JP3296056B2 - Method for producing polyamideimide and / or polyimide solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyamideimide or / and polyimide resin solution dissolved in a general-purpose solvent from a polyamideimide or / and polyimide solution dissolved in a high boiling point polar solvent by solvent replacement.

[0002]

2. Description of the Related Art Conventionally, polyamide-imide and / or polyimide coating agents and adhesives have been known to be N-methyl-
It has been polymerized and adjusted in a high boiling point and high polar solvent such as 2-pyrrolidone and used.

[0003]

When a polyamideimide or / and polyimide solution using such a high-boiling point and high-polarity solvent is used as a coating agent or an adhesive, the drying conditions are high temperature and long time, and various industrial processes are required. Was subject to various restrictions. In order to overcome this, synthesis of polyamideimide and / or polyimide in a general-purpose solvent has been studied, but there is a problem that the composition is restricted and the degree of polymerization is hardly increased.

An object of the present invention is to provide a method for efficiently removing a solvent from a polyamideimide or / and polyimide solution dissolved in a high boiling point polar solvent and re-dissolving the same in a general-purpose solvent.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on means capable of promptly replacing a high-boiling solvent with a general-purpose solvent, and as a result, have finally completed the present invention. The present invention is characterized in that a polyamideimide or / and polyimide solution dissolved in a high boiling point polar solvent is coagulated into a thread in a coagulation bath composed of a poor solvent, dried, and then redissolved in another solvent. The present invention relates to a method for producing a polyamideimide and / or a polyimide resin solution.
That is, by applying the principle of wet spinning, polyamideimide or / and polyimide dissolved in a high-boiling-point polar solvent is coagulated in a poor solvent to form a thread, the high-boiling-point polar solvent is removed, the coagulated product is dried, and then a general-purpose solvent is dried. This is a method for producing a polyamide-imide and / or polyimide resin solution that is easily industrially mass-produced and re-dissolved in water.

The polyamideimide and / or polyimide used in the present invention can be prepared from an acid component and an isocyanate (amine) component by a conventional method such as an isocyanate method or an acid chloride method with a high boiling point such as an amide solvent or γ-butyrolactone. It is synthesized in a highly polar solvent.

The acid component used for synthesizing the polyamideimide and / or polyimide used in the present invention includes the following polycarboxylic acids, acid chlorides or acid anhydrides, but is not necessