture is left to stir, powders are precipitated as the imidization proceeds. After the slurry obtained by these methods is collected under reduced pressure and dried, an esterimide powder is obtained. These can be sufficiently dried with hot air or the like to obtain the ester imide used for the tubular article according to the present invention.

Further, in order to obtain a polyisoimide copolymer, it is necessary to use the above-mentioned reactants in the formation of the ester imide,
That is, the diamine and the tetracarboxylic dianhydride may be replaced with a diimide such as dichlorocarbodiimide (DCC) and a carboxylic acid such as trifluoroacetic acid, and the same reaction as that of the ester imide may be performed.

The ester imide as a main component of the resin composition according to the present invention obtained as described above has a clear glass transition point between 150 ° C. and 350 ° C. depending on its composition, By processing at a temperature close to the point, a tubular article can be easily produced. Further, it shows an excellent low water absorption, and the water absorption is 1% or less under conditions of immersion in pure water at 20 ° C. for 24 hours. Furthermore, it shows excellent dielectric properties, and has a dielectric constant of 1 or less at 1 MHz in the Q-meter method. In addition, Q meter method is JISC6
481 means a method of measuring a dielectric constant by measuring according to 481.

Next, the fluororesin which is a component of the resin composition according to the present invention will be described. The fluororesin is not particularly limited, but is represented by the general formula (2):

[0054]

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(In the formula, R represents F, Cl, CF _{3 or} an alkoxy group.) It is preferable that the resin is at least one kind of a resin represented by the formula: In particular,

[0056]

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When polytetrafluoroethylene represented by the formula (1) is used, the melting point is preferably 325 ° C. or more. The melting point of polytetrafluoroethylene is determined by its molecular weight.
If it is less than 5000, the thermal decomposition temperature is low and the heat resistance is poor.

The fluorine-based resin, which is the main component of the resin composition, has non-adhesion and water repellency due to its structure having a fluorine atom. In addition, it has a low coefficient of friction, chemical resistance and heat resistance.

The esterimide and the fluororesin thus obtained may be used alone for producing the resin composition according to the present invention and the tubular article comprising the same.
There is no problem even if an inorganic filler is mixed to improve heat conduction. In addition, there is no problem even if an inorganic filler is mixed for imparting conductivity. On this occasion,
Examples of the so-called inorganic filler include conductive carbon, talc, whisker titanate, boron nitride, mica, and the like, but are not limited thereto. If the performance of the esterimide and the fluororesin is not significantly reduced, stabilizers, lubricants, surfactants, pigments, compatibilizers, resins other than the esterimide and the fluororesin, and the like may be added. Is not particularly limited.

The mixing ratio between the ester imide and the fluororesin is not particularly limited. However, if the addition amount of the ester imide is less than 5%, the melt viscosity becomes high and extrusion molding becomes difficult. Further, even when the addition amount of the fluororesin is as small as about 5%, the characteristics are exhibited, but when the addition amount is extremely small as 1% or less, the friction coefficient of the surface becomes high and the effect is not exhibited. . Therefore, the proportion of the ester imide is preferably 5% to 99%, more preferably 10% to 99%.
95% is good.

The above-mentioned ester imide and the fluorine resin are mixed and melted to obtain the resin composition according to the present invention. Here, the shape of the ester imide and the fluorine-based resin at the time of mixing the resin composition is not limited to a powder, a solid, or a slurry, but it is preferable to mix in a powder form. The mixing order is not particularly limited.

The condition for the melting and heating must be a temperature not lower than the melting points of the ester imide and the fluororesin obtained by the above-mentioned production method. Specifically, the temperature is usually preferably 50 to 100 ° C. higher than the melting point. Further, the melt viscosity is preferably from 10 ³ to 10 ⁵ poise.

The resin composition according to the present invention is suitable for processing a molded article by a melt extrusion method. This melt extrusion method is a method of continuously molding an endless long product, and has a very high molding ability and is a very economical molding method. More specifically, a mixture of the ester imide and the fluororesin obtained by the above-described production method is put into a hopper, and heated to a temperature equal to or higher than the melting point of the ester imide and the fluororesin in a heating cylinder (barrel) to melt the mixture. It is extruded with a screw while giving a shape with a die (die) at the tip, and this is cooled and solidified with water or air to form a tubular article. In addition, molded products having various cross-sectional shapes such as a film, a sheet, a pipe, and a profile extrusion can be produced depending on the shape of the die.

Here, as a melt extruder used for producing the resin composition according to the present invention, a general melt extruder which can be easily analogized by those skilled in the art can be used.

The resin composition according to the present invention has a relatively low glass transition point of 150 ° C. to 350 ° C. of the ester imide represented by the general formula (1) as a constituent, and has a melt viscosity after melting. , It can be easily extruded by a melt extrusion method. Therefore, it is possible to obtain a molded product that is inexpensive and has excellent dimensional accuracy and film thickness accuracy, and thus it is suitable as a raw material for a resin molded product by an extrusion molding method.

