JPS59189123A - Production of polyimide resin solution - Google Patents

Abstract

PURPOSE:To produce a solution of a polyimide resin soluble in a halogenated phenol compound and excellent in storage stability, by polymerizing a specified tetracarboxylic acid component with a specified aromatic diamine component under a specified condition and dehydrating the product. CONSTITUTION:A polyimide resin solution is obtained by (i) pre-reacting a substantially equimolar mixture of a tetracarboxulic acid component based on 3,3', 4,4'-benzophenonetetracarboxylic acids and an aromatic diamine component based on 4,4'-diaminodiphenyl ether at 100-200 deg.C in a hydrogenated phenolic compound (e.g., p-chlorophenol) to a reduced specific viscosity <=0.1, while removing the water of condensation formed, (ii) post-polymerizing the mixture at atmospheric pressure under reflux of water until the rotation viscosity reaches a definite value, and (iii) dehydrating the product at about 60-140 deg.C (preferably, dried with zeolite to a water content of about 1/50mol or below).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a halogenated phenolic compound, a polyimide resin bath, and a method for producing a polyimide resin bath. The polyimide uq I+, which has a high stability and stability, is suitable for the manufacturing method of baths.

Traditionally, the polyimide side was produced using tetracarboxylic acid dianhydride and aroma:f! Group siamin: Due to polar bathing in southern China, a method was adopted in which polyamide acid was produced by heating it to temperatures above 60'C and reacting with a bamboo sword, and converting it into a molded product, dehydrating it, and diimidizing it by heat. L ox public failure number 36-10999 public 'f,
t (tJsP, 5.179, 614).As a method for horiimide-side shikayoku shin-giri direct-up samurai, Japanese Patent Application Laid-Open No. 55-65
227+-y public♀ pillow, 3.5'.

4. 4'-biphenyltetracarboxylic acid b=w, 27 fulvone component, 4.4'-diaminodienyl ether, main component, and aromatic diamine diamine component in approximately equal moles; In one stage in an organic polar solvent at high temperature while removing condensed water.

Heavy@, imidize and produce polyimide resin solution.
A method is described.

In addition, as a method for producing polyimide resin solution in the presence of water, Japanese Patent Publication No. 47-79907;
No. 6-58524 S.

The above-mentioned Japanese Patent Publication No. 19907/1987 describes the reaction of butanetetracarboxylic acids as an acid component and an aromatic diamine in approximately equimolar amounts in a solvent, and in the presence of water in a reflux system. There is no description of the method for producing the polyicide resin m-liquid.

5.5' in Japanese Unexamined Patent Publication No. 56-58524.

4. Acid component in 4'-bi2-enyltetracarboxylic acids, 4
．． 4'-diaminodiphenyl ether was used as the aromatic diamine component, and the initial reaction was carried out in a phenol compound.
A method for producing a polyimide resin solution is described in which the reaction is carried out in the presence of moisture in a sealed state.

The packaging method rJ1 of the above two known documents is converted to rJ by the manufacturing method of 7ζ, and A6 is the one that still satisfies the storage stability of #j number after manufacturing, and rJ is η・t1ko0 Not invented. Kasumi conducted various studies on the manufacturing method of a polyimide resin solution with low storage stability (0), and came up with this invention. Tetracarbo mainly composed of benzoneenonetetracarboxylic acids: /'L
H, H and the aromatic diamine component whose main component is 4,47-diamid-2-enyl ether, n? It is convenient to use one unit, and the initial coating is carried out using a halogenated phenol compound as a 8 km medium, and the initial coating is carried out with water removal from the reduction stand at a reaction temperature of 100 to 200°C until the reduced specific viscosity becomes 0.1 or more. After that, the water was refluxed under atmospheric pressure.

Resistance α and Ding O This invention's ttW% constant component of Jx is removed in the presence of moisture. The water contained in the XL is the same as the water present when the
By reducing the amount of water, the NFC polyimide resin solution has excellent storage stability.

