JPS61181832A - 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%), 2,4-diaminotoluene (the content is preferably 20mol%) and 1,3-bis(m-aminophenyl)tetramethyldisiloxane (the content is preferably 0.1-30mol%) are used as essential components of the diamine component.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to the production of a tough heat-resistant resin having dihetero imide rings and furan rings in the polymer main chain with excellent light transmittance. The objective is to improve the heat resistance, abrasion resistance, chemical resistance, electrical insulation, film-forming properties, flexibility, and Material for electronic devices with excellent mechanical properties.

Electrical insulation materials, coatings, adhesives, paints, molded products, fJN
The purpose of the present invention is to provide heat-resistant resins that are useful as layered products, fibers, or film materials, and in particular, to provide heat-resistant resins that are useful as alignment films for liquid crystal display elements for electronic devices (there are two types).

[Prior art]

Conventionally, polymers having a 1-hetero ring in the main chain, such as imide, imidazole, thiazole, oxazole, oxadiazole, triazole, quinoxaline, thiadiazole, oxazinone, quinazoline, imidazopyrrolone, isoindoroquinazolone, etc., are heat resistant. It is well known that it is superior. However, these known polymers have rigid polymer main chains, and when formed into films, films, or coatings (=poor flexibility, flexibility, elongation, or adhesion), for example, alignment films for liquid crystals. When used as a liquid crystal, it cannot withstand rubbing work and the liquid crystal cannot be properly aligned and cannot function as a display element.In addition, these polymers become extremely colored when heated during curing, resulting in a brown or blackish-brown color. (For this reason, for example, when used as an alignment film for liquid crystal, the liquid crystal display element becomes brownish and the field of view becomes dark.

The contrast decreases and the display element no longer functions as a display element. From this point of view, various studies have been made in the past in order to achieve a balance between heat resistance, flexibility, light color property, and adhesiveness, but it has generally been the case that when one is good, the other is bad.

[Purpose of the invention]

As a result of studies aimed at overcoming such drawbacks, the present invention has developed a system that uses 2,8-diaminodiphenylene oxide, 2,4-diaminotoluene, and 1.3-diaminodiphenylene oxide as diamine components.
-bis(m-aminophenyl)tetramethyldisiloxane and 3.3' as the tetracarboxylic dianhydride component.
, 4. It was discovered that by using 4'-benzophenone tetracarboxylic dianhydride as an essential component, a heat-resistant resin with a good balance of heat resistance, flexibility, light color, and adhesiveness could be obtained. Complete the 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 (2.8-diaminodiphenylene oquinide is used as the diamine component; 2.
4-diaminotoluene and 1,3-bis(m-aminophenyl)tetramethyldisiloxane; This is a method for producing a heat-resistant resin characterized by using an anhydride as an essential component.

Among the diamines used in the present invention, essential components are 2,8-diaminodiphenylene oxide, 2,4-diaminotoluene, and 1,3-bis(m-aminophenyl)tetramethyldisiloxane. 2. One way to make 8-diaminodiphenylene oxide is shown in the reaction formula as follows (
Two.

2.8-dibromodiphenylene oxide 2.8-diaminodiphenylene oxide Reference: University of Fukui Faculty of Engineering Research Report 16 (2123
8<768) Of course, diamines other than those mentioned above can also be used. For example, 1m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'
-Diamino diphenyl sulfone, 3.3'-diaminodiphenylsulfone, 4.4'-diaminodiphenyl ether, 2.6-cyamitsupyridine, bis(4-aminophenyl)phosphine oquindo, bis(4-aminophenyl)- N-methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxypenzidine, 2,4-bis(
β-amino-t-butyl)toluene, bis(p-β-amino-t-butylphenyl)ether, p-bis(2methyl-4-aminopentyl)benzene, p-bis(l,
t-dimethyl-5-aminopentyl)benzene, m-xylylenediamine, p-xylylenediamine, bis(p
-Aminopropoquine)methane, ethylenediamine, propylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 3-methylheptamethylenediamine, 4.4-dimethylheptamethylenediamine% 2゜11-diaminodecane, 1.2-bis(3
-aminopropoxy)ethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine,
2.5-dimethylhexamethylene diamine, 2.5-dimetelnonamethylene diamine, 1.4-cyaminone clohexane, 2.12-diaminooctadecane, 2.5-
Diamino-1,3,4-oxadiazole 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-dicarboxyphenyl)propane dianhydride, 3.4.9.10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, ethylenetetracarboxylic dianhydride anhydride, 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-cyclonaphthalene-1.4,5
．． 8-tetracarboxylic dianhydride, 2.7-cyclonaphthalene-1.45.8-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, 1.2
, 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%.