Next, a tubular article made of the resin composition according to the present invention will be described together with a method for producing the tubular article. The tubular article according to the present invention, which is in the shape of the resin composition formed by extrusion, can be formed into a tube according to the shape of the die.

More specifically, for example, as shown in FIG. 1, in an extrusion molding step 10, a mixture of an ester imide and a fluorine-based resin is put into a hopper 12, and a mixture of the ester imide and the fluorine resin is heated in a heating cylinder (barrel) 14. It is heated and melted to a temperature higher than the melting point of the system resin. Next, while giving shape by a ring-shaped die (die) 16 at the tip, it is extruded into a tube shape with a screw 18 and formed into a predetermined thickness and size, and this is cooled and solidified with water or air to form a book. The tubular article 20 made of the resin composition according to the present invention is molded.

The shape of the ester imide and the fluorine-based resin at the time of mixing may be basically in the form of a powder, a solid, or a slurry, but is preferably in the form of a powder. In other words, when used in a sufficiently dried state, the decomposition of the resin and the deterioration of the thermoplastic fluidity are prevented, and the phenomenon that bubbles and the like are generated in the film can be prevented, and a tubular article excellent in dimensional accuracy and film thickness accuracy can be obtained. You can.

The tubular article according to the present invention obtained as described above can be manufactured at a lower cost as compared with the conventional method in which a thin film is formed by a casting method and further joined in a tubular shape. It has no joints and has the properties of esterimide and fluororesin. Specifically, it combines excellent heat resistance, workability, chemical resistance, low friction coefficient, low water absorption, and dielectric properties. Have. In addition, by sufficiently drying and using the powder of the resin composition having a low melt viscosity,
A tubular article excellent in dimensional accuracy and film thickness accuracy can be obtained.

The resin composition according to the present invention obtained as described above and a tubular article comprising the same have excellent properties such as heat resistance, radiation resistance, abrasion resistance, low water absorption, and low coefficient of friction.
In particular, it has excellent characteristics of dimensional accuracy and film thickness accuracy.
It is suitable for various uses such as a wire insulation film and precision electric and electronic members.

In the above, an example of the embodiment has been described in order to clarify the usefulness of the resin composition according to the present invention, the tubular article made of the same, and the method for producing the same. However, the present invention is not limited to this embodiment. Instead, the present invention can be implemented in various modified, changed, and modified aspects based on the knowledge of those skilled in the art without departing from the spirit thereof.

[0072]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the scope of these examples.

First, the method for producing the ester imide used in the examples of the present invention will be specifically described, but the present invention is not limited to these examples. (Example 1) 15.6 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter, referred to as BAPP) and dimethylformamide (hereinafter, referred to as DMF) 25 are placed in a 50-ml volumetric flask (1). 0.4 g was taken, stirred using a stirrer, and dissolved sufficiently. Further, 1.0 g of BAPP and DM were added to another 50 ml volumetric flask (2).
10.0 g of F was taken and sufficiently dissolved. On the other hand, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter referred to as ESDA) 1 is placed in a 500 ml three-necked flask equipped with a stirrer.
1.9 g, 6.4 g of 3,3 ', 4,4'-benzophenyltetracarboxylic dianhydride (hereinafter referred to as BTDA), and D
25.0 g of MF was added, and the mixture was stirred and dissolved sufficiently while cooling with ice water and replacing the atmosphere in the flask with nitrogen.
Then, while stirring the BAPP solution in the 50 ml three-necked flask (1) obtained in advance, the 500 ml
It was quickly charged into a three-necked flask. After standing for about 30 minutes while stirring, the BA in a 50 ml volumetric flask (2) was
The PP solution was gradually introduced into the three-necked flask while paying attention to the viscosity of the solution in the three-necked flask. Viscosity 1500
When poise was reached, 85.2 g of DMF was further added, and stirring was continued until the mixture became uniform. Further, the BAPP solution in the 50 ml volumetric flask (2) was gradually charged into the three-necked flask while paying attention to the viscosity of the solution in the three-necked flask. After reaching the maximum viscosity, the introduction of the BAPP solution was terminated, and the mixture was allowed to stand with stirring for 1 hour to obtain a polyamic acid polymer solution.

DMF 187.2 was added to this polyamic acid solution.
g, β-picoline 5.0 g, and acetic anhydride 8.0 g,
The mixture was stirred for 2 hours under ice cooling. Thereafter, this solution was gradually dropped into methanol stirred at a high speed. The filamentous polyimide precipitated in methanol was dried at 150 ° C. for 30 minutes, pulverized by a mixer, and heated at 250 ° C. for 2 minutes to completely perform imidization to obtain a polyimide powder.

A resin powder in which the ester imide and polytetrafluoroethylene were mixed at a ratio of 90% of the ester imide was extruded at 340 ° C. in a cylinder to obtain a tube having a diameter of 20 mm. In this tube, A
Based on STM D-570 standard, 2
The water absorption after soaking for 4 hours was 0.3%. Also,
It was 0.2 when the coefficient of static friction was measured based on ASTM D-1894 standard.

[0076] (Comparative Example 1) and the monomer trimellitic acid dianhydride used 4,4 ^'- the exception that the diaminodiphenyl ether is a polyimide powder was prepared in the same manner as in Example 1, polytetrafluorocarbon powder 50 Extrusion molding was attempted for powders mixed by%, but the melt viscosity was too high to extrude.

(Comparative Example 2) An ester imide prepared in the same manner as in Example 1 was extruded alone to prepare a tube. The water absorption of the tube was 0.4%, and the coefficient of static friction was 0.55.

(Comparative Example 3) Polytetrafluoroethylene was extruded at a cylinder temperature of 340 ° C.
Extrusion was not possible due to high melt viscosity.

[0079]

As described above, as shown in the specific embodiments,
Since the tubular article according to the present invention is formed by extruding a tube-like film by a melt extrusion method using a resin mainly composed of an ester imide and a fluororesin, a tubular article without a joint is obtained. A tubular article having both excellent properties of ester imide and fluorine resin can be obtained.

Specifically, the resin composition according to the present invention and the tubular article made of the same are particularly resistant to heat resistance and heat resistance because the esterimide represented by the general formula (1) and the fluororesin have excellent properties. Excellent radiation properties, mechanical properties, dimensional stability, film forming accuracy, flame retardancy, abrasion resistance, low expansion coefficient, water repellency, offset properties, electrical properties, etc. When the film is formed, the film becomes more excellent in dimensional accuracy and film thickness accuracy.

The obtained tubular article has no joint,
It is possible to obtain a tubular material that can sufficiently exhibit the properties of the ester imide and the fluororesin that are the raw materials. Further, the ester imide represented by the general formula (1) can be easily extruded by a melt extrusion method, and a tubular article which is inexpensive and has excellent dimensional accuracy and film thickness accuracy can be obtained. Further, in the method for producing a tubular article according to the present invention, when the esterimide and the fluororesin are sufficiently dried and used, the decomposition of the resin and the deterioration of the thermoplastic fluidity cause the film to be foamed or the like. And a tubular article having excellent dimensional accuracy and film thickness accuracy can be obtained.

Accordingly, the resin composition according to the present invention and a tubular article made of the same include, for example, FPC (flexible printed circuit board), insulating films for electric wires, seat belts, food trays, medical parts such as catheters, optical parts and materials, Further, it is suitable for precision electric / electronic members utilizing heat resistance, for example, various belts and fixing rollers of copying machines and printers. Further, since the dimensional accuracy is good, it can be used for a drive belt of precision equipment and the like. Furthermore, various uses can be expected in all other fields.

[Brief description of the drawings]

FIG. 1 is an example of an extrusion forming step for forming a tubular article according to the present invention.

[Explanation of symbols]

 10; an extruder 12 for molding the resin composition according to the present invention 12; a hopper 14; a cylinder (barrel) 16; a die 18; a screw 20;

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29K 79:00 B29L 23:00

Claims (10)

[Claims] 1. A resin composition comprising at least a polyimide having an ester group and a fluorinated resin. 2. The polyimide having an ester group,
General formula (1) (In the formula, Ar ₁ and Ar _{2 each} represent a divalent organic group, Ar ₃ represents a tetravalent organic group. Further, n and p are positive integers of 1 or more, m
Represents 0 or a positive integer of 1 or more. The resin composition according to claim 1, wherein 3. The polyimide having an ester group,
Ar ₁ in the general formula (1) is The resin composition according to claim 1, wherein the resin composition is selected from divalent organic groups represented by the following formulae. 4. The polyimide having an ester group,
Ar ₂ in the general formula (1) is represented by the following chemical formulas (3) and (4): Embedded image The resin composition according to any one of claims 1 to 3, wherein the resin composition is selected from divalent organic groups represented by the following formulae. 5. The polyimide having an ester group,
Ar ₃ in the general formula (1) is a compound represented by the formulas (5) and (6). Embedded image The resin composition according to any one of claims 1 to 4, wherein the resin composition is selected from tetravalent organic groups represented by the following formulae. 6. The fluororesin represented by the general formula (2): The resin composition according to claim 1, wherein R is selected from F, Cl, CF ₃ , and an alkoxy group. 7. The resin composition according to claim 1, wherein when the fluorine-based resin is polytetrafluoroethylene, its melting point is 325 ° C. or more. 8. The resin composition according to claim 1, wherein the resin composition comprises at least a polyimide having an ester group and a fluorine-based resin. Tubular material. 9. The method according to claim 1, wherein at least polyimide containing an ester group and a fluororesin are mixed, heated to a temperature higher than the melting point of the resin, melted, and extruded. Or a method for molding a resin composition according to the above. 10. The resin composition according to claim 1, wherein at least a polyimide having an ester group and a fluorine-based resin are mixed and heated to a temperature equal to or higher than the melting point of the resin to be melted. And forming a film into a tube by extrusion molding.