JPS61181830A - Production of heat-resistant resin - Google Patents

Abstract

PURPOSE:To improve the balance of the obtained polyimide resin among heat resistance, flexibility, color lightness, adhesiveness, etc., by using specified compounds as tetracarboxylic acid dianhydride and diamine components. CONSTITUTION:3,3'4,4'-Benzophenonetetracarboxylic acid dianhydride is used as an essential component of the tetracarboxylic acid dianhydride component (the content is preferably 20mol% or higher). 2,8-Diaminodiphenylene oxide (the content is preferably 0.5-50mol%), 1,4-bis(3-aminopropyldimethylsilyl) benzene (the content is preferably 0.1-30mol%) and 2,4-diaminotoluene (the content is preferably 20mol% or higher) are used as essential components of the diamine component.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing a strong heat-resistant resin having a hetero imide ring and a furan ring in the polymer main chain (; = is related to. Its purpose is to
The cured resin imidized by ring-closing treatment has the heat resistance, abrasion resistance, chemical resistance, electrical insulation properties, and
We provide heat-resistant resins with excellent film-forming properties, flexibility, and mechanical properties that are useful as materials for electronic devices, electrical insulation materials, coatings, adhesives, paints, molded products, laminates, fibers, and film materials. In particular, we provide heat-resistant resins useful as alignment films for liquid crystal display elements for electronic devices.

[Prior art]

Conventionally, polymers with diheterocycles (such as imide, imidazole, thiazole, oxazole, oxadiazole, triazole, quinoxaline, thiadiazole, oxazinone, quinazoline, imidazopyrrolone, isoindolo, quinazolone, etc.) in the main chain of the polymer have high heat resistance. However, these known polymers have a rigid main chain, and when made into a film, film, or coating, they exhibit poor flexibility, flexibility, elongation, or adhesion. Therefore, when used as an alignment film for liquid crystal, for example, it cannot withstand rubbing work, and the liquid crystal cannot function as a display element due to sufficient alignment. When heated during curing, the coalescence becomes significantly colored and becomes brown or blackish brown (2). Therefore, when used as an alignment film for liquid crystal, for example, the liquid crystal display element becomes brownish, the field of view becomes dark, the contrast decreases, and the function as a display element is impaired. From this perspective, various studies have been conducted in the past to achieve a balance between heat resistance, flexibility, light color property, and adhesiveness, but as a rule, when one improves, the other deteriorates. there were.

[Purpose of the invention]

As a result of studies aimed at overcoming such drawbacks, the present invention has developed the following diamine components: 2,8-diaminodiphenylene oxide, 2,4-diaminotoluene, and 1,4-diaminodiphenylene oxide.
-bis(3-aminopropyldimethylsilyl)benzene, also as a tetracarboxylic dianhydride component, 3.3'
, 4,4'-benzophenonetetracarboxylic dianhydride as essential components (Secondly, a heat-resistant resin with a good balance of heat resistance, flexibility, light color, and adhesiveness can be obtained) Discover and complete the present invention (=
It has arrived.

[Structure of the invention]

In the present invention, a diamine and a tetracarboxylic dianhydride are reacted to form an imide ring (= in which 2,8-diaminodiphenylene oxide and 2,4-
Diaminotoluene, 1,4-bis(3-aminopropyldimethylsilyl)benzene, and 313-4,4'-benzophenonetetracarboxylic dianhydride are used as essential components. This is a method for producing a heat-resistant resin.

Among the diamines used in the present invention, essential components are 2,8-diaminodiphenylene oxide, 2,4-97 minotoluene, and 1,4-bis(3-aminopropyldimethylsilyl)benzene. One way to make 2,8-diaminodiphenylene oxide is shown in the following reaction formula (two reactions).

