JPS6065028A - Aromatic polyester-amide film - Google Patents

Abstract

PURPOSE:A film excellent in heat resistance, high-temperature electrical properties, etc., obtained from an aromatic polyester-amide prepared by polycondensing an aromatic dicarboxylic acid with an aromatic hydroxyamino compound and an aromatic diamino compound. CONSTITUTION:An aromatic dicarboxylic acid (dianhydride) (A) of formula I (wherein R1-R4 are each H or the like, Z1 is O or the like, n1 is 0 or 1, R15 and R16 are each a halogen or the like) is polycondensed with an aromatic hydroxyamino compound (B) of formula II (wherein R5-R8 are each H or the like, and Z2 is O or the like) and an aromatic diamino compound (C) of formula III(wherein R9-R14 are each H or the like, Z3 is O or the like, and n2 is 0-2) in such amounts that the molar ratio of the total of components B and C to component A is 1:1.1-1.1:1 and the molar ratio of component C to component B is 99:1-1:99. The resulting aromatic polyester-amide comprising structural units of formulas IV, V, and VI and having a logarithmic viscosity of 0.3-6dl/g is formed into the titled film.

Description

Detailed Description of the Invention [Technical Field to Which the Invention Pertains] The present invention relates to an aromatic polyesteramide film with improved heat resistance, particularly mechanical performance and electrical insulation properties at high temperatures - [Technical background of the invention and its properties] Problems] Aromatic polyesters and aromatic polyamides have been known as engineering plastics. The former has low hygroscopicity and excellent moist heat properties, but has poor thermal stability and is difficult to mold.

Furthermore, it has the disadvantage of being susceptible to hydrolysis. Although the latter has excellent heat resistance, it is generally highly hygroscopic and has a high melting point, making it extremely difficult to mold.

For this reason, a homogeneous film with good heat resistance has not been obtained from these engineering plastics. For example, extrusion-molded films made from aromatic polyesters, which are copolymers of terephthalic acid dichloride and ino7tal dichloride and 2,2-bis(4'-hydroxyphenyl)propane, have excellent mechanical and electrical properties. It is useful as an electrical insulating material, but in recent years electrical
Considering the heat resistance required for high performance, high reliability, maintenance-free, etc. of m-child parts, it did not have satisfactory heat resistance. On the other hand, aromatic polyamide fibers, which are copolymers such as m (or p)-phenylene terephthalamide and m (p)-phenylene terephthalamide, are widely used in synthetic paper and other materials. However, aromatic polyamide film L has drawbacks such as brittleness, dielectric breakdown η(, poor pressure and heat deterioration resistance, etc.)
As a high-performance film, it was still unsatisfactory.

Therefore, in order to eliminate the drawbacks of aromatic polyester and aromatic polyamide, and to obtain a polymer that combines the excellent properties of both, aromatic polyester amide, which has ester bonds and amide bonds in the same molecule, has been developed. Research progressed.

For example, in Japanese Patent Publication No. 39-26012, aromatic polyesteramide was prepared from 2,2-bis(4'-hydroxyphenyl)propane, hexamethylene diamine, and phthalic acid dichloride (inphthalic acid dichloride:terephthalic acid dichloride -50:50). A method for obtaining the is disclosed. Although this polymer had a softening temperature of 228 to 236°C, its thermal stability at high temperatures was poor and unsatisfactory.

Also, for example, according to Japanese Patent Publication No. 48-19237, 2
．． 2-bis(4'-hydroxyphenyl)propane, 2
．． A reed aromatic polyesteramide is obtained from 2-bis(4'-aminophenyl)propane and terephthaloyl chloride by an interfacial polymerization method.

However, although this polymer has a high secondary transition temperature of 262°C, its decomposition temperature is low at 350°C or higher.
It also has the disadvantage of being poorly soluble in many organic solvents.

Furthermore, Japanese Patent Publication No. 54-20555 describes a method for obtaining aromatic polyesteramide from inphthalic acid chloride, 4-amino-4'-hydroxydiphenyl ether and 4,4'-diaminodiphenyl ether, and the decomposition temperature is 365°C.
It was low.

As described above, conventional aromatic polyesteramide L has various drawbacks and is still unsatisfactory as a heat-resistant film.
It has not yet reached the point where it has become commercially viable.

