JPS61176632A - Production of heat-resistant resin - Google Patents

Abstract

PURPOSE:To obtain a polyimide resin, having balanced heat-resistance, flexibility, colorlessness and adhesivity, and high light transmittance and toughness, by using a specific tetracarboxylic acid dianhydride and a specific diamine as essential components. CONSTITUTION:The objective polyimide resin is derived from a tetracarboxylic acid dianhydride component composed of (>=20mol%) 3,3',4,4'- benzophenonetetracarboxylic acid dianhydride and a diamine component composed of (0.5-50mol%) 2,8-diaminodiphenylene oxide, (>=20mol%) 3,3'- diaminodiphenylsulfone and (0.1-30mol%) 1,3-bis(m-aminophenyl) tetramethyldisiloxane. The reaction of both components is carried out preferably at an equimolar ratio.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a strong heat-resistant resin having excellent light transmittance and having a hetero imide ring and a furan ring in the polymer main chain. It is. The purpose is that the cured resin imidized by the ring-closing process has excellent heat resistance, abrasion resistance, chemical resistance, electrical insulation, film-forming properties, flexibility, mechanical properties, etc. as a polyimide resin. We provide heat-resistant resins that are useful as materials for electronic devices, electrical insulation materials, coatings, adhesives, paints, molded products, laminates, fibers, and film materials, but especially for liquid crystal displays for electronic devices. The present invention provides a heat-resistant resin useful as an alignment film for elements.

[Prior art]

Conventionally, polymers having heterocycles such as imide, imidazole, thiazole, oxazole, oxadiazole, triazole, quinoxaline, thiadiazole, oxazinone, quinazoline, imidazopyrrolone, isoindoroquinazolone, etc. in the main chain of the polymer have good heat resistance. 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, they have poor flexibility, flexibility, elongation, or adhesiveness. Therefore, when used as an alignment film for liquid crystal, for example, it cannot withstand rubbing work and cannot fully align the liquid crystal, making it unable to function as a display element. Furthermore, when these polymers are heated during curing, they become significantly colored, becoming brown or blackish brown. Therefore, when used as an alignment film for a liquid crystal, for example, the liquid crystal display element becomes brownish, the visual field becomes dark, the contrast decreases, and it 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 to overcome these drawbacks, the present invention uses 2,8-diaminodiphenylene oxide, 3,3'-diaminodiphenylsulfont, 1,3-bis(m-7 Heat resistance and flexibility are achieved by using 3.3'- and 4.4'-benzophenonetetracarboxylic dianhydride as essential components. The present invention was completed based on the discovery that a heat-resistant resin with a good balance of light color and adhesiveness can be obtained.

[Structure of the invention]

In the present invention, when a diamine and a tetracarboxylic dianhydride are reacted to form an imide ring, 2,8-diaminodiphenylene oxide and 3,3
'-Diaminodiphenylsulfont, 1,3-bis(3
-aminophenyl)tetramethyldisiloxane,
3.3' as tetracarboxylic dianhydride? 4.4'
- A method for producing a heat-resistant resin, characterized by using benzophenone tetracarboxylic dianhydride as an essential component.

Among the diamines used in the present invention, essential components are 2°8-diaminodiphenylene oxide, 3,3'-diaminodiphenylsulfone, and 1,3-bis(m-aminophenyl)tetramethyldisiloxane. The reaction formula for one method of producing 2.8-diaminodiphenylene oxide is as follows.

Diphenylene oxide 2,8-dibromodiphenylene oxide 2,8-diaminodiphenylene oxide Reference: University of Fukui Faculty of Engineering Research Report 16 (2) 238
('68) Of course, diamines other than those mentioned above can also be used. For example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, benzidine, 4,4/-diaminodiphenyl sulfide, 4°4'
-diaminodiphenylsulfone, 414'-diaminodiphenyl ether, 2,6-diamitupyridine, bis(
4-aminophenyl)phosphine oxyto, bis(4-
(aminophenyl)-N-methylamine, 1.5-diaminonaphthalene, 3.3'-dimethyl-4I4'-diaminobiphenyl, 3.3'-dimethoxybenzidine, 2.
4-bis(β-amino-t-butyl)toluene, bis(
p-β-amino-t-butylphenyl)ether, p-
Bis(2methyl-4-aminoynthyl)benzene, p-
Bis(Ll-dimethyl-5-amino-4-ethyl)benzene, m-xylylenediamine, p-xylylenediamine,
Bis(p-aminocyclohexyl)methane, ethylenediamine, propylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine,
Nonamethylene diamine, decamethylene diamine, 3-methyl hebutamethylene diamine, 4,4-dimethyl hebutamethylene diamine, 2゜11-diaminodecane, 1.2
-bis(3-aminoproxy)ethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine,
These include 2,5-dimethylnonamethylene diamine, 1,4-diaminocyclohexane, 2,12-diaminooctadecane, and 2,5-diamino-1,3,4-oxadiazole.