Diphenylene oxide 2.8-Diaminodiphenylene oxide Reference: University of Fukui Faculty of Engineering Research Report 16 (2) 2
38 ('68) Of course, diamines other than those mentioned above can also be used. For example, m-phenylene diamine, p-phenylene diamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4 chiamino diphenyl sulfide, 4,4'-
Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 2,6-cyamitubiridine, bis(4-aminophenyl)phosphine oxyto, bis(4-aminophenyl)-N-methylamine , 1,5-diaminonaphthalene, 3.3'-dimethyl-4,4'-diaminobiphenyl, 3. Gordimethquin benzidine, 2,4-bis(β-
Amino-1-butyl)toluene, bis(p-β-amino-t-butylphenyl)ether% p-bis(2methyl-4-aminopentyl)benzene, p-bis(1,
l-dimethyl-5-aminopendel)benzene, m-xylylenediamine, p-quinlylenediamine, bis(p
-aminopropoquine)methane, ethylenediamine, pro-diamine, hexamethylenediamine.

Heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 3-methyl hebutamethylene diamine, 4,4-dimethyl hebutamethylene diamine, 2,11-diaminodecane, 1.2-
Bis(3-aminopropoquine)ethane, 2,2-dimethylpropylenediamine, 3-methquinequinamethylenediamine, 2,5-dimethylhexamethylenediamine, 2
, 5-dimethylnonamethylenediamine, 1,4-cyaminone clohexane, 2,12-diaminooctadecane, 2,5-diamino-1,3,4-okinasiazole, and the like.

Also, among the tetracarboxylic dianhydrides used in the present invention,
The essential component is 3.3', 4.4'-benzophenonetetracarboxylic dianhydride. However, other tetracarboxylic dianhydrides can of course also be used. For example, pyromellitic 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-helentitracarboxylic dianhydride, bis(3,4-dicarboxydiphenyl)
Ether dianhydride, ethylenetetracarboxylic 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 Acid dianhydride, 2,6-dichloronaphthalene = 1°4.5
．． 8-Tetracarboxylic dianhydride, 2,7-cyclonaphthalene-1.4,5.8-tetracarboxylic dianhydride, 2,3,4.7-titrachloronaphthalene-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, bis(2,3
-dicarboxyphenyl)methane dianhydride, bis(3,
4-dicarboxyphenyl)sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, l.

2.3.4-butanetetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, and the like.

The amount of 2,8-diaminodiphenylene oxide, which is an essential component, is preferably 0.5 to 50 mol%.

0.5 mol% is preferred. If it is less than 0.5 mol%, the effect of improving heat resistance strength is small, and if it is more than 50 mol%, the molecular weight does not increase, probably due to steric hindrance of the molecular structure. Also 2.4-
The amount of diaminotoluene and 3.3',414'-benzophenonetetracarboxylic dianhydride used is preferably 20 mol% or more, and if it is less than this, the effect of improving coloration is small. Further, the amount of 1,4-bis(3-aminopropyldimethylsilyl)benzene used is 0.1 to 30 mol%.
is preferred. If it is less than 0.1 mol %, the effect of color-free and adhesive improvement is small, and if it is more than 30 mol %, the cured product becomes brittle.

In the present invention (the reaction between diamines and tetracarboxylic dianhydrides is preferably carried out in equimolar amounts as much as possible,
The degree of polymerization also increases. If the amount of either raw material is increased by 5% or more, the degree of polymerization will decrease significantly, resulting in a low-molecular ornament with poor film forming properties.Usually, 1 to 3% more of one of the raw materials is used. 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 the tetracarboxylic dianhydride or diamines.

The organic polar solvent must be a solvent for at least one, preferably both, of the reaction components, except that it is inert to the system and is a solvent for the product.

Typical solvents of this type include N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylformamide.
-diethylformamide, N,N-diethylacetamide, N,N-dimethylmethquinacetamide, dimethylsulfondo, hexamethylphosphoamide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetramethylene There are sulfones, etc., and these solvents are used alone or in combination.

In addition, non-solvents such as benzene, benzonitrile, dioxane, phthyrolactone, xylene, toluene, and cyclohexine, which are used in combination as solvents, can be used as dispersion media for raw materials, reaction regulators, or solvents for products. It is used as a volatilization regulator, film smoothing agent, etc.

It is generally preferred that the present invention be carried out under hydrothermal conditions.

This is because tetracarboxylic dianhydride may ring-open from water (2), inactivating it, and stopping the reaction.

