JPS61141734A - Production of heat-resistant resin - Google Patents

Abstract

PURPOSE:To obtain a resin excellent in flexibility, heat resistance, etc., by reacting a component comprising 2,8-diaminodiphenylene oxide and 4,4'- diaminodiphenyl ether with an aromatic tetracarboxylic acid dianhydride. CONSTITUTION:An aromatic diamine component comprising 2,8-diaminodi phenylene oxide and 4,4'-diaminodiphenyl ether as essential components each in an amount of at least 10wt% and, optionally, other aromatic diamines (e.g., m-phenylenediamine) is reacted with an aromatic tetracarboxylic acid dianhydride (e.g., pyromellitic dianhydride or benzophenonetetracarboxylic dianhydride) and the product is imidated to obtain the purpose heat-resistant polyimide resin. The obtained resin can be suitably used for forming, e.g., coat ing films for protecting the surfaces of electronic parts.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a method for producing a heat-resistant resin having a mixture of a hetero imide ring and a heptad ring in the polymer main chain.

The purpose of this is that the cured resin imidized by ring-closing treatment has excellent flexibility, properties, and heat resistance, and also has the abrasion resistance, chemical resistance, electrical insulation, and film-forming properties of a polyimide resin. It is an object of the present invention to provide a heat-resistant resin that 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, etc., and has excellent mechanical properties.

[Prior Art 1 Conventionally, heat-resistant polymers having heterocycles such as imide, imidazole, thiazole, oxadiazole, triazole, quinoxaline, thiadiazole, oxazinone, quinazoline, imigzopyrrolone, isoindoquinazolone, etc. in the polymer main chain have been used. It is already known that it is an excellent 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 conducted in the past, and the use of 4,4'-diami/diphenyl ether as one of the amine components in the raw materials for producing heat-resistant resins has been compared to other amines such as phenylene diamine and benzidine. It is also known that improved polymers with better flexibility, flexibility, elongation, etc. can be obtained compared to those using conventional methods such as diaminodiphenylmethane, diaminodiphenyl sulfone, and the like.

However, those made of 4,4'-diaminosyphenyl ether had a serious drawback of reduced heat resistance.

[Objective of the Invention 1] As a result of studies to overcome the above-described drawbacks, the present invention is based on the following: 2,8-di7-minodi-7-ylene oxide and 4,4'-diaminosynylene ether as essential components as amine components. It was discovered that by using the resin, a heat-resistant resin with excellent heat resistance and physical properties such as flexibility, flexibility, and elongation can be obtained, which is well-balanced in practical use. It has arrived.

[Structure 7 & of the Invention] The present invention reacts an aromatic tetracarboxylic dianhydride with an aromatic diamine to form an imide ring using 2,8-diaminodiphenylene oxide and 4,4゛ as aromatic diamine. - Diaminodiphenyl ether.

The reaction formula is as follows.

2,8-diamino aromatic tetracarboxylic 4,4°
- Diaminodiphenylene oxide acid dianhydride
Nophenyl ether The aromatic tetracarboxylic dianhydride used in the present invention is pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, 2.3, 6.7
-su7talentetracarboxylic dianhydride, 3.3',4
．． 4'-diphenyltetracarboxylic dianhydride, 1,2
, 5.6-naphthalenetetracarboxylic dianhydride, 2,
2°3,3′-diphenyltetracarboxylic acid difi hydrate, 2.2-bis(3,4-dicarboxydiphenyl)furopane dianhydride, 3.4.9. to-perylenetetracarboxylic dianhydride, bis(3g4-dicarboxydiphenyl)ether dianhydride, naphthalene-1,2,4゜5
-Tetracarboxylic dianhydride, naphthalene-1,4,5
゜8-Tetracarboxylic dianhydride, 4,8-tmethyl-
1゜2.3,5,6. ? -Hexahit asu7 talen-1
．． 2,5゜6-tetracarboxylic dianhydride, 2,6-cyclona7talene-1.4,5.8-tetracarboxylic dianhydride, 2゜7-cyclona7talene-1.4,5.
8-tetracarboxylic dianhydride, 2,3,4.7-titrachlorona 7talene-1.4.5.8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride compound, 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)furopane dianhydride, 1,
1-bis(2,3-dicarboxy7enyl)ethane dianhydride, i,i-bis(3,4-dicarboxyphenyl)
Ethane dianhydride, bis(2,3-dicarboxy7enyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dihydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, Anhydride, thio7ene-2.3,4.5
-tetracarboxylic dianhydride, etc.

Further, among the aromatic diamines used in the present invention, essential components are 2,8-diaminodiphenylene oxide and 4,4'-noamino diphenyl ether. 2. Oxide showing an example of how to make 8-diaminophenylene oxide using a reaction formula Phenylene oxide [References Nifukui University Faculty of Engineering Research Report 16 (2) 238 ('68)] Of course, aromatic diamines other than the above may also be used. I can do it.