[Purpose of the invention]

The object of the present invention is to eliminate such drawbacks and provide ii.
The object of the present invention is to provide a film made of aromatic polyesteramide, which is a useful copolymer having excellent electrical insulation properties, mechanical performance, and processability at high temperatures.

[Summary of the invention]

The present invention relates to the general formula (summer), (1) and C): (wherein R
□ to R12 may be the same or different, and each is a hydrogen atom or a halogen atom.

Represents a nitro group, phenyl group, cyano group, alkyl group having 1 to 5 carbon atoms, or alkoxy group having 1 to 5 carbon atoms; R1
3 and R□4 may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; 2□ to z3 may be the same or different;
Direct bond, oxygen atom, sulfur atom, sulfonyl group, carbonyl group, 7-chloroalkylene group having 5 to 15 carbon atoms, alkylene group having 1 to 7 carbon atoms, alkylidene group having 2 to 7 carbon atoms, or 2 to 7 carbon atoms, respectively. 7 represents an alkenylene group; nl u O paternal 1, n24dO1l or 2
The molar ratio of the structural unit of formula (Il) to the structural unit of formula (II) is 99
:1 to 1:99 and the logarithmic viscosity is 0.3 to 6. O
The film is made of an aromatic polyesteramide having the following formula: d//P.

The aromatic polyester abad used in the present invention has the general formula: [In the formula, R15 and R16 are halogen atoms, hydroxyl groups or functional groups: l(□, -0-(In the formula, R17 has 1 carbon number ~5 represents an alkyl group or a phenyl group; lζ□ to R4, Z□ and !1□ are the same as the above-mentioned groups, and fb ; Eb ) Bonic acid or its derivatives.

6R8 (in the formula, R5-R8 and z2 are the same as the above-mentioned groups) and an aromatic hydroxyamino compound represented by (in the formula,
R0 to R14* The aromatic diamino compound represented by ZB and nga (same meaning as above) and the total amount of compound and compound 0 to compound (g) are in a molar ratio of 1:1
．． 1 to 1.121, and compound 0 to compound (b) is produced by polycondensation zeta in a molar ratio of 99=1 to 1:99.

In the substituents R-R-4 of formulas (1)-■,
A fluorine atom is a fluorine atom, a chlorine atom, an odor atom, or an iodine atom, and an alkyl group with 1 to 5 carbon atoms is a methyl group, ethyl group, propyl group, inglovir group, butyl group, or tert-butyl group. or pentyl group, etc., and the alkoxy group having 1 to 5 carbon atoms refers to methoxy group, ethoxy group, propoxy group, impropoxy group, butoxy group, ter
These include t-butoxy group, linear pentoxy group, and the like. Substituent 2
In 1 to z3, the cycloalkylene group having 5 to 15 carbon atoms is a cyclopentele group, a cyclohexyredi group, a cyclodecarylene group, a cyclodecarylene group, a cyclononylene group, a cyclodecarylene group, and a cyclosidecarylene group.

7 A chlortridecalylene group, a cyclotetradecarylene group, a cyclobentadecarylene group, etc., carbon #! iL
i~7 alkylene group and methylene group, ethylene group,
Propylene group, butylene group, amylene group.

Hexylene group, pentamethylene group, 1-methylhexamethylene group, etc., and alkylidene groups having 2 to 7 carbon atoms and i'! ,, ethylidene group, inethylidene group, globylidene group, butylidene group, pentylidene group, hexylidene group, hexylidene tin, inylidene group, inglopylidene group, imbutylidene group, impentylidene group,
Rashi with inohexylidene group or inhebutylidene group, etc.
Alkenylene group having 2 to 7 carbon atoms tohamenylene group, clobenylene group, 1-butenylene group, 2-butenylene group, 1-
Methyl-2-butenylene group, 1,1-dimethyl-2-butenylene group, 1-methylene-3,3-dimethylglobylene group, 3-methyl-3-ethylpropylene group, or 2. −
Such as methyl-2-butenylene group.