If it is less than 0.5 mol %, the effect of improving heat resistance strength is small, and if it is more than 0.5 mol %, the molecular weight does not increase, probably due to steric hindrance of the molecular structure. Also, 2,4-diaminotoluene and 3.3'
% 4.4'-benzophenonetetracarboxylic dianhydride is preferably used in an amount of 20 mol % or more, and if it is less than 20 mol %, the effect of improving coloration is small. Further, the amount of 1,3-bis(m-aminophenyl)tetramethyldisiloxane used is preferably 0.1 to 30 mol%. 0.1 mol%
If the amount is less than 0.0%, the effect of colorless removal and improvement of adhesiveness will be small, and if the amount is more than 1% by mole, the cured product will be 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 increases by 5% or more, the degree of polymerization will drop significantly and a low-molecular-weight ornament with poor film-forming properties will be produced, so care must be taken. Usually, it is common practice to use 1 to 3% more of one raw material in order 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.

Other than being inert to the system and being a solvent to the product, the organic polar solvent must be a solvent to at least one, preferably both, of the reaction components.

Typical solvents of this type include N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylformamide.
-diethylformamide, N,N-diethylacetamide, N,N-dimethylmethquinacetamide, dimethylforfoquinde, hexamethylphosphoamide, N-methyl-2-pyrrolidone, pyridine, dimethylnulfone, tetramethylenesulfone, dimethyl Examples include tetramethylene sulfone, and these solvents may be used alone or in combination.

Other non-solvents that can be used in combination as solvents include benzene, benzonitrile, dioxane, butyrolactone, xylene, toluene, and nclohexane.
It is used as a dispersion medium for raw materials, a reaction control agent, a volatilization control agent for solvents from products, a film smoothing agent, etc.

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

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

For this reason, the water content in the raw materials is r8tg! It is also necessary to remove the moisture inside.

However, on the other hand, 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.

As the inert gas, general (dry nitrogen gas) is used.

The reaction in the present invention (-) can be carried out in various ways as follows.

(1) Diamines and tetracarboxylic dianhydride are mixed in advance, and the mixture is added little by little to an organic solvent (while stirring). It is advantageous.

(2) On the other hand, there is also a method in which a solvent is added while stirring.

(3) General (2) A commonly used method is to dissolve only diamines in a solvent and then add tetracarboxylic dianhydride at a rate 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) Also, among the diamines, after first reacting one part of the diamine compound and tetracarboxylic dianhydride,
There is also a method in which the remaining diamine compound is reacted, or the reverse method.

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

The reaction temperature is preferably 0 to 100°C. If the temperature is below 0°C, the reaction rate will be slow, and if the temperature is above 100°C, the produced polyamic acid will gradually (because the two-ring closure reaction will start).

Usually, the reaction is carried out at around 20°C. The degree of polymerization of polyamic acid can be controlled (planned).

In order to control the degree of polymerization (=, it is also possible to end-block with phthalic anhydride or aniline, or add water to ring-open one of the acid anhydride groups to inactivate it.

The polyamic acid product produced by method C of the present invention is used (= various Nran coupling agents, poran coupling agents, titanate coupling agents, aluminum coupling agents and other chelate adhesives). A property/adhesion improver, various solvents, and flow agents may be added, and in addition to these, a small amount of a normal acidifying agent, an amine curing agent, a polyamide curing agent, and a curing accelerator such as imidazole or tertiary amine. may also be added, as well as flexibility agents and viscosity modifiers such as rubber, polysulfide, polyester, and low molecular weight Evoquin, talc, clay, mica,
Fillers such as feldspar powder, quartz powder, and magnesium oxide, colorants such as carbon black and phthalocyanine blue, flame retardants such as tetrabromophenylmethane and tributyl phosphate, and flame retardant aids such as antimony trioxide and barium metaborate. Agility may also be added, and the addition of these opens up more uses than two.