Examples include +1-phenylenediamine, ρ-phenylenediamine:y, 4,4'-diaminodiphenylpropane, 4I
4”-diaminodiphenylmethane, benzidine, 4.4
'-Diaminodiphenylsulfyl', 4.4'-noaminodiphenylsulfone, 3.3'-diaminodiphenylsulfone, 2゜6-zimitupyridine, bis(4-7
Minophenyl)phosphine oxide, bis(4-7minophenyl)-N-methylamine, 1.5-')aminonaphthalene, 3I3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenne' Non, 2.4
-Bis(β-7 minnow monobutyl)toluene, His(n
-β-amino-butylphenyl) ether, p-bis(2methyl-4-7minopentyl)benzepe p-bis(1,■-dimethyl-5-7minopentyl)benzene,
These include tri-xylylene diamine, ρ-xylylene diamine, bis(p-7 minocyclohexyl)methane, and the like.

2. The amount of 8-diaminodiphenylene oxide used is 1
It is preferably 0% by weight or more, and if it is less than this, the effect of improving heat resistance is 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.

In the present invention, it is preferable that the reaction between the aromatic tetracarboxylic dianhydride and the aromatic diamine be carried out in equimolar amounts as much as possible; Care must be taken because 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.

Usually, using 1 to 3% more of one raw material improves workability.
This is often done to improve workability.

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-diaminosphenyl oxide.

In addition to being inert to the system and being a solvent to the product, this property is 8! The polar solvent must be solvent for at least one, preferably both, of the reaction components.

Typical solvents of this type are N,N-dimethylformamide, N,N-diethyl 7cetamide, and N.

N-diethylformamide, N,N-diethyl 7-cetamide, N,N-dimethylmethoxyacetamide, dimethyl-resulfoxyr, hexamethyl-7-osphoramide, N-
Examples include methyl-2-pyrrolidone, pyridine, dimethylsulfone, tetramethylenesulfone, and dimethyltetramethylenesulfone, and these solvents may be used alone or in combination.

In addition, non-solvents such as benzene, benzonitrile, dioxane, butyrolactone, xylene, toluene, and cyclohexane are also used in combination as solvents, and are used as dispersion media for raw materials, reaction conditioning agents, or for evaporation of solvents from products. Used as a regulator, film smoothing agent, etc.

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) The method of pre-mixing diamines and tetracarboxylic dianhydride and adding the mixture little by little into an organic solvent while stirring is relatively advantageous in exothermic reactions such as those for polyimide resins. be.

(2) Conversely, there is also a method of adding a solvent to a mixture of diamines and tetracarboxylic dianhydride without stirring.

(3) A commonly used method is to dissolve only diamines in a solvent and add tetracarboxylic dianhydride to this in a proportion that allows control of the reaction rate.

(4) Alternatively, diamines and tetracarboxylic dianhydride may be separately dissolved in a solvent and the two solutions may be slowly added 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.

The reaction temperature is preferably 0 to 100°C. This is because when the temperature is below 0°C, the reaction rate is slow, and when the temperature 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 heptalic acid anhydride or aniline, or add water to ring-open one of the acid anhydride groups to inactivate it.

When used, the polyamic acid product produced by the method of the present invention can be used to improve the adhesion and adhesion of various silane coupling agents, borane coupling agents, nathanate coupling agents, aluminum coupling agents, and other chelate-based coupling agents. In addition to these, small amounts of ordinary acid curing agents, amine curing agents, polyamide curing agents, and curing accelerators such as imidazole and tertiary amines may be added. Also, flexibility additives and viscosity modifiers such as rubber, polysulfide, polyester, and low-molecular epoxy, talc, clay, mica,
Fillers such as feldspar powder, quartz powder, magnesium oxide,
Coloring agents such as carbon black, 7 taroshi 7 nin blue,
Small amounts of flame retardants such as tetraprophenylmethane, tributyl phosphate, and flame retardant aids such as heptimony trioxide and barium mechaborate may also be added, and the addition of these opens up many applications.

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 of the former heating dehydration treatment is usually 50'C or higher,
In particular, a temperature range of 150°C or higher and 200 to 400°C is preferred.

In this case, although air may be used as the atmosphere, it is often preferable to use a non-oxidizing atmosphere 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.
These are particularly effective when used in the coexistence of basic substances such as pyridine and quinoline.

(Effect of the invention 1) The polymer using 2,8-noamino diphenylene oxide and 4,41-diaminodiphenyl ether according to the method of the present invention has better heat resistance than conventionally obtained heat resistant resins. It is an extremely heat-resistant resin with well-balanced flexibility.