Methods for removing condensed water in the initial reaction mentioned above include expulsion using an inert gas, removal as an azeotropic mixture using a solvent such as toluene, and removal using zeolite, but the methods using inert gas and zeolite are the most effective. This is preferable because it can be carried out at a relatively low reaction temperature.

According to the present invention, a polyimide resin having an imidization rate of 90% or more, particularly 95% or more, and even 98% or more can be obtained.

Moreover, according to the present invention, it is possible to directly obtain a uniform and transparent polyimide resin solution with a glaze concentration of up to 50%. In addition, it is possible to remove and concentrate the compound into a halogenated phenol compound*' by diluting it with a halogenated phenol adduct or using a variety of methods.

According to this invention, the polyimide liquid bath liquid manufactured by the formula:
By completely forming a thin film of resin solution and removing the solvent from the resin solution, it is possible to easily create a superior n'fc polyurethane film.Q It is also useful as an insulating varnish for enamel. We would like to congratulate you more specifically on the following inventions.

Tetracarboxylic compound 1; J, conveniently used in the present invention
It is mainly composed of 3.3', 4.4'-benzoneenonetetracarboxylic acids, and is preferred.

5.5',4.4'-benzo dicarboxylic/tetracarboxylic acids account for about 50 mol% or more of the tetracarbo/acid component.

Preferably 65 mol% or more, more preferably 70 mol%
All you need is 6n.

1m He 5.514.4'-Benzyaenonetetracarboxylic acids and F; 1.5', 4.4'-benzo21nonetetracarboxylic acid, its acid anhydride v+, esterified product, % K5, 5', 4,4'-benzoneenonetetracarboxylic acid dianhydride (hereinafter referred to as BTDA) is suitable (hereinafter referred to as BTDA) (due to the formation of a polymer insoluble in the dihalogenated phenolic adduct during the course of the reaction). If the liquid becomes cloudy and the liquid becomes cloudy, it is preferable to use the above-mentioned 5.5', 4.4'-benzenetone carboxylic acid. pyromellitic dianhydride,
2,3.6.7-2talenetetracarboxylic dianhydride, 5.5',4.4'-diphenyltetracarboxylic dianhydride, 1,2゜5.6-naphthalenetetracarboxylic dianhydride Anhydride, 2.2', 5.6'-dinenyltetracarboxylic dianhydride 'f'/J, 2.2-bis(
3,4,-dicarboxyphenyl)globanni anhydride,
Bis(6,4-dicarboxy 2-enyl) sulfone dianhydride, 5.4.9.10-perylenetetracarboxylic dianhydride, bis(6,4-dicarboxy 2-enyl) ether dianhydride.

Naphthalene-1+2.4.5-Tetracarboxylic dianhydride, Naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2.6-dichloronaphthalene-1,4°5.8
-tetracarboxylic dianhydride, 2.7-cyclopentane-1.4,5.8-tetracarboxylic dianhydride, 2
．． 6.6.7-Tetrachlorna 2talene-1,4,5,
8-tetracarboxylic dianhydride, enanthrene-1,
s, 9.10-tetracarboxylic dianhydride, 2.2
-bis(2,3-dicarboxy 2-dicarboxylic acid) 2m water 9m, 1.1-bis(2,5-dicarboxyphenyl)ethane dianhydride 11.1-bis(6,4-dicarboxylphenyl) Xyphenylene ethane dianhydride, bis(2,5-
Dito Ruboxy 2 Eninori Methani Anhydride, Bis(6,4
-dicarboxy(2-enyl)methane dianhydride, bis(3,
4-dicarboxyphenyl)sulfone dianhydride 9a *benzene 1.2.3.4-tetracarboxylic dianhydride, 2,6゜2-3-benzophenonetetracarboxylic acid di#c hydrate, 2.6.5' , 4'-benzoneenonetetracarboxylic dianhydride, pyrazine-2,5,5,6-tetracarboxylic dianhydride, thionene-2,5,4,5
-Tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, decahydronaphthalene-1,4,5°8-
Tetracarboxylic dianhydride, 4,8-dimethyl-1,2
,5,5,6,7-hexahydrof2talene-1.2.
5.6-Tetracarboxylic dianhydride, cyclopentane-
1,2,,5,4-tetracarboxylic dianhydride, pyrrolidine-2,5,4,5-tetracarboxylic dianhydride,
1.2.3.4-butanetetracarboxylic dianhydride,
bicyclo-(2,2,2)-otato(7)-ene-2,
3,5,6-tetracarboxylic dianhydride.