Furthermore, among the tetracarboxylic dianhydrides used in the present invention,
The essential component is 3t 3'+ 4t 4'-benzophenone tetracarboxylic 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
t6-naphthalenetetracarboxylic dianhydride, 2,2'
, 3.3'-diphenyltetracarboxylic dianhydride,
2.2-bis(3,4-dicarboxydiphenyl)pronoξ dianhydride, 3,4.9110-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxydiphenyl)ether dianhydride, ethylenetetra Carboxylic dianhydride, naphthalene-1=2-4,5-tetracarboxylic dianhydride, naphthalene-1+4*5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2゜3t 5
e 6+ 7-hexahytronaphthalene-1e2.5.
6-tetracarboxylic dianhydride, 2I6-cyclopentane-L4t5t8-tetracarboxylic dianhydride, 2.7
-cyclonaphthalene-1e4=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)furonogundianhydride, 1,1-bis(
2,3-dicarboxyphenyl)ethane dianhydride, 1.
1-bis(at4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-1,293,4- These include 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%.

Below α5 momole, the heat resistance strength improvement effect is 11・'4〈
If the molar ratio is 50 molar or more, the molecular weight will not increase due to steric hindrance in the molecular structure. Further, the amount of 3,3'-diaminodiphenylsulfont 31 a't 414'-benzophenone tetracarboxylic dianhydride used is preferably 20 moles or more, and if it is less than this, the effect of improving coloration is small. Further, the amount of 1,3-bis(m-aminophenyl)tetramethyldisiloxane used is preferably α1 to 30 molar. If the O content is less than 11 mole, the effect of colorless removal and improvement of adhesiveness will be small, and if it is more than 30 mole, the cured product will become 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 product 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 disol moment that does not react with the tetracarboxylic dianhydride or diamines.

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-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoamide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone,
Tetramethylene sulfone, dimethyltetramethylene sulfone, etc. 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 cyclohexane.
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 the tetracarboxylic dianhydride may be ring-opened by water, 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, 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 I-limide 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 add tetracarboxylic dianhydride to this in a proportion that allows control of the reaction rate.

(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 the diamine compound among the diamines is reacted with tetracarboxylic dianhydride, and one in which the remaining diamine compound and tetracarboxylic dianhydride are reacted, Another option is to mix it before use.

The reaction temperature is preferably 0 to 100°C. If the temperature is below 0°C, the reaction rate is slow, and if it is above 100°C, 7 Q
This is because the amic acid gradually starts a ring-closing reaction.

Usually, the reaction is carried out at around 20°C. d) The degree of polymerization of reamic acid can be controlled in a planned manner.

In order to control the degree of polymerization, one of the acid anhydride groups can be ring-opened and inactivated by adding water to a polymer end-capped with phthalic anhydride or aniline.

The monoreamic acid product produced by the method of the present invention can be used with various silane coupling agents, borane coupling agents, titanate coupling agents, aluminum coupling agents, and other chelate-based adhesives. Adhesion/adhesion improvers, solvents, and 7o-agents may be added. In addition, curing accelerators such as ordinary acid curing agents, amine curing agents, lyamide curing agents, imidazole, tertiary amines, etc. may be added. A small amount of agent may be added, and rubber, lysulfide, pyriester, and low molecular weight agents may be added with flexibility agents and viscosity modifiers such as xylene, talc, clay, mica,
Fillers such as feldspar powder, quartz powder, and magnesium oxide, colorants such as carbon black and phthalocyanine blue, flame release agents such as tetrabromophenylmethane and tributyl phosphate, and flame retardant aids such as antimony trioxide and barium metaborate. Small amounts may be added, and their addition opens up many uses.