Specific examples of the compound represented by the general formula (IV) include terephthalic acid, inphthalic acid, 4,4'-diphenylene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, and 4,4'-diphenyl sulfide. Dicarboxylic acid, 2,2-diphenyl-propane-4', 4'
-dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenylketone dicarboxylic acid, or phthalic acid, and derivatives of these dicarboxylic acids include terephthalic acid dichloride, terephthalic acid dipromide, and inphthalic acid dichloride. , inphthalic acid dipromide, 2-chlorothyrentalic acid dichloride, 2 e 6-
Schiff o.

Examples include terephthalic acid dichloride, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, diphenyl terephthalate, dimethyl inptalate, diethyl inctalate, and diphenyl isophthalate. Furthermore, the hydrogen atom of the benzene nucleus of these compounds is inert to polycondensation, such as a chlorine atom, a bromine atom, a methyl group,
The compound may be di-substituted with at least one substituent selected from the group consisting of an ether group and a cyano group.

In the production of aromatic polyester abad, 11! selected from the group consisting of these! lI or two or more types are used. In addition, as other dicarboxylic acids or derivatives thereof, for example, naphthalene carboxylic acid or derivatives thereof can also be used.

Specific examples of the compound represented by the general formula (b) are:
4-hydroxy-4'-aminodiphenyl, 4-hydroxy-4'-7minodiphenylmethane, 2,2-(
4'-hydroxy-4-aminodiphenyl)propane, 2.2-(4-hydroxy-4'-aminodiphenyl)butane, 1.1-(4'-hydroxy-4-aminodiphenyl)cyclohexane, 2,2 - (4'-hydro-3-methyl-4-agonodiphenyl)propane, 2,2-(4'-hydroxy-3N,5-dimethyl-4'-aminodiphenyl)propane, 2,2
- (4'-hydroxy-3〃-bromo-4#-aminodiphenyl)propane, 2,2-(4'-hydroxy-
31-cyano-41-aminodiphenyl)propane, 2
．． 2-(4'-hydroxy-3#-methoxy-41-aminodiphenyl)propane S3-methyl-4-hydroxy-4'-aminodiphenyl, 3,3'-dimethyl-4
-Hydroxy-4'-aminodiphenyl, 3,5-dimethyl-4-hydroxy-4'-ami/jinenyl, 3-
Methyl-4-hydroxy-4'-aminodiphenyl sulfide, 3-methyl-4-hydroxy-4'-aminodiphenylmethane, 3.5-dimethyl-4-hydroxy-4'-aminodiphenylmethane, 2.2-(3- Methyl-4-hydroxy-4'-aminodiphenyl)propane, 2,2-(3',3#-dimethyl-4'-hydroxy-41-aminodiphenyl)furopane, 2,2-
(3', 5'-dimethyl-4'-hydroxy-4
1-75hasiphenyl)propane ri-2-(3'-ether-4'-hydro-17-4N-adnodiphenyl)propane, 2.2-(3'-tert-butyl-4-hydrogear 4〃- aminodiphenyl)propane, 2, 2
- (3'-Chloro-4'-hydroxy-41F-aminodiphenyl)filoban, 2.2-(3').

3〃-dichloro-4'-hydroxy-41-adnodiphenyl)propane, 2,2-(3', :('''
-dibromo 4'-hydroxy 4-aminodiphenyl)propane, 2, 2- (3', 5', 3',
5'-tetrabromo-4'-hydroxy-4#-aminodiphenyl)propane, 3,3-(4'-hydroxy-4〃-aminodiphenyl)pentane, 4-menal-2,4-(4'-hydroxy-4) 〃-Aminodiphenyl)-1-pentene, 4-methyl-2,4-(4'-
hydroxy-4''-7minodiphenyl)-2-pentene or t:j 4-methyl-2,4-('4'-hydrothine-3#-methyl-4'-7mi/diphenyl)-1-benzone, etc. In the present invention, one or more selected from the group consisting of these are used.

Specific examples of the compound represented by the general formula (VD) include:
m-phenylenediamine, p-7enylenediamine, 2
．． 4-) Relenecyabane, 4,4'-diaminodiphenyl, 4,4'-diaminodiphenyl ether s4+4'
-Diaminodiphenyl sulfone 4.4'-Diaminodihenyl sulfide, 4.4'-') -CN-ethelamino)diphenyl ether, 4.4'-Diaminodiphenylmethane, 2,2-(4').

4I-diaminodiphenyl)propane% 3.3'-diaminodiphenylketone, 2,2-(4',4'
-di-N-methylaminodiphenyl)propa:', 11
4-bis(4'-aminophenoxy)benzene, 4-methyl-2,4-bis(4'-aminophenyl)-1-pentene, 4-methyl-2,4-bis(4'-aminophenyl)-2 -Pentene, α, d-(4.

4'-cyabanodiphenyl)-p-diinpropylbenzene, α, C1'-(4,4'-diaminodiphenyl)
-p-diynebutylbenzene, α, α'-(4.

4'-diaminodiphenyl)-m-diinpropylbenzene, 1,5-diaminonaphthalene,
Phenylenethiain, 4-methyl-2°4-bis(4'
-aminophenyl)pentane, 4,4'-diabanodiphenyl ketone, 3,3'-cyabanodiphenyl ketone, or 3,3'-diaminodiphenylsulfone, and furthermore, aromatic diamino compounds such as When the hydrogen atom of the aromatic nucleus of You may also obtain cy-substituted compounds. In the present invention, one or more selected from the group consisting of these are used. Furthermore, as other aromatic cyano compounds, for example, 1,5-diaminonaphthalene, 5
(or 6)-amino-1-(4'-aminophenyl)-
1,3,3-1-rimeterindane and the like can also be used.

The manufacturing method of the present invention can be implemented in various ways. That is, for example, (1) a method in which a polycondensation reaction is carried out in a homogeneous bath in the presence of an inert organic solvent and a tertiary amine using an aromatic dicarboxylic acid or a derivative thereof as a starting material; (2) Heterogeneous resistance of basic compounds in the presence of hydroxyl solutions using aromatic dicarboxylic acids or their derivatives as starting materials and to which an inert organic solvent and optionally tertiary abans were added as catalysts. Method of carrying out polycondensation reaction in liquid, (
3) A method of carrying out a polycondensation reaction by melting under heating and reduced pressure in the absence of a solvent may be mentioned.

The reaction conditions for each of the above reactions will be explained in detail below.

The blending ratio of the reaction raw materials in the present invention is 8f for the aromatic dicarboxylic acid represented by the above formula 0 or its derivative 4y.
It is preferable that the molar ratio of the aromatic hydroxyamino compound represented by the formula (I) and the aromatic diamino compound represented by the above formula is j: 1.1 to 1.1:t. That is, it is most preferable that the compound ω is used in an equimolar amount with respect to the composite material of the needle wire compound (1) and the compound (b), and it is possible to use the total amount in excess or deficiency within the range of 10 moles or less. If the company using these compounds deviates from this range, it will be difficult to obtain a polymer having a desired degree of polymerization. In addition, the use stage of compound (9) is 99 for the joint BY sewing of compound (VD and compound (b)).
Morchi range. If the intoxication caused by this solid compound falls outside of this range, the significance of combining the two will be lost.
The molding of the aromatic polyester amide becomes difficult.

In the reaction (1), first, an aromatic dicarboxylic acid represented by the general formula 〇 or a derivative thereof is reacted with an aromatic hydroxya() compound represented by the general formula ~). The reaction conditions at this time are: s %i inert f [in a gas atmosphere, under stirring, -Il in a temperature range of 0 to 120 °C [; (, more preferably 1
Specifically, in the temperature range of -20 to 100'C, 0°5
It is preferable that the reaction is allowed to occur for up to 12 hours.

Next, the 'I' product Vt obtained by the above reaction is reacted with the aromatic Schiff'-hano compound represented by the general formula CD.

For example, inert gas such as nitrogen 5. ``j-Uj4'' under stirring in a temperature range of -40 to 120°C, more preferably in a temperature range of -20 to 80°C, 0
．． It is preferable to react for 5 to 13 hours.

The reaction of (2) involves the reaction of an aromatic dicarboxylic acid or a derivative thereof represented by the general formula 〇, an aromatic hydrodiamino compound represented by the general formula The reaction conditions at this time are, for example, under stirring at a temperature range of -40 to 100°C, more preferably in a temperature range of -20 to 80°C, for 0.1 to 12 hours. Preferably, it is something that causes a reaction.

Examples of the inert organic solvent used in the reaction of +1+ (2) above include methylene chloride, chloroform, carbon tetrachloride, 1,1,2-)lichloroethane,
selected from the group consisting of chlorobenzene, benzene, toluene, xylene, tetrahydrofuran, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-hyrrolidone, dimethylsulfoxide, sulfolane, pyridine and m-cresol Examples include IWP or two or more types. In addition, it is preferable that the amount of tertiary aban used in the reaction (1) above is greater than that used by our company with respect to the by-product acid; Accordingly, the tertiary amine used as a catalyst is preferably in the range of 1xio-" to 1ob for aromatic dicarboxylic acids or derivatives thereof. Specific examples of this tertiary amine include trietheramine, trietheramine, n-propylamine, tri-n-butylamine, N-methylmorpholine, N
-ethylmorpholine, N,N-dimethylaniline, N,
One or more selected from the group consisting of N-dimethyl-m(or p-)-)luidine, quinoline, and pyridine can be used. Further, it is preferable that the amount of the basic compound used in the reaction (2) is equal to or more than 4 times the amount of the acid to be produced as a by-product. In this basic compound, lT+, example and 17, alkali metal hydroxide, alkali 4i: One or more types of rice can be cultivated.

The polycondensation reaction mineral (3), an aromatic dicarboxylic acid represented by the general formula (1) or a derivative thereof, an aromatic hydroxyamino compound represented by the general formula (V), and an aromatic dicarboxylic acid represented by the general formula (VD). The process is carried out in one step in a molten state with a bath additive. The reaction conditions at this time were 10
-400°C, more preferably 50-350°C
℃ temperature range and 400 to 0.001 mHj pressure range, more preferably 200 to 0.002 Ayu HP
It is preferable that the reaction be carried out at a pressure range of 3 to 50 hours. This polycondensation reaction is continued until the desired melt viscosity is reached. Incidentally, it is also possible to use a linear basic catalyst in this reaction. OX1
The range of 0% to 1% is preferable.Specific examples of this basic catalyst include alkali gold M1 alkali metal hydroxide-oxide: alcolade; Examples include group carboxylic acid salts.

In addition, when producing aromatic polyester amide, aromatic monohuman compounds are used as end treatment agents or molecular control agents for the purpose of improving the thermal stability and melt viscosity of the polymer. It is also possible to add group monoabano compounds, specific examples of these compounds include phenol and cresols.

Xylenols, o (or p)-phenylphenol, 2-phenyl-2-(4'-hydroxyphenyl)propane, 1(also 112)-7toll, aniline, toluidine, 2,4-dimethylaniline, 2 -aminobiphenyl, 4-aminobiphenyl, 2-phenyl-2-
(4'-Abanoneenyl)propane, 1 (or 2)-
Aminonaphthalene, etc. can be removed.

In the present invention, aromatic polyester amide is used to provide a film with practical mechanical strength.

Aromatic polyester ester 0, 5-I N-methyl-
Dissolve the solution in 100 ml of 2-hyrolidone for 3 minutes.
The logarithmic viscosity measured at 0°C is 0.3 to 6. It is imperative that you give up on your child. In the present invention, the logarithmic viscosity is expressed by the following formula.

(In the formula, t is the flow time of the polymer solution, to is the flow time of only the organic solvent, and the concentration of the c-line polymer.) The melt extrusion method and the casting method will be described in detail below.

(Melt extrusion method) From a wide slit nozzle (e.g. T-die) heated to a temperature that allows expansion bath melt molding of aromatic polyesteramide, to a drum or endless belt in heated air or an inert gas atmosphere such as nitrogen. It is formed into an extruded film on a support of Nato. Extrusion can be carried out at any temperature higher than the softening point of the polymer and higher than the X-ray melting point, but the extrusion temperature is usually 250 to 400, taking into consideration the composition of the aromatic polyester amide, thermal decomposition, fluidity of the melt, etc. It is preferable to carry out in the range of 'C. Depending on the method of producing the film-wire aromatic polyester amide, it may be produced by extruding a polymer powder or chip pellets heated and melted, or the melt may be extruded after the polymerization is completed, as in the case of melt polymerization. It may also be manufactured by extrusion.

The unstretched extruded film made of aromatic polyesteramide thus obtained is strong, has good transparency, and has excellent one-dimensional stability. The stretched film can be heated and stretched uniaxially and biaxially. The heating stretching may be carried out on a solidified film after shaping, or may be carried out in a continuous process subsequent to the film manufacturing process.

Stretching is preferably carried out at a temperature in the range of 160 to 350°C, more preferably in the range of 170 to 330°C.

The stretching ratio varies depending on the polymer composition, but for uniaxial stretching, the range is preferably 1.2 to 5 times, and for biaxial stretching, the range is preferably 1.2 to 4.5 times in each direction. In addition, in biaxial stretching, it is preferable that the area magnification by stretching is 1.5 to 1.5.
It is preferable to set the range to 16 times.

Biaxial stretching #'i can be carried out by sequential biaxial stretching in which the stretching is performed in one direction and then in a direction perpendicular to this direction, or by simultaneous biaxial stretching in which stretching is performed in the above two directions at the same time. .

(Casting method) In this method, a film is obtained from a Dogue solution in which 5 to 40% by weight of aromatic polyester amide is dissolved in an organic solvent.

When an inorganic salt (for example, lithium chloride, lithium bromide) is added to the dope solution as a polymer solubilizing agent, or when inorganic salts produced as by-products during polymer production remain, wet or dry methods can be used. When the solubilizing agent and by-product inorganic salt are not included, the dry method is used.

To form a film using the wet method, the Dawg liquid is passed through the slit from 0 to
Direct extrusion into a film-forming bath consisting of water or a mixed system of water and organic solvent (generally containing 50% or more of water) maintained at a temperature of 100°C, or supporting a drum, endless belt, etc. The film is then extruded onto the film, and then introduced together with the support into the above film forming bath, and if necessary, the film is stretched in the longitudinal direction within a range of 0.5 to 3.0 times.
The film of the present invention is dried by drying at a temperature of 0 to 450°C for up to 2 hours.

Film formation by the wet-dry method involves extruding the Dawg solution through slits onto a support such as a drum or endless belt to form a thin film. Raise the foot temperature in the range from room temperature to 250°C to prevent voids and bubbles from scattering, and then scatter and concentrate the organic solvent within 90 minutes.

・-ml of the dried and then peeled film from the support
As with the hot and wet method, the inorganic salts and solvent remaining in the film were extracted by one person under tension in a bath, and then 150 ml of water was added.
The film of the present invention is dried at a temperature range of ~450°C for up to 2 hours! iru. A thin film of Dawg R5 is cast onto a support such as a drum or an endless belt using a slit or a doctor knife and heated in an atmosphere of hot air or an inert gas such as nitrogen. F from room temperature to 300°C to avoid voids and bubbles caused by rapid solvent scattering from the thin film light 1111.
W'l! within 990 minutes by constant temperature or temperature increase within the range of ! The unstretched film of the present invention is obtained by scattering, concentrating, and drying the inorganic thickening agent, and then drying the film peeled from the support until the residual volatile content becomes 2 or less. Of course, in this case, it is also possible to obtain a film from the Dawg liquid by a wet method or a wet-dry method.

The film thus obtained can be uniaxially and biaxially stretched under the same conditions as for the extruded film described above to obtain a stretched film.

When forming the extruded film of the present invention, lubricants such as silicon oxide and aerosil; bath melt viscosity modifiers such as octyl phthalate, triphenyl phosphate, and tricresyl phosphate; stabilizers or antioxidants such as Lille phosphites;
Additives such as ultraviolet absorbers such as 0-oxybenzophenone derivatives and benzotriazole derivatives; furthermore, flame retardants and anti-inflammatory agents can be present to improve the physical properties of Fil J. These additives can be present in either the aromatic polyester amide manufacturing process or the film forming process.

Further, it is possible to make these additives present even when forming a film by a casting method.

〔Effect of the invention〕

The aromatic polyesteramide film of the present invention has superior heat resistance, mechanical strength and dimensional stability compared to aromatic polyester films. Also, the film of the dud 8+1 is
The disadvantages of aromatic polyamide films are that they dissolvate in organic solvents, which necessitates the use of dissolution aids such as lithium bromide; highly concentrated solutions exhibit anisotropy, making it difficult to form into films; It eliminates the drawbacks of aromatic polyamide films, such as their high properties, and is more easily soluble in organic solvents than aromatic polyamide films, and is easy to form into films despite their high glass transition temperature. Due to its structural characteristics, it can be stretched well, and has the advantage of being free from voids, scratches, fish eyes, etc., and has extremely good uniformity, transparency, and the like.

As described above, the film of the present invention has excellent heat resistance, toughness, and electrical insulation properties, so it can be used not only for general packaging, but also for insulation barriers, capacitors, electrical spacers, and VTR.
Analysis of aeration tape, base material for mica tape, base material for flexible printed circuit boards, laminate parts of film and metal, insulating tape for electric wires, film for greenhouses, and micropores added by neutron irradiation and etching treatment. filtration materials and industrial p filtration materials for brewing, pure water production, etc., or separation membranes;
It can be used in a wide range of applications, including composites with gray, 7-eye bar or carbon fiber, color 7-otocobee, and acoustic vibration films.1) Its practical value is extremely great.

[Embodiments of the invention]

The present invention will be explained below with reference to production examples and examples.

In addition, in the production examples and examples, where it says "1 part" means "1 part heavy".
All performance evaluations in the examples are based on JIS
Measurements were made at 25"C in accordance with C2318. The measurement frequency of volume resistivity, dielectric constant, and dielectric loss tangent was 50 Hz.

Production Example 1 1.082 parts of p-phenylenediamine, 2.2-(4'
-hydroxy-4N-abanodiphenyl)furopane 20
．． 0.042 part of 457B3o-hydroxydinenyl was dissolved in 400 parts of dehydrated tetrahydrofuran, and then 22.3 parts of triethylamine was added to maintain the temperature at -20'C. Next, inphthalic acid dichloride 12.1 s
A mixture of 0 parts and 8.144 parts of terental acid dichloride was gradually added to the sushi atmosphere] and 1 iJ for 1 hour at 0°C.
Stirring was continued for 5 hours and 111 J at 25°C. After the reaction
, diluted with 180 parts of N-dimethylacetoacetate, and the mother liquor from which the triethylamine J true acid salt produced was separated by Ui was mixed with a homogenizer (mixtured) and discharged into stirred ethanol to obtain a polymer ?1=lr. First, separate the polymer, wash it with ethanol, dry it under reduced pressure, and remove the pale yellow polymer.

The logarithmic viscosity of the obtained polymer was (1,91 dll/Sr
Met.

This polymer will hereinafter be referred to as Polymer A.

Production Example 2 2.002 parts of 4.4′-cyabanodiphenyl ether,
2,2-(4'-hydroxy-4〃-aminodiphenyl)propane 20.457i[! , p-hydroxyschifnyl 0,042 gB 222.3 parts of triethyl rare was added to 500 parts of cyclohexane until completely dissolved, and the mixture was maintained at -30°C. Next, 14.210 parts of inphthalic acid dichloride and terephthal β
A mixture of 6.114 parts of 2 dichloride was added under a nitrogen atmosphere.

The mixture was added gradually and stirring continued for 2 hours at 0°C and 3 hours at 25°C. After that, the procedure was the same as in Production Example 1, and the logarithmic viscosity [0,98
dll/! A pale white polymer was obtained. This polymer will be referred to as Polymer B hereinafter.

Production Example 3 50.05 parts of 4.4'-cya inodiphenyl ether was dissolved in 300 parts of anhydrous N,N-dimethylacetamide, and this solution was maintained at 0°C to dissolve inphthalic acid dichloride 2.
A mixture of 2.33 parts of prephthalic acid dichloride and 22.33 parts of 9-'! ? The mixture was gradually added under a positive atmosphere and stirred for 2 hours at this temperature for 1 t. Separately 2,2
- (4'-hydroxy-411-a is nodiphenyl)
14.206 parts of propane and 12.2 parts of triethylamine.
7 parts dehydrated and 300 parts of tetrahydrofuran to Lf'!
? Then, this solution was maintained at -10°C, and 9.389 parts of inphthalic acid dichloride and 9.9 parts of prephthalic acid dichloride were added.
389 parts of the mixture were slowly added to the tube and stirred at this temperature for 1 hour and at 25° C. for 31+1 hours. This reaction e is then held at 0°C.

Said anti+6? The color was injected over 30 minutes, then stirring was continued at this temperature for 3 hours. Thereafter, in the same manner as in production row 1, a pale white polyester with a viscosity of 1.2 dll/1 was prepared. This polymer was mixed with polymer C and ffr.