2.6.5',4'-biphenyltetracarboxylic dianhydride, s, 4. s', 4'-biphenyltetracarboxylic dianhydride vlJs 2+5+2'+5' -H2z
= Lutetrazylic dianhydride, bis(3,4-dicarboxy2enyl)dimethine and silaniic anhydride? l, bis(3,4-dicarboxyphenyl)methyl 2enylsilanihydride, bis(5,4-dicarboxyphenyl)
Anhydrous? /1. Bis(2,5-dicarboxyphenyl)dimetersilanihydride, 1.4-
Bis(3,4-dicarboxinyldimetersilyl)
Benzene dianhydride, 1,6-bis(5,4-dicarboxy2enyl)-1,1,3,6,-tetramethedisiloxane dianhydride, /xy, Chill H anhydride 1) ethylene glycol bis(trimellitic anhydride) % 2,2-
Bis(6,4-dicarboxyphenyl)hexafluoroflobanni hydrate.

2.2-bis(4-(5,4,-dicarboxy-2-enoxy)phenyl)hexanerologlobanonikumasuimono, 4.4
'-Bis(5,4-dicarboquinone enoxydine enyl sulundi)

The aromatic diamine component U used in the present invention VLk,
4.4'-Diaminodiphenyl ether is the king and the king! ; L, 4.4'-diaminodiphenyl ether (hereinafter referred to as DLlt!) or aromatic diamine component in an amount of 70 mol% or more, preferably 75 mol% or more, and preferably 80 mol% or more. Me) L is good.

If the amount of LADE is less than 70 mol%, it is not preferable because during the reaction V (a polymer which is not bathable for the halogenated phenol compound is formed) and the reaction mixture becomes cloudy when cooled to the reaction slag.

1) 1) E and V are used for this purpose @2 aromatic diamine is 2.2-bis(4-amino-2enyl) globan%
2+6''-cyaminohyridine, bis-(4-aminoaenyl)diethercy2no, bis-(4-amino-phenyl)diphenyl 7rane, benzidine, 3,6-cyclorubenzidine, 3゜6'-dimethoxybenzidine,
Bis-(4-amino-phenyl)etherphosphine oxide, bis-(4-amine-2-enyl)-N-bunalamine, bis-(4-amino-phenyl)-N-metheramine, 5.5'- Dimethyl-4,4'-diadiminocufninyl, N-(3-aminophenyl)-4-aminobenzamide, 4-aminophenyl-6-huminobenzoic acid, 5,5'-dinonal-4°4'-diaminodiphenylmethane , 6,5'-dimethoxy-4,47-
Diaminodiphenylmethane, 3,6'-diethoxy-4
, 4'-diaminodiphenylmethane, 5,5'-dicarboxy-4,4'-cyanodiphenylmethane s
5+6'-cyclolo 4.4'-diaminodiphenylmethane, 5+5'-cyclolo 4.4'-diaminodiphenylmethane, 3.3'-dibrome-4,4
'-Diaminodiphenylmethane, 5,5'-dihydroxy-4,4'-diaminodiphenylmethane.