The haliamic acid product produced by the method of the present invention is diimidized and cured by heating or by using a dehydrating agent. The heating temperature for the former heating dehydration treatment is usually 50°C or higher, especially 15°C.
The temperature range is preferably 0°C or higher and 200 to 400°C. In this case, air may be used as the atmosphere, but non-oxidizing conditions such as reduced pressure or inert gas are often preferable. 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. In addition, solid dehydrating agents include zeolite-based Molecule Sheep, silica gel, and activated alumina, 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 3,3'-diaminodiphenylsulfone,
! :, a polymer containing 1,3-bis(m-aminophenyl)tetramethyldisiloxane and 3.3',4,4'-benzophenonetetracarboxylic dianhydride as essential components has high heat resistance and flexibility. It is an excellent heat-resistant resin with a good balance of hardness, light color, and adhesiveness.

That is, the polymer synthesized by the method of the present invention has 298-
By using diaminodiphenylene oxide, 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 provide excellent flexibility due to a spring-like effect.

Furthermore, 3.3′-diaminodiphenylsulfone and 3+3
A heat-resistant resin with little coloring can be obtained, probably because the introduction of the ',4,4'-benzophenonetetracarboxylic dianhydride prevents the main chain from forming a conjugated structure. Furthermore, 1.3-
By introducing bis(m-aminophenyl)tetramethyldisiloxane, the imide group content is diluted, resulting in a heat-resistant resin with little coloring and good adhesive properties.

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, semiconductors, transistors, and linear ICs.

Hybrid IC, light emitting diode, LSI, super LSI
It is a wiring structure for electronic circuits such as.

Next, since the heat-resistant resin of the present invention is light in color, 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 a plastic film substrate on which a transparent conductive film containing tin oxide or indium oxide as a main component is formed by a dipping method, a spin coating method, a spray method, a printing method, etc. After heating and curing,
Rubbing treatment. 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 nemate liquid crystals such as thick base type liquid crystals, phenylcyclohexane type liquid crystals, azoxy type liquid crystals, azo type liquid crystals, biphenyl type liquid crystals, ester type liquid crystals, phenyl-pyrimidine deaf liquid crystals, and the above-mentioned 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 nematic liquid crystals. Other high-temperature coaching varnishes are used as electric wire coatings, magnet wires, dip coatings for various electrical parts, and protective coatings for metal parts.They are also used as impregnated varnishes, glass cloth, fused silica cloth, graphite fibers, and boron fibers. Used for impregnation of radar domes, printed circuit boards,
Used in radioactive waste storage containers, turbine blades, spacecraft and other structural components that require high-temperature performance and excellent electrical properties.
It is also used as an interior material for waveguides in convenience stores, 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 ethylene tetrafluoride, and is used for piston rings, valve seats, bearings, seals, etc. In addition, 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 29.73 of purified anhydrous 2,8-diaminodiphenylene oxide was placed in a four-neck Seno Z rubble flask equipped with a temperature needle, a stirrer, a raw material inlet, and a dry nitrogen gas inlet.
5 F (15 mol %), 173.810 f (70 mol qb) of 3,3'-diaminodiphenylsulfone, and 47.483 f (15 mol qb) of 1,3-bis(m-aminophenyl)tetramethyldisiloxane. %) and shi,
To this, 95 g of anhydrous N-methyl-2-pyrrolidone,
A mixed solvent containing 5 parts by weight of xylene was added in an amount sufficient to make the solid content ratio in the total raw materials 15 parts by weight to 1%, and dissolved. Dry nitrogen gas was kept flowing throughout the entire process from the reaction preparation stage to product removal.

Then purified anhydrous 3.3', 4.4'-benzophenonetetracarboxylic dianhydride 322.230 f
(100 mol mol was added little by little while stirring, but since it was an exothermic reaction, it was cooled by circulating cold water of about 15°C in an external water tank.The internal temperature of the addition diameter was set at 20°C, After stirring for an hour, the reaction was completed.