A dope solution with a polymer concentration of 20 times was prepared by dehydrating Polymer A and dissolving it in 6N,N-dimethylacetamide. Uniform cooling with a thickness of 300μm.

2 degrees Celsius for 4 degrees Celsius at 150 degrees Celsius from room temperature under a distillate atmosphere.
While rising at a speed of g1, the bath agent is scattered and self-supporting τ, with a rate of 1/1. 1;J answered no. Next, insert this film into a fixed length frame, turn the direction force by 1 at 2 o'clock with 180'IC, and make a uniform transparent film of 5oμn+ (1).

In addition, the TJ'l nLr self-supporting film was stretched by a biaxial stretching machine at a temperature of 150 degrees Celsius at a temperature of 150 degrees Celsius, then stretched in two directions at the same time by a factor of 1 degree, then placed in a frame of a fixed length, and heated at 180 degrees Celsius for 2 hours.
A stretched film of m was obtained. The performance of these films is
Shown in the table.

Example 2 Powders of Polymer A and Polymer B were each pelletized using an extruder. This pellet was melted at 350°C and the slit width was 1. (1%, land length 10118I
A flat sheet with a thickness of 200 μm is extruded from a T-die onto a casting drum heated to 100°C. A blue transparent unstretched film was obtained. A biaxially stretched film was obtained by biaxially stretching the unstretched film by 2.0 times at 11E at a temperature of 200°C in a downward direction.

The performance of these films is shown in Table 1. 1. Example 3 Polymer Ct was dissolved in dehydrated N,N-dimethylacetamide to prepare a dope solution containing 18 needles in a polymer concentrated box.

Apply this dope onto a glass plate using an applicator for 35 minutes.
It was uniformly cast to a thickness of 0 μm and heated under nitrogen atmosphere from room temperature to 1.
A self-supporting film was obtained by increasing the temperature to 50° C. at a rate of 2° C. per minute and scattering the pre-stretching agent. Next, this film was set in a foot-long frame and heated at 190℃ for 2 hours to make it 62μ
A uniform and transparent unstretched film of m was obtained. The tensile strength of this film is 12.7 Kq/mtr? , the elongation at break is 29 inches, and the volume resistivity is 9.1. 6 with a dielectric constant of 13.8 and a dielectric constant of 0.4.

Examples 4 to 9 Aromatic diamino compounds include 1m-phenylenecyabane, 4,4'-diaminodiphenylmethane, and 4 in place of 4,4'-diaminodiphenyl ether, respectively.
, 4'-diaminodiphenylsulfone, 3-polydiaminodiphenylketone, 2.4-)lylenediamine, 3,
A polymer was prepared in the same manner as in Example 1, except that 3'-dichloro-4,4'-diaminodiphenylmethane was used. In addition, 2,2-(4'-avanophenyl)
(The molar ratio of 4'-hydroxyenylnopropane and these aromatic diamino compounds is 9:1.Next, these polymers were mixed using the same method as in Mtd3 to obtain a Miji-stretched film. Ta.

The results are shown in Table 2.

Claims (4)

[Claims] (1) General formula (1) , Ol) and (in the formula,
R□ to R□2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a nitro group, a phenyl group, a cyano group, an alkyl group having 1 to 5 carbon atoms, or a carbon number 1
~5 represents an alkoxy group; R03 and R, 4B may be the same or different, and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; 20 to z3 are the same or different %1, respectively; tangential bond, oxygen atom, sulfur atom, sulfonyl group, carbonyl group, cycloalkylene group with carbon number 5 to 15, carbon number 1 to
7 represents an alkylene group, an alkylidene group having 2 to 7 carbon atoms, or an alkenylene group having 2 to 7 carbon atoms; n□ represents 0 or 1, n2 represents 0.1 or 2; , each unit is connected by an amide bond and/or Nisder bond, and the structural unit of formula (1) and formula (1)
The molar ratio of the structural units is in the range of 99:1 to 1:99, and the logarithmic viscosity is in the range of 0.3 to 6. A film made of aromatic polyesteramide characterized by being Odn/P. (2) The film is unstretched.
Item 1: Self-published film. (3) The film according to claim 1, wherein the film is stretched. (4) The film according to claim 1, wherein the film is biaxially stretched.