5.6 fudisulfo 4.4'-diaminodiphenylmethane, 5.5'-dimethyl-4,4'-diaminodiphenyl ether, 3. ．． 5'-dimethoxy-4,4
'-Diaminodine 1 nyl ether, 5.6'-jethoxy-4,4'-cyaminodine enyl ether, 6
+5'-Cylboxy 4.4'-Diamino 72enyl ether, 6,6'-dichloro-4,4'-diaminodine 1-nyl ether, 3.6'-dihydroxy4.
4'-diaminodienyl ether, 3.3'-disulfo-4°4'-diaminodiphenyl ether, 6.
6'-dimethyl-4,4'-diaminodiphenylsulfone, 6°6'-dimethoxy-4,47-diaphilonodieneylsulfone, 6.6'-jethoxy-4,4'-diaminodiphenylsulfone, 6, 6'-dicarphoquine-4,47-diamicinyl sulfone + 3,3'
ytalo o -C4'-Sifminodiphenylsulfone, 3,3'-dihydroxy-4,4'-diaminodiphenylsulfone, 6,5'-disulfo-4,4
'-Diamino diphenyl sulfone, 6,5'-dinonal-4,4'-cyamino di-2enylzuloban, 3
．． 5'-dimethoxy-4,4'-diaminodiphenylpropane, 6.5'-cy c-to+cy 4,4'-diaminodiphenylgloban, 6,6'-dicarboxy-4
, 4'-diaminodienylgloban, 3,3'-dichloro-4,47-diaminodienyl 7°loban,
5.5'-dihydroxy-4゜4'-cyaminodiphenylpropane s 31.5'-';sulfo4.4'-diaminodiphenylgloban,6゜6'-dimethyl-4,
4'-diaminodiphenyl sulfide, 5.5'
-dimethoxy-4,4'-diaminodiphenylsul2ido, 6,5'-jethoxy-4,4'-cyabafuji2
enylsul2ad, 5,5'-dicarboxy-4
, 47-diaminodiphenyl sulfide, 3.3
'-dichloro-4,4'-diaminodiphenylsulfide, 5,5'-dihydroquine-4,4'-diaminodiphenylsulfide, 6°6'-disulfo-4+47
-diaminodiphenyl sulfide, 6.6-diaminodihenylmethane, 6.6'-diaminodiphenyl ether, 3.5'-diaminodiphenylsulfone, 6.5'-diaminodiphenylpropane, 3
．． 3'-diaminodiphenyl sulfide, 2.4-diaminotoluene, 2.6-diaminotoluene, rose-2
Enylene diamine, meta-phenylene diamine, 4
．． 4'-Sia ε large 2-enylpropane, '4.4'-
Diaminodiphenylmethane, 5.3'-diaminobennone, 4.47-diaminodi2enylsulunite, 'L4'/aminodiphenylsulfone,
3.4'-diaminodiphenyl ether, 1.5-diamino-naphthalene, 5.5'-dimethoyacivedicin, 2゜4-bis(baked-amino-1-bunal)toluene, bis-(barabeta-amino- t-butyrunenyl) ether, bis-(halabetamenaludertaaminobentel)benzene, and superlar(1
,1-dinonal-5-amino-pentyl)benzene, 1
-ia 70 building-2,4-methanelenedia (/, r
N-xylene diamine etc.

The fecal dose ratio with the aromatic diamine component is used in a static mole, and the imidization process is performed in line 71').

The usage ratio of the four components is katana, nashi mo terashiku l〈tada good izu n7D, one component is 10 compared to the other component.
Preferably within 5 mol%; preferably within 5 mol%;

Inventively, as a reaction bath medium, it is convenient to use a halogenated enol of 5 qvJta, and if the water removal group and the halogen atom are attached to the carbon forming the benzene tau, the melting point should be 100. 'C or less, preferably 80℃ increase,
The boiling point is below 3000C) 31
At temperatures below 280°C, the halogenated phenol compound 7j becomes -tt. The halogen atom bonded to the benzene nucleus is preferably a salt or bromine, although it does not require VC. Further, the halogenated phenol compound may be one in which a lower alkyl group such as methyl, ethyl, or norobyl is substituted with a halogen atom and a lower alkyl group such as ethyl or norobyl as a substituent other than the hydroxyl atom.

:+What is the enolization of halides in inventions? llλ 0-chlorophenol, m-chlorophenol, p~dichloro2enol o-bromophenol, m
-Chlorphenol, p-fromphenol, 2-chloro-4-hydroxytoluene, 2-chloro-5-hydroxytoluene, 6-chloro-6-hydroxytoluene 4
2-7'rom-4
-H)” Roxytoluene, 2-bromo-5-hydroxytoluene, 2.4. Dichloro-2-enol, 2.6
．． - Dichloro 2-enol, 2.4.6-dolychlorophenol, 2.4.6-trifluorome 2-enol, etc. are listed in 713 publications / 8 degrees.
Chlor 2-enol m-Chlor 2-enol, p-Brom 2
1-norm-7-romenol, 2.4 citalol-2enol, 2,4.6) dichlorophenol, 2,4-dinorom-2enol, 2,4.6-triflom-2enol, or halogenated 2 of 01 8
Fa 2 or more buildings (/J?M bath medium is preferred.

However, uninventively, the halo-saponified phenol compound and other polar baths are added within 60% and used.

In accordance with the present invention, the concentration of 8M'f of each component is 2 to 60%, more preferably 6 to 2%, more preferably 4 to 2%. 15 summer child% and l
In the present invention, the temperature of the initial reaction is preferably 100 to 200°C.
The temperature may be 7J, but preferably 100 to 180°C, preferably 100 to 160°C. It is preferable to keep the reaction humidity at a low level, but it is unlikely that the reaction temperature will be oxidized within the above range.If the reaction temperature is lower than 100°C, imidization will not proceed to the light level, and the temperature will be very high. It is rounded and rounded, and the imidization rate is 4# I'l delicious sword and samurai rL7Z. Also anti-work 6
If the temperature is higher than 200°C, it tends to become kelp, resulting in a resin bath with no fluidity or a tsukufat bath liquid, which is not unreasonable. Known methods such as expulsion using inert scum may be used to remove dirt from the reduction table, but is it easy to reduce the specific viscosity? It is preferable to remove the condensed water at the second stage in order to maintain the ff1l level.

In addition, the specific viscosity of the reduced specific viscosity after entering the wafer is preferably 0.1 or more, preferably 0.1 to 2.0, more preferably 0.1.
It's ~1.5. The reaction was carried out using a reflux tube under atmospheric pressure in a device with a reduced specific viscosity of 0.1 diameter and a single molecule door. At least one F9T of the device is open.
It's better to have something like that.

In addition, it is best to adjust the reaction vorticity of the reaction vorticity in the range of 100 to 200°C, but preferably in the range of 180°C to LrX1QQ to 160°C.

Is it good to have a sigmoidal leakage degree σ-foot with a ton of weight on the foot?

If you pay 15 yen for the previous B, you may be poor. If the viscosity is higher than 100℃, the imidization will not be repeated and the imidization rate will be low. Do not hit the ball with the ball as it can easily result in an uneven number of resin baths.

In addition, as a result of the 9 o'clock Boki, the result of the semi-nakatori water-sugar reaction, the theoretically produced amount is 1150-1 of Tsumugi-kai Mizuhire.
2 mol M(1) and nW is 67 mol/'O, preferably 1/40 to 1/2 mol, more preferably -fL(σ1/2
He is a 5-1/2 mole child. It is effective for fried sweets that are less than the near 1-kake, excluding shunri./''\σ〈.

Due to the large amount of editing, the reaction time was a bit scary. As a result of the initial reaction, the water content was filled to 8 t.
'、J @ @1 Add water grapes so that there are people within the range of J
It's good.

In addition, the rotational viscosity during the reaction time of Shunadai is -1 to 1)
X-reaction time of 2% is good, but it is usually 1 to 50 hours.

In the second aspect of the invention, there is a known method of removing water from the oil bath after drying it with an inert scum and using a drying agent. It is better to dehydrate with water (7 days).

It is better to keep the temperature as low as possible when dehydrating with zeolite, but it is best to set it at 60 to 140 degrees Celsius under a lamp, but it is also possible to use a sieve. It is preferable that the amount of water a#i' of h brother water, 1 polyimide crosslinking bath liquid, and 1,150 mol or less for miyama fL heart water child.