That is, 1) 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 provide excellent flexibility due to a spring-like effect.

Specifically, the present invention is used as a coating film for protecting the surfaces of various electronic equipment, and as a heat-resistant insulating film for forming multilayer wiring thereon.

For example, it is a wiring structure for electronic circuits such as semiconductors, transistors, linear ICs, hybrid ICs, light emitting diodes, LSIs, and very large scale integrated circuits.

Furthermore, it is also used to impart heat resistance to various materials, to prevent microwaves, and to prevent radiation.

Examples include waveguides such as Humputer, atomic equipment, and interior materials for X-ray equipment.

Next, it is used as a coaching 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 impregnating varnish for glass cloth, fused silica cloth, etc.
It is used to impregnate graphite fibers and boron fibers, and is used in radar domes, printed circuit boards, radioactive waste containers, turbine blades, and structural parts of spacecraft and ponds that require high temperature performance and excellent electrical properties. It is also used as an interior material for waveguides in computers, atomic equipment, and X-ray equipment to prevent radiation.

Graphite powder, graphite fiber, molybdenum disulfide, and polytetrafluoroethylene are also used as molding materials to create self-lubricating sliding surfaces, such as piston rings,
It is used for 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, and 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 according to the present invention can be used in many other applications.

[Example 1 The present invention will be explained below with reference to Examples.

Example 1 0.5 mol (49.71% by weight) of purified anhydrous 2.8-noamindiphenylene oxide was placed in a four-neck separable 7 rack equipped with a thermometer, stirrer and dry nitrogen gas inlet. ) and 0.5 mol (50.3% by weight) of 4,4'-diaminonophenyl ether, and a mixed solvent of 95% anhydrous N-methyl-2-pyrrolidone and 5% toluene.
An amount sufficient to make the solid content of all raw materials 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 acid anhydride was added little by little while increasing the temperature, and the mixture was cooled by circulating cold water at about 15° C. in an external water tank to prevent heat generation.

After the addition, the internal temperature was set at 20° C. and stirring was continued for 10 hours to complete the reaction.

The resulting product is a yellow transparent, extremely viscous polyamic acid, with an intrinsic viscosity of 0.81 (30
°C).

Next, this polyamic acid was dropped onto a glass plate, and was heated with a spinner at 200 rpm/min for 10 seconds, then for 15 minutes.
It was rotated for 30 seconds at 00 rpm/min to form a film.

This was heated to 80°C1 then 150°C1250" under reduced pressure.
The mixture was sequentially heated at C1350''C for 30 minutes each to cause dehydration and ring closure, thereby obtaining a 20 μm yellow-brown transparent and tough polyimide resin film.

The infrared absorption spectrum of this film is 1780
Strong absorption based on the imide ring was observed at cm-' and 730 cm-', and strong absorption based on the 7-ran ring was observed at 1200 co+-'.

This film has a high temperature stability and extremely high heat resistance, and was measured using a differential thermal balance analyzer at a heating rate of 5°C/va in the air.
The thermal decomposition onset temperature of the film at in was 470°C.

Example 2 Using the same apparatus and method as in Example 1, 0.3 mol (28.6% by weight) of 2,8-diaminodiphenylene oxide and 4
゜4゛-diaminonophenyl ether 0.5 mol (48
, 11°C%) and further 0.2 mol (23.3% by weight) of 4,4'-diaminodiphenyl ether-3-carbonamide. Mol was reacted. The obtained product was a colorless and transparent extremely viscous polyamic acid, and had an intrinsic viscosity of 0.81.

In addition, the obtained film is a yellow transparent polyimide O (greasy film) with extremely high flexibility and excellent heat resistance.
The thermal decomposition initiation temperature was 450°C.

Comparative Example 1 A diamine component was prepared using the same equipment and method as in Example 1.
4,4'-diaminodiphenyl ether only 1 mol (1
00% by weight).

The obtained film had extremely high flexibility and properties, but the thermal decomposition onset temperature was only 360°C.

Comparative Example 2 Using the same apparatus and method as in Example 1, 4 was added as a diamine component.
．． 4′-diaminodiphenyl ether 0.92 mol (9
2.1% by weight) and 0.08 mol (7.9% by weight) of 2,8-noaminodiphenylene oxide.

The obtained film had very high properties of fair and slow properties, but the thermal decomposition initiation temperature was extremely low at 370°C.

Claims (3)

[Claims] (1) When reacting aromatic tetracarboxylic dianhydride and aromatic diamine to form an imide ring, 2,8-diaminodiphenylene oxide and 4,4'-diaminodiphenyl ether are essential components as aromatic diamine components. A method for producing a heat-resistant resin, characterized by: (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.