The polyamicuccinic acid product produced by the method of the present invention is cured by imidization by heating or by 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, air may be used as the atmosphere, but a non-oxidizing atmosphere such as reduced pressure or an inert gas is often preferable. As the latter dehydrating agent, carboxylic anhydrides such as acetic anhydride, propionic anhydride, and benzoic anhydride are often used. big.

In addition, solid dehydrating agents include zeolite-based Molecuyer Lube, silica gel, and activated alumina, which are more effective when used after being slightly heated.

〔Effect of the invention〕

The method of the present invention (according to two methods, 2,8-diaminodiphenylene oxide, 2,4-diaminotoluene, 1,3-
A polymer containing bis(m-aminophenyl)tetrametheldine loxane and 3.3',4.4'-benzophenonetetracarboxylic dianhydride as essential components has heat resistance, flexibility, light color, and adhesive properties. It is an excellent heat-resistant resin with a good balance of properties.

That is, the method of the present invention (the polymer synthesized from two steps.

2. Use of 8-diaminodiphenylene oxide (it has a bi-molecular structure (-1), which has many aromatic rings and heterocycles, and has excellent heat resistance. Also, the main chain has a helical shape. Therefore, C2 is considered to have excellent flexibility due to its spring-like effect.

Further (2,4-diaminotoluene and 3.3',4.4'
-Introduction of benzophenone tetracarboxylic dianhydride 1:
Perhaps because the main chain is less able to form a conjugated structure, a heat-resistant resin with less coloring can be obtained. Furthermore, C2, 1.3-bis (m
-Introduction of (aminophenyl)tetramethyldisiloxane (
Second, the imide group content is diluted, resulting in less coloring and a heat-resistant resin with good adhesive properties.

Specifically, the present invention is used as a coating film for protecting the surfaces of various electronic equipment, and also as a heat-resistant insulating film for C2 multilayer wiring.

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

(2) Invention C: Since the heat-resistant resin is light in color, it can also be used as an alignment film for liquid crystal display devices.

Namely, (1) the polymer solution of the present invention is coated on a glass substrate or plastic film substrate (C) on which a transparent conductive film containing tin oxide or indium oxide as the main component is coated, (2) by a dipping method, a one-turn 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 Schiff base type liquid crystals, phenylcyclohexane type liquid crystals, and azoquine type liquid crystals.

Nematic liquid crystals such as azo type liquid crystal, biphenyl type liquid crystal, ester type liquid crystal, and phenyl/pyrimidine type liquid crystal.

The above nematic liquid crystals (bi-optical substances, cholesterol compounds, biphenyl derivatives with optically active substituents,
Examples include cholesteric liquid crystals containing optically active compounds such as phenylbenzoate.

In addition, it is used as a coaching varnish for high temperatures, as a coating for electrical wires, magnet wires, dip coatings for various electrical parts, and as a protective coating for metal parts. Impregnated with boron fibers (binary), radar domes, printed circuit boards, radioactive waste containers, turbine blades, spacecraft and other structural parts requiring high temperature performance and good electrical properties (binary, microwave It is also used as an interior material for waveguides such as combinators, atomic equipment, and X-ray equipment to prevent 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, and is used for piston rings, valve seats, bearings, seals, etc. , also by adding glass fiber, graphite fiber and boron fiber,
Jet engine parts and high-strength structural molded parts are made here.

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

〔Example〕

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

Example 1 Purified anhydrous 2 was placed in a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet.
．． 8-Diaminodiphenylene oxide 29.7351
1 (15 mol%) and 2,4-diaminotoluene 85.5
1'l (70 mol%) and %1.3-bis(m-aminophenyl)tetramethyldisiloxane 47.483g (
15 mol%), and a mixed solvent of 95% by weight of N-methyl-2-pyrrolidone dianhydride and 5% by weight of toluene.
An amount sufficient to make the solid content of the total raw materials 15% by weight was added and dissolved. Dry nitrogen gas was allowed to flow throughout the entire process from the preparation stage of the 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, cold water at about 15° C. was circulated in external water tank C to cool it. After the addition, the internal temperature was set at .degree. C. and stirred for 12 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% N-methyl-2-pyrrolidone solution was Q, 80 (30°C).