In addition, depending on the amount of zeolite used in the present invention, it is also possible to carry out the aging process without removing the zeolite used in the initial reaction.
O1 can be used as a natural zeolite or as a manufactured product.
0 zeonite, which may be referred to as a nine-axis agent, is almost the same as a water molecule, or even less than a water molecule, and should be smaller than a bath medium molecule or a toilet monomer molecule, but 6~ 5A is preferred. 11 This zeolite (1) has a shape (there is no limit to binding or lining, but pellet-like or spherical is preferable. In addition, according to the present invention, the reduced specific viscosity is 1" and the anchor is 5) at 0°C and concentration 0. .19/100ml The water content in the 0-horidumide resin bath was measured using the p-thalolphenol bath medium and was added using the Karl Fisson-Yar method. In total, the wave train (L70C with sidewall 0) Below, Example 2 and comparisons & auctions were made.

[〇 formation to initial reactants]

12. Strain meter, stirring device, and BTDA at the foot of the light. a 8 g ((J, 04 mol) pyromellitic acid'-) anhydride 218 g (0.01 mol) DDE 90 g (0.045 mol) and p-phenylenediamine 0.54 g (0.05 mol) were heated to 50°C. Add 7tp to 260g of chlorophenol at RT, stir.
The valve cylinder was completed in about 1.5 hours at 15U'G"f.16
When the mixture was heated to 0° C., 3.6 g of fc4A molecular sieves (;tU Kojun Mulwa #), which had been stored in a phosphorus pentoxide dessicator, was added. 2 o'clock after shuka IWJ 150℃
When the reaction was carried out, a transparent polyimide resin bath solution (initial reactant A) without any filtration was used. , concentration 0.1g/
Measured in 100ml of solvent as p-thalolphenol bathing medium (fc), water content 0.05% (reinforced shrinkage 0
．． 07 mol) and 几.

[Initial reaction,? l B (/J Taisei)

BTDA 16.1 g (0.05 mol) DDE was added to a four-lobe flask equipped with a thermometer stirrer and a nitrogen inlet tube.
10.0 g (0.05 mol) p kept at 50°C
- 7 people were exposed to 220 g of chlorophenol and heated to 120° C. while heating. The reaction was then carried out at 120°C for 20 minutes to prepare a transparent polyimide resin bath solution (initial reactant B).
The moisture content was 0.51% (theoretical yield poly 0.697).

[Method for producing film] A polyimide resin bath solution was cast by floating Vc on one glass of soil, and the result was a complete failure. The produced °C film was heated in an oven at 100 °C for approximately 1 inch + M, l l)-chlor 2-ethanol km.
I removed the polyimide film. Further, the polyimide film was heated in an open shell at 400 DEG C. to remove the actual Vc and p-olphenol, thereby producing a polyimide film.

Example 1 Lake degree elbow, inertial stirring surface, four loafers prepared for return to Guangzhou and official service 1,
X KoK, -vi J47J)y: LC, thing A 2
The temperature was raised to 80° C.1 while adjusting D Og AJ. 1.2 g of water (water amount added to 100.2 moles of Osho).
The temperature was raised to 150°C to complete the reaction. The viscosity of the reaction solution increased over time, and after 15 hours it became 7c.

After the temperature was raised to 160°C, the mixture was heated for 20 hours, the temperature was lowered to 90°C, and 6g of 4A remolecular sieves (Wako JR Co., Ltd.) were added. This width plate "T: 1 o'clock" was stirred to obtain a viscous polyimide & (fat bath).

Infrared spectroscopic analysis of the polyimide tree was carried out at 1 780 cm-'l/C. 75% imidization rate for just one sword
It was found that all of the above polyimide resins have /)c.

The storage stability of the polyimide resin solution shown in Figure 1 is shown in Figure 1.The reduced specific viscosity of the polyimide resin solution is
2, 11, moisture content 0.012% (a.
/, +0.017mo/1=) The rotational viscosity at 70°C is 478
I met Boise. In addition, a 7-layer film was prepared from a polyimide resin solution with an attached coating of atRspun'M Soft 16.9
kg/mm, d anti-elongation 52% and pBk starting width of o-f7ζ part) 450℃ and quotient (example 1 of 0 ratio yield with heat resistance) Molecular without the 8th screen / - ugly and no situation water π line
In addition to O, it is transparent and sticky with vaJi and PJ Muku.
7 Samurai 8Z polyimide toilet bathing ridges.

