JPS6353210B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a heat-resistant resin having a mixture of a hetero imide ring and a furan ring in a polymer main chain. The purpose of this is that the cured resin imidized by ring-closing treatment has excellent flexibility and heat resistance, and also has the abrasion resistance, chemical resistance, electrical insulation, and film-forming properties of a polyimide resin. The object of the present invention is to provide a heat-resistant resin that has excellent mechanical properties and is useful as a material for electronic devices, an electrical insulating material, a coating, an adhesive, a paint, a molded product, a laminate, a fiber, or a film material. [Prior Art] Conventionally, polymers having a heterocycle such as imide, imidazole, thiazole, oxadiazole, triazole, quinoxaline, thiadiazole, oxazinone, quinazoline, imidazopyrrolone, isoindoquinazolone, etc. in the polymer main chain have been used. It is already known that it is an excellent heat-resistant resin. However, these known polymers have rigid polymer main chains, and when made into films, membranes, fibers, etc., have poor flexibility, flexibility, elongation, etc., and are unsatisfactory for practical use. From this point of view, various studies have been carried out in the past, and 4,4'-diaminodiphenyl ether has been used as one of the amine components in the raw materials for producing heat-resistant resins. , diaminodiphenylmethane, diaminodiphenyl sulfone, etc., it is also known that improved polymers with better flexibility, flexibility, elongation, etc. can be obtained. However, those made of 4,4'-diaminodiphenyl ether had a serious drawback of reduced heat resistance. [Object of the Invention] As a result of studies aimed at overcoming the above-described drawbacks, the present invention uses 2,8-diaminodiphenylene oxide, 4,4'-diaminodiphenyl ether, and p-phenylenediamine as amine components. The present invention was completed after discovering that by using the above, it is possible to obtain a heat-resistant resin that has excellent heat resistance and physical properties such as flexibility, flexibility, and elongation, and has a well-balanced practicality. This is what I have come to do. [Structure of the Invention] The present invention involves reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine to form an imide ring using 2,8-diaminodiphenylene oxide and 4,4' as the aromatic diamine. - A method for producing a heat-resistant resin, characterized by using diaminodiphenyl ether and p-phenylenediamine. The reaction formula is as follows.

[Table] The aromatic tetracarboxylic dianhydrides used in the present invention are pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 2,3,6,7-
naphthalenetetracarboxylic dianhydride, 3,3',
4,4'-diphenyltetracarboxylic dianhydride,
1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxydiphenyl) Propane dianhydride, 3,4,
9,10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxydiphenyl)ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4, 5,
8-Tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- Dichloronaphthalene-1,4,
5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,4,7-tetrachloronaphthalene-1,4,5 , 8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,
2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, pyrazine 2,3,5,6-tetracarboxylic dianhydride, 2,2- Bis(2,5-dicarboxyphenyl)propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride anhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, Thiophene-2,3,4,5-tetracarboxylic dianhydride and the like. Furthermore, among the aromatic diamines used in the present invention, essential components are 2,8-diaminodiphenylene oxide, 4,4'-diaminodiphenyl ether, and p.