Therefore, it is necessary to remove both the moisture in the raw materials and the moisture in the solvent.

However, in order to adjust the progress of the reaction and control the degree of resin polymerization, water is sometimes added.

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 method in the present invention (=) can be carried out in various ways as follows.

It is done in a method.

(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 for exothermic reactions such as polyimide resins.

(2) On the contrary, there is also a method of adding a solvent while stirring.

(3) General (= A commonly used method is to dissolve only diamines in a solvent and then add tetracarboxylic dianhydride in a proportion that allows the reaction rate to be controlled. (4) Also, diamines It is also possible to dissolve the dianhydride and tetracarboxylic dianhydride separately (solvent C2) and then slowly add the two solutions in the reactor.

(5) Further, 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 react them in a reactor.

C6) Among the diamines, there is also a method in which a portion of the diamine compound is reacted with tetracarboxylic dianhydride (=) and then the remaining diamine compound is reacted, or the reverse method is also available.

(In addition to this, some diamine compounds and tetracarboxylic dianhydride are reacted together, and the remaining diamine compound and tetracarboxylic dianhydride are reacted together before use.) (There is also a method of mixing the two.

The reaction temperature is preferably 0 to 100°C. This is because if the temperature is 0°C or lower, the reaction rate is slow, and if the temperature is 100°C or higher, 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 planned (= controlled).

To control the degree of polymerization (=, no phthalate
It is also possible to end-block with a hydrate or aniline, or add water to open one of the acid anhydride groups and inactivate it.

The polyamic acid product produced by the method (2) of the present invention is used (= various silane coupling agents, borane coupling agents, titanate coupling agents, aluminum coupling agents and other chelate adhesives). A property/adhesion improver, various solvents, flow agents may be added, and these (= in addition, small amounts of ordinary acid curing agents, amine curing agents, polyamide curing agents, and curing accelerators such as imidazole and tertiary amines) may also be added, as well as flexibility additives and viscosity modifiers such as rubber, polysulfide, polyester, and low-molecular epoxy; fillers such as talc, clay, mica, feldspar powder, quartz powder, and magnesium oxide;
Colorants such as carbon black and phthalocyanine blue,
Small amounts of flame retardants such as tetrabromophenylmethane, tributyl phosphate, flame retardant aids such as antisulfur dioxide, barium metaborate, etc. may also be added, and the addition of these opens up many uses.

The polyamic acid product produced by the method of the present invention is cured by imidization by heating or by using a dehydrating agent.

The heating temperature for the former heating and dehydration treatment is usually 50°C or higher Special c1
The temperature range is preferably 50°C or higher and 200 to 400°C.

In this case, although the atmosphere may not be suitable in some cases, it is often preferable to use a non-oxidizing atmosphere such as reduced pressure or an inert gas. For the latter, acetic anhydride and propionic anhydride are used as dehydrating agents.

Carboxylic anhydrides such as benzoic anhydride are often used, but these are particularly effective when used in the coexistence of a basic substance such as pyridine or quinoline. Also, solid dehydrating agents include zeolite-based moleki, silica gel,
There are activated aluminas, etc., which are more effective when used after being slightly heated.

〔Effect of the invention〕

According to the method of the invention, 2,8-diaminodiphenylene oxide and 2,4-diaminotoluene.

The polymer, which uses 1.4-bis(3-aminoprobyldimethylsilyl)benzene and 3.3',4,4'-benzophenonetetracarboxylic dianhydride as essential components, has heat resistance, flexibility, and light color. It is an excellent heat-resistant resin with a good balance of strength and adhesion.

That is, the polymer synthesized by the method of the present invention has a 2.8-
Use of diaminodiphenylene oxide C: It has a large number of aromatic rings and heterocycles in its molecular structure, and has excellent heat resistance. In addition, the main chain has a helical shape, which is thought to give it excellent flexibility due to a spring-like effect.

Furthermore, 2,4-diaminotoluene, 3.3'% 4.4
′-Introduction of benzophenone tetracarboxylic dianhydride (
:Probably because the main chain is less able to form a conjugated structure, a heat-resistant resin with less coloring can be obtained. Furthermore (2, 1.4-bis(
Introduction of 3-aminopropyldimethysilyl)benzene (
Second, the imide group content is diluted, resulting in a heat-resistant resin with less coloring and good adhesiveness.