Samurai and γL7 Kohorii ξ Dokii Fat Kasumitake's preservation team was defeated by the sandpiper.

Comparative example 2 Kaketo 1 ↑ and the fourth 77 with a great iron picket 1↑
S: I to B'FDAI 2.88g (C1.0.4 mol)
, PMDA 2.18 g (0.01 mol), υLE
EshiUg (0,045 mol), PPDo, 54gC0
, 005 mol) to 5σ℃L, /) p-chlorophenol 260g, and the temperature rose from 160°C to 160°C in 91.5 hours. ,
6) In response to 5L, transparent and viscous polyimide was produced. The storage stability of the samurai polyimide resin was seriously criticized.

Comparative Example 6 Transparent and viscous polyimide was prepared in the same manner as in General Example 1, except that the autocrane was used on Shunketsudai, and the dehydration was carried out using Molecular Sheaves on Goarandai Shutai 4A. Resin bath liquid boiled.

Comparative Example 4 Four flasks equipped with a knitting elbow, stirring device, and reflux cold shoulder tube VC Initial reactant B 200 g (7 L per person) Nagashi 16
0"'C reeds caused the temperature to rise." The reaction solution was heated to 0160°C, which was heated to 0160°C after 60 hours.
After incubating for 5 hours, the temperature was lowered to 7 U'''c vc, 4
I drank 20g of A's Molecular Twos. At this temperature, the reduced specific viscosity of the polyimide resin solution was 0.16, which was 0.16, and a film 9c was prepared. Only 1 inch of film could be made, which was extremely brittle and could not withstand heavy use.

Ratio 4! ￥1 5 BTDA, PMDA 1,2,3,4-butane tetrab The reduced specific viscosity of the obtained initial ash material C was 0.61% and 0.06%.
(6 ml of tightening water - U of waste, 0.8 mol).

The first M Shigeo 1 product C20C20O water 0.2 g (water content is a, 21 moles @ Naon? In addition to being absent from the Emperor's visit to the Emperor, it is also transparent as a general rule 1. The storage stability of the samurai-made polyimide toilet fat bath is very good.
However, the knitting resistance was low at approximately 350°C.
It was a small amount of material for binding 1.

By adopting the above-mentioned fabric manufacturing method, a transparent and uniform polyimide finely assembled bath solution with excellent storage stability can be obtained.

4.1 田's Iihaya / 2 Kinmeizu 01 + 0 lol Shimuno 1 O Yohihi Naku Tari 1~5 V (,
Samurai et al. 7'L 7 This polyimide immortal IJn bathing and obliterating female pressure is a boa grand.

Representative Patent Attorney Kuni Wakabayashi 1 Number of days (weeks) for rotational viscosity Procedural amendment (spontaneous) 1980B, 6 1123 11 Mr. Commissioner of the Japan Patent Office 1. Indication of the case 1988 Patent Application No. 65259 No. 2, Name of the invention: Method of manufacturing polyimide resin 6, Relationship with the case of the person making the amendment Patent applicant name: +4451 Hitachi Chemical Co., Ltd. - 14,
2) "Polyiside" o "4." on the third negative line 13 of the specification
Riamido” and correction children 0

Claims (1)

[Scope of Claims] Tetracarboxylic acids whose main component is 1, 5.5', 4.4'-benzoneenonetetracarphonic acids, and 4.4
The aromatic diamine component containing '-diaminodine enyl ether as a main component and the grapes are conveniently used in such a manner that the number of moles of both components is approximately equal, and used as a solvent for the halogenated phenol adduct. At a reaction flow rate of 100 to 200°C, the initial reaction was carried out while removing water until the reduced specific viscosity was 0.1 or more. : While the rotational viscosity is kept constant, the polyimide is made to have a sexual characteristic that is its quick dehydration/b. 2. The zeolite is used to remove the water from the shoes while allowing the initial reaction to occur, which is a feature of pregnancy and 7) IP! A method for producing a polyimide-side B ¥1 bath towel as described in Item 1 of FFUJηKihan4. 3. Polyimide resin bath solution (1) production method described in 0.