- phenylenediamine. An example of how to make 2,8-diaminophenylene oxide is shown in the following reaction formula. [Reference: University of Fukui Faculty of Engineering Research Report 16(2)238
('68)] Of course, aromatic diamines other than those mentioned above can also be used. For example, m-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone. , 3,3'-diaminodiphenylsulfone, 2,6-diaminopyridine, bis(4-aminophenyl)phosphine oxide, bis(4-aminophenyl)-N-methylamine, 1,5-diaminonaphthalene, 3,3 '-dimethyl-4,4'-
Diaminobiphenyl, 3,3'-dimethoxybenzidine, 2,4-bis(β-amino-t-butyl)
Toluene, bis(p-β-amino-t-butylphenyl) ether, p-bis(2methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, m-xylyne These include diamine, p-xylylene diamine, bis(p-aminocyclohexyl)methane, and the like. The amount of 2,8-diaminodiphenylene oxide used is preferably 10% by weight or more, and if it is less than this, the effect of improving heat resistance strength will be small. Further, the amount of 4,4'-diaminodiphenyl ether used is preferably 10% by weight or more, and if it is less than this, the effect of improving flexibility will be small. Further, the amount of p-phenylenediamine used is preferably 10% by weight or more, and if it is less than this, the effect of improving the heat resistance temperature will be small. In the present invention, the reaction between the aromatic tetracarboxylic dianhydride and the aromatic diamine is preferably carried out in equimolar amounts as much as possible, and the degree of polymerization is also increased. If the amount of either raw material increases by 5% or more, the degree of polymerization will drop significantly and a low molecular weight product with poor film-forming properties will be obtained, so care must be taken. Usually, using 1 to 3% more of one raw material means that
This is often done to improve workability and processability. The solvent of the reaction system in the present invention is an organic polar solvent whose functional group has a dipole moment that does not react with tetracarboxylic dianhydride or 2,8-diaminodiphenylene oxide. In addition to being inert to the system and solvent to the product, the organic polar solvent must be solvent to at least one, preferably both, of the reaction components. Typical solvents of this type are N,N-
Dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N
-Diethyl acetamide, N,N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexamethyl phosphoamide, N-methyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, etc. These solvents can be used alone or used in combination. Other solvents that can be used in combination include benzene, benzonitrile, dioxane,
Nonsolvents such as butyrolactone, xylene, toluene, and cyclohexane are used as dispersion media for raw materials, reaction regulators, volatilization regulators for solvents from products, film leveling agents, and the like. It is generally preferred that the present invention be carried out under anhydrous conditions. This is because the tetracarboxylic dianhydride is ring-opened by water, becomes inactivated, and there is a risk of stopping the reaction. Therefore, it is necessary to remove both the moisture in the raw materials and the moisture in the solvent. However, water is sometimes intentionally added to adjust the progress of the reaction and control the degree of resin polymerization. Further, the present invention is preferably carried out in an inert gas atmosphere. This is to prevent oxidation of diamines. Dry nitrogen gas is generally used as the inert gas. The reaction in the present invention can be carried out in the following various ways. (1) Diamines and tetracarboxylic dianhydride are mixed in advance, and the mixture is added little by little to an organic solvent while stirring. This method is relatively advantageous in exothermic reactions such as those for polyimide resins. (2) Conversely, there is also a method of adding a solvent to a mixture of diamines and tetracarboxylic dianhydride while stirring. (3) A commonly used method is to dissolve only diamines in a solvent, and then add tetracarboxylic dianhydride to this in a proportion that allows the reaction rate to be controlled. (4) It is also possible to dissolve diamines and tetracarboxylic dianhydride separately in a solvent and then slowly add the two solutions in a reactor. (5) Furthermore, it is also possible to prepare in advance a polyamic acid product containing an excess of diamines and a polyamic acid product containing an excess of tetracarboxylic dianhydride, and then further react them in a reactor. (6) Among the diamines, there is also a method in which a part of the diamine compound and tetracarboxylic dianhydride are first reacted and then the remaining diamine compound is reacted, or the reverse method is also available. (7) In addition, one in which a part of diamine compounds among diamines is reacted with tetracarboxylic dianhydride, and one in which the remaining diamine compound among diamines is reacted with tetracarboxylic dianhydride. Another option is to mix them before use. The reaction temperature is preferably 0 to 100°C. This is because if the temperature is below 0°C, the reaction rate is slow, and if it is above 100°C, the produced polyamic acid gradually starts the ring-closing reaction. Usually, the reaction is carried out at around 20°C. The degree of polymerization of polyamic acid can be controlled in a planned manner. In order to control the degree of polymerization, it is also possible to end-block with phthalic anhydride or aniline, or add water to open one of the acid anhydride groups and inactivate it. When used, the polyamic acid product produced by the method of the present invention has the adhesion and adhesion properties of various silane coupling agents, borane coupling agents, titanate coupling agents, aluminum coupling agents, and other chelate coupling agents. Improvers, various solvents, and flow agents may be added, and in addition to these, ordinary acid curing agents, amine curing agents,