The obtained product was a transparent yellow and extremely viscous monoreamic acid solution, and the intrinsic viscosity of the 0.5 weight solution of N-methyl-2-pyrrolidone was 0.83 (30°C).

Next, a 5% by weight solution of Konobori amic acid in N-dimethylacetamide was dropped onto a glass plate, and spun at 40 Orpm/min for 10 seconds with a spinner.
and rotate at 2000 rpm/min for 20 seconds.
It was evenly distributed. Under reduced pressure, 80°C, 150°C,
The mixture was sequentially heated at 250° C. and 350° C. for 30 minutes each to cause dehydration and ring closure, thereby obtaining a pale yellow transparent and tough monoimide resin film with a thickness of 1 μm. Looking at the infrared absorption spectrum of this film, strong absorption based on the imide ring was observed at 1780 m-1 and 730 an-', and strong absorption based on the furan ring was observed at 1200 m-1.

This film has extremely excellent heat resistance, and the starting temperature of thermal decomposition in air was 520°C at a heating rate of 5°C/min, as measured by a differential thermal balance analyzer. The film strength was also high, and the tensile strength at 200° C. was excellent at 16 kf/m. Further, the film had excellent light color property, and the light transmittance was 92% at 400 nm. Furthermore, a sellotape peeling test on a glass plate (JIS-D-0202
) had a peeling rate of 0eIII and excellent adhesion.

Example 2 Using the same apparatus and method as in Example 1, 2,8-diaminodiphenylene oxide 19.823f (10 mo"S
) (!: 3,3'-diaminodiphenylsulfone 1
24゜150 f (50 mok To) ト4s4'
-Shifumi/Schif x Nyl Ether 40.048
f (20 mol qII) and 1,3-bis(m-aminophenyl)tetramethyldisiloxane 63.310 f
(20 molt) and 193.338f (60 molt) of 3.3',4,4'-benzophenonetetracarboxylic dianhydride.
momol) and pyromellitic dianhydride 87.248 t
(40 molti) was reacted.

The obtained product was a transparent yellow and extremely viscous amic acid solution with an intrinsic viscosity of 0.88.0 The obtained film was transparent and pale yellow, had high toughness, and had a thermal decomposition initiation temperature. is 515℃, hot tensile strength is 14 kg/-
The light transmittance was 90 and the peeling rate of the tape was excellent.

Comparative Example 1 Using the same apparatus and method as in Example 1, 248.300 f (100% ruti) of 3,3'-diaminodiphenylsulfone and 322 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride were prepared. .230 F (100 molti)
was reacted with.

The obtained film had excellent pale color, but the thermal decomposition onset temperature was only 305°C, the hot tensile strength was 4 kg/ws, and the cellophane tape peeling rate was 90.
It was so bad that it could not withstand the rubbing work.

Comparative Example 2 Using the same apparatus and method as in Example 1, 3,3'-diaminodiphenylsulfone 19B, 640 f (80 mol 1
,! = 1.3-bis(m-aminophenyl)tetramethyldisiloxane 63.310 r (20 mol ts) and 313',4,4'-benzophenonetetracarboxylic dianhydride 322.230 f (100 mol ts) reacted.

The obtained film had excellent light color properties and good adhesion, but the thermal decomposition initiation temperature was only 360° C. and the hot tensile strength was only 4 kti/mL.

Comparative Example 3 Using the same apparatus and method as in Example 1, 19.823 f (10 mol) of 2,8-diaminodiphenylene oxide and 223.f of 3,3'-diaminodiphenylsulfone were prepared.
470 f (90 molti) and 3,314,4'-benzophenonetetracarboxylic dianhydride 322.230
r (100 mol ts).

The obtained film had excellent pale color, high thermal decomposition initiation temperature, and strong hot tensile strength, but the cellophane tape peeling rate was poor at 1 oos.

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, 3,3'-diaminodiphenylsulfone, and 1,3-bis(m-aminophenyl)tetramethyldisiloxane. (2) Claim 1, characterized in that it contains 20 mol% or more of 3,3',4,4'-benzophenone tetracarboxylic dianhydride as a tetracarboxylic dianhydride component. A method for producing the heat-resistant resin described above. (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 3,3'-diaminodiphenylsulfone 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. manufacturing method.