Here are some specific uses for which the present invention is used:

First, it is used as a coating film to protect the surface of various electronic equipment, and also as a heat-resistant insulating film for multilayer wiring.

For example, it is a wiring structure for electronic circuits such as semiconductors, transistors, linear ICs, hybrid IC1 light emitting diodes, LSIs, and very large scale integrated circuits.

Next, the present invention (because the second heat-resistant resin is light-colored,
It can also be used as an alignment film for liquid crystal display devices.

That is, the polymer solution of the present invention is applied to a glass substrate or plastic film substrate 1 on which a transparent conductive film containing tin oxide or injecum oxide as a main component is formed, by a dipping method, a spin coating method, a spray method, a printing method, etc. After coating and curing by heating, it is rubbed.

The rubbing method can be performed using gauze, puff polishing, or other conventional means. Liquid crystals that can be used in combination with the alignment film of the present invention include nematic liquid crystals such as Schiff base type liquid crystals, phenyl-chrohechitin type liquid crystals, azoxy type liquid crystals, azo type liquid crystals, biphenyl type liquid crystals, ester type liquid crystals, and phenyl-pyrimidine type liquid crystals. Examples include cholesteric liquid crystals in which optically active compounds such as optically active substances, cholesterol compounds, biphenyl derivatives having optically active substituents, and phenylbenzoate are added to the above-mentioned nematic liquid crystals.

In addition, it is used as a coaching varnish for high temperatures, as a coating for electric wires, magnet wires, dip coatings for various electrical parts, and as a protective coating for metal parts.

Used for impregnation of glass cloth, fused silica cloth, graphite fibers and boron fibers, radar domes, printed circuit boards, radioactive waste containers, turbine blades, and spacecraft requiring high temperature performance and excellent electrical properties.

It is used for other structural parts, and as an interior material for computer nanowaveguides, atomic equipment, and X-ray equipment to prevent microwaves and radiation.

Graphite powder, graphite fiber, molybdenum disulfide, and polytetrafluoroethylene are also added as molding materials to create self-lubricating sliding surfaces (for use in piston rings, valve seats, bearings, seals, etc.). It is also used with the addition of glass, graphite, and boron fibers to make jet engine parts and high-strength structural molded parts.

It is also used as a high-temperature adhesive for bonding electrical circuit parts and for bonding structural parts of spacecraft.

〔Example〕

The present invention will be explained from the following Examples (Second).

Example 1 39.646 ml of purified anhydrous 2,8-diaminodiphenylene oxide was placed in a four-cross separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet.
Il (20 mol%) and 2,4-diaminotoluene 85
．． 519f9 (70 mol%) and 1.4-bis(3-
Aminopropyldimethylsilyl)benzene 30.862
Ii (10 mol %) was mixed with a mixed solvent of 95% by weight of anhydrous N-methyl-2-pyrrolidone and 5% by weight of Kin 2, and the solid content in the total raw materials was 15% by weight. Add enough amount to dissolve. Dry nitrogen gas was allowed to flow throughout the entire process from the preparatory stage of one reaction to the removal of the product.

Next, 322.230 g (10
0 mol%) was added little by little with stirring, but since it was an exothermic reaction, it was cooled by circulating cold water at about 15°C in an external water tank.The temperature at the end of the addition was set at 20°C. The mixture was stirred for 10 hours to complete the reaction.

The obtained product was a transparent yellow and extremely viscous polyamic acid solution, and the intrinsic viscosity of the 0.5 weight N-methyl-2-pyrrolidone solution was 0.64 (30°C).

Next (:%) A 5% solution of this polyamic acid in N-dimethylacetamide was placed on a glass plate (2 parts) and spun with a spinner at 40 rpm/min for 10 seconds and then at 2000 rpm/n+in for 1/2 second. , uniform (=
Coated. This was heated at 80°C, 150°C, and 250°C under reduced pressure.
℃.

The infrared absorption spectrum of this film was examined at 1780fi-' and 739m-'. Imide ring (2-based strong absorption and 1200cIL''-'lnifuran ring (
Two strong absorptions were observed.

This film has extremely excellent heat resistance, and the thermal decomposition initiation temperature in air was 500°C at a heating rate of 5°C/min as measured using a differential thermal balance analyzer.

The film strength is also high, with a tensile strength of 1 when heated at 200°C.
It was excellent at 3KF/-. Further, the film had a light color C2 excellent light transmittance of 92% at 400°C.

Furthermore, a sellotape peeling test (JIS
-D-2020) had excellent adhesiveness with a peeling rate of 0%.

Example 2 Using the same apparatus and method as in Example 1, 2,8-diaminodiphenylene oxide 19.823.9 (10 mol%
), 73.302 g (6o mol %) of 2,4-diaminotoluene, and 40.4'-diaminodiphenyl ether.
048, F (20 mol%) and 1,4-bis(3-aminopropyl9)frunril)benzene 30.8621
! (10 mol%) and 3.3',4.4'-benzophenonetetracarboxylic dianhydride 161.115II (
50 mol%) and pyromellitic dianhydride 109.06O
It was reacted with N (50 mol%).

The obtained product was a transparent yellow and extremely viscous polyamic acid solution with an inherent viscosity of 0.168. The obtained film was transparent and pale yellow, had a high toughness (G), had a thermal decomposition initiation temperature of 500°C, and had a hot tensile strength of 13 Kp/j.
The light transmittance was 90% and the cellophane tape peeling rate was 0%, which were excellent.

Comparative Example 1 Using the same apparatus and method as in Example 1, 2.4-diaminotoluene 122.170, F (100 mol%) and 3.
3',4,4'-benzophenonetetracarboxylic dianhydride 322.230 # (100 mol %) was reacted.

Although the obtained film had excellent light color property, the thermal decomposition initiation temperature was only 320°C.

The hot tensile strength was 59/-, the cellophane tape peeling rate was poor at 95%, and it could not withstand rubbing work.

Comparative Example 2 Using the same apparatus and method as in Example 1, 9r of 2,4-diaminotoluene, 36 g (80 mol%) and 61.
721 (20 mol%) and 3.3',4.4'-benzophenonetetracarboxylic dianhydride 322.230
, P (100 mol%) were reacted.

The obtained film had excellent light color (= excellent adhesion), but the thermal decomposition initiation temperature was only 320° C. and the hot tensile strength was only 5 KP/mfL.

Comparative Example 3 Using the same apparatus and method as in Example 1, 9.523i (io mol%) of 2.8-diaminodiphenylene oxide, 109.953 g (90 mol%) of 2.4-diaminotoluene, and 3.3' , 4,4'-benzophenonetetracarboxylic dianhydride 322.230.9 (100 mol%
) were reacted. The obtained film had considerably excellent light color property, high thermal decomposition initiation temperature, and strong hot tensile strength, but the cellophane tape peeling rate was poor at 100%.

Claims (5)

[Claims] (1) 3,3',4,4'-benzophenone tetracarboxylic dianhydride is used as the tetracarboxylic dianhydride component of the polyimide resin consisting of tetracarboxylic dianhydride and diamine, and 2 , 8-diaminodiphenylene oxide, 2,4-diaminotoluene, and 1,4-bis(3-aminopropyldimethylsilyl)
A method for producing a heat-resistant resin characterized by containing benzene as an essential component. (2) Claim 1, characterized in that the content of 3,3',4,4'-benzophenonetetracarboxylic dianhydride is 20 mol% or more as the tetracarboxylic dianhydride component. A method for producing heat-resistant resin. (3) The method for producing a heat-resistant resin according to claim 1, which contains 0.5 to 50 mol% of 2,8-diaminodiphenylene oxide as a diamine component. (4) The method for producing a heat-resistant resin according to claim 1, which contains 20 mol% or more of 2,4-diaminotoluene as a diamine component. (5) Production of a heat-resistant resin according to claim 1, which contains 0.1 to 30 mol% of 1,4-bis(3-aminopropyldimethylsilyl)benzene as a diamine component. Method.