Small amounts of polyamide curing agents and curing accelerators such as imidazole and tertiary amines may be added, as well as flexibility agents and viscosity modifiers such as rubbers, polysulfides, polyesters, low molecular weight epoxies, talc, clay, mica, Feldspar powder, quartz powder, fillers such as magnesium oxide, carbon black,
Small amounts of colorants such as phthalocyanine blue, flame retardants such as tetrabromophenylmethane and tributyl phosphate, and flame retardant aids such as antimony trioxide and barium metaborate may be added; This opens up many uses. The polyamic acid product produced by the method of the present invention is imidized and cured by heating or by using a dehydrating agent. The heating temperature for the former heating and dehydration treatment is usually 50°C or higher, particularly preferably in the range of 150°C or higher and 200 to 400°C. Although air may be used as the atmosphere in this case, it is often preferable to use non-oxidizing conditions such as reduced pressure or inert gas. As the latter dehydrating agent, carboxylic anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride are often used, and these are particularly effective when used in the coexistence of basic substances such as pyridine and quinoline. [Effects of the Invention] According to the method of the present invention, a polymer using 2,8-diaminodiphenylene oxide, 4,4'-diaminodiphenyl ether, and p-phenylenediamine has a heat resistance that has not been obtained conventionally. Compared to other resins, it is an extremely heat-resistant resin with a good balance of heat resistance and flexibility. That is, the polymer synthesized by the method of the present invention has a large number of aromatic rings and heterocycles in its molecular structure, and therefore has excellent heat resistance. In addition, the main chain of the molecule has a helical shape, which is thought to give it excellent flexibility due to its spring-like effect. Specifically, the uses of the present invention are as follows:
First, it is used as a coating film to protect the surfaces of various electronic equipment, and as a heat-resistant insulating film for multilayer wiring on top of it. For example, semiconductors, transistors, linear ICs,
Hybrid IC, light emitting diode, LSI, super LSI
It is a wiring structure for electronic circuits such as. Furthermore, it is also used to impart heat resistance to various materials, to prevent microwaves, and to prevent radiation. Examples include waveguides for computers, atomic equipment, and interior materials for X-ray equipment. Next, it is used as a coating varnish for high temperatures, such as electric wire coating, magnet wire, dip coating for various electrical parts, and protective coating for metal parts.It is also used as an impregnation varnish for glass cloth, fused silica cloth, graphite fiber, boron, etc. Used for fiber impregnation, radar domes, printed circuit boards, radioactive waste containers, turbine blades, spacecraft requiring high temperature performance and excellent electrical properties,
It is used in other structural parts, and as an interior material for waveguides in computers, atomic equipment, and X-ray equipment to prevent microwaves and radiation. It is also used as a molding material to create self-lubricating sliding surfaces by adding graphite powder, graphite fiber, molybdenum disulfide, and polytetrafluoroethylene to piston rings, valve seats, bearings, seals, etc. It is also used to make jet engine parts, high-strength structural molded parts, etc. by adding glass fiber, graphite fiber, or boron fiber. It is also used as a high-temperature adhesive for bonding electrical circuit parts and structural parts of spacecraft. The heat-resistant resin of the present invention can be used in many other applications. [Example] The present invention will be explained below with reference to Examples. Example 1 In a four-necked separable flask equipped with a thermometer, a stirrer, and a dry nitrogen gas inlet, 0.2 mol (23.0% by weight) of purified anhydrous 2,8-diaminodiphenylene oxide and 4,4'- Take 0.5 mol (58.2% by weight) of diaminodiphenyl ether and 0.3 mol (18.8% by weight) of p-phenylenediamine, and add a mixed solvent of 95% anhydrous N-methyl-2-pyrrolidone and 5% toluene to it. An amount sufficient to bring the solid content of the raw materials to 15% was added and dissolved. Dry nitrogen gas is allowed to flow throughout the entire process from the beginning to the end of the reaction. Next, 1 mol of purified anhydrous pyromellitic dianhydride is added little by little while stirring.
Because it generated heat, cold water at approximately 15°C was circulated in an external water tank to cool it. After addition, the internal temperature was then increased to 20°C.
The reaction was completed by stirring continuously for 10 hours. The obtained product is a yellow transparent extremely viscous polyamic acid with an intrinsic viscosity of 1.18 at 0.5% NMP.
(30℃). Next, drop this polyamic acid onto a glass plate and use a spinner at 200 rpm/min for 10 seconds.
It was rotated for 30 seconds at 1500 rpm/min to form a film. This was heated to 80℃ under reduced pressure, then 150℃, 250℃,
Heat at 350℃ for 30 minutes each to dehydrate and close the ring.
A 20 μm yellow-brown transparent and tough polyimide resin film was obtained. Taking the infrared absorption spectrum of this film,
Strong absorption based on the imide ring was observed at 1780 cm ^-1 and 730 cm ^-1 and strong absorption based on the furan ring was observed at 1200 cm ^-1 . This film has undergone 10,000 bending tests (JIS-
P-8115) does not generate cracks, has great flexibility, and has excellent heat resistance.The temperature at which the film starts to decompose when heated at a heating rate of 5°C/min in air using a differential thermal balance analyzer is 530°C. It was warm at ℃. Furthermore, the tensile strength at 200°C was excellent at 15 kg/mm ² . Example 2 Using the same apparatus and method as in Example 1, 0.4 mol (55.0% by weight) of 2,8-diaminodiphenylene oxide and 0.6 mol (45.0% by weight) of p-phenylenediamine were mixed into 3,3',4 , 1 mol of 4'-benzophenone tetracarboxylic dianhydride were reacted. To this obtained product, an equal amount of a product of 1 mole of 4,4'-diaminodiphenyl ether and 1 mole of pyromellitic dianhydride, which had been reacted in advance, was mixed. The resulting mixture was a colorless and transparent extremely viscous polyamic acid with an intrinsic viscosity of 0.91. In addition, the obtained film is a polyimide resin film that is yellow and transparent, shows no cracks even after a 10,000-fold bending test (JIS-P-8115), and is extremely flexible.It also has excellent heat resistance, and the temperature at which thermal decomposition starts is low. It was 500℃. Moreover, the tensile strength at 200°C was excellent at 13 Kg/mm ² . Comparative Example 1 Using the same apparatus and method as in Example 1, a reaction was carried out using only 1 mole (100% by weight) of 4,4'-diaminodiphenyl ether as the diamine component. The obtained film showed no cracks even after 10,000 bending tests (JIS-P-8115) and was extremely flexible; however, the temperature at which thermal decomposition started was
It was only 360℃. Comparative Example 2 Using the same apparatus and method as in Example 1, a reaction was carried out using only 1 mole of p-phenylenediamine as the amine component. The resulting cured product had an extremely high thermal decomposition temperature of 550°C, but was too rigid to be made into a film. Comparative Example 3 Using the same equipment and method as in Example 1, 4,4'-diaminodiphenyl ether 0.6 was used as the diamine component.
mol and 0.4 mol of p-phenylenediamine were used to react. The obtained film showed extremely high flexibility without cracking even after a 10,000-fold bending test (JIS-P-8115), and had an excellent thermal decomposition onset temperature of 490°C, but the tensile strength at 200°C was The weight was only 8Kg/ ^mm2 .

Claims (1)

[Scope of Claims] 1. 2,8-diaminodiphenylene oxide and 4,4'-diaminodiphenyl ether as components of the aromatic diamine of the polyimide resin comprising aromatic tetracarboxylic dianhydride and aromatic diamine. and p-phenylenediamine as essential components, and the molar ratio of aromatic tetracarboxylic dianhydride and aromatic diamine to aromatic tetracarboxylic dianhydride:
Aromatic diamine: 100:95-105, 0-100℃
A method for producing a heat-resistant resin, characterized in that the reaction is carried out at a temperature of . 2. The method for producing a heat-resistant resin according to claim 1, which contains 10% by weight or more of 2,8-diaminodiphenylene oxide as an aromatic diamine component. 3. The method for producing a heat-resistant resin according to claim 1, which contains 10% by weight or more of 4,4'-diaminodiphenyl ether as an aromatic diamine component. 4. The method for producing a heat-resistant resin according to claim 1, which contains 10% by weight or more of p-phenylenediamine as an aromatic diamine component.