Next, a 5% by weight solution of this polyamic acid in N-dimethylacetamide was placed on a glass plate (2 times) and spun at 40 rpm/min for 10 seconds using a spinner, then spun at 2000 rpm/min for (9) seconds. Scattering, uniform (= applied. This was applied under reduced pressure at 80℃, 150℃, 2
Heating was performed at 50°C and 350°C for 30 minutes each to cause dehydration and ring closure to obtain a pale yellow, transparent, and strong polyimide resin film with a thickness of 1 μm. Looking at the infrared absorption spectrum of this film, the infrared absorption spectrum was 1780 cm-' and 730cm-'
C imide ring (strong absorption of two groups, 1200α-1
A strong absorption was observed for both furan ring C groups.

This film has extremely excellent heat resistance, and the thermal decomposition initiation temperature in air was 515°C at a heating rate of 5°C/min as measured by 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 with a score of 6 to 9/-. Furthermore, the film had excellent hypochromicity (-) and a light transmittance of 93% at 400 nm.

Further (2. Sellotape peeling test on glass plate (JI)
SD-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%
) and 2,4-diaminotoluene 61.085.9 (5
0 mol%) and 4,4'-diaminodiphenyl ether 4
0.048II (20 mol%) and 1.3-bis(m-
(aminophenyl)tetramethyldisilochitin 63.3)
0# (20 mol%) and 3.3',4.4'-benzophenonetetracarboxylic dianhydride 161.111 (
50 mol%) and pyromellitic dianhydride 109.060
, 9 (50 mol%) (: Reacted.

The obtained product was a transparent yellow and extremely viscous polyamic acid solution with an inherent viscosity of 0.78. The obtained film was pale yellow and transparent, had a high toughness of C:, had a thermal decomposition initiation temperature of 510°C, and had a hot tensile strength of 14 KP/ml.
The light transmittance was excellent, 91%, and the cellophane tape peeling rate was 0%.

Comparative Example 1 Using the same apparatus and method as in Example 1, 2.4-cyamite k:cy 122.1701i (100%)
3.3',4.4'-benzophenonetetracarboxylic dianhydride 322.230.9 (100 mol %) was reacted.

The obtained film had excellent light color property, but the thermal decomposition initiation temperature was 320°C, the hot tensile strength was 5 Kp/-, and the cellophane tape peeling rate was 95%, making it difficult to perform controlled rubbing. It was not something that could withstand.

Comparative Example 2 Using the same apparatus and method as in Example 1, 2,4-diaminotolu x y 97.7361 (80 mol%) and 1.3-
His(m-aminophenyl)tetrametheldine loxay
63.3) 0Jj (20 mol%) and 3.3', 4
．． 4'-benzophenonetetracarboxylic dianhydride 32
2.230.9 (Zo.

% by mole).

The obtained film had good adhesion and light color, but had a thermal decomposition onset temperature of less than 340°C and a hot tensile strength of less than 5KP/ml.

Comparative Example 3 19.823jl (10 mol%) of 2,8-diaminodiphenylene oxide was produced using the same apparatus and method as in Example 1.
and 2,4-diaminotoluene 109.953.91 (9
0 mol %) and 3.3',4.4'-benzophenonetetracarboxylic acid di,anhydride 322.23011 (100 mol %) were reacted.

The obtained film had excellent light color (; thermal decomposition initiation temperature was high and hot tensile strength was strong, but the cellophane tape peeling rate was poor at 100%).

Claims (5)

[Claims] (1) 3,3',4,4'-benzophenone tetracarboxylic dianhydride as the diamine component, 2, 8-diaminodiphenylene oxide, 2,4-diaminotoluene and 1
, 3-bis(m-aminophenyl)tetramethyldisiloxane 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) The heat-resistant resin according to claim 1, which contains 0.1 to 30 mol% of 1,3-bis(m-aminophenyl)tetramethyldisiloxane as a diamine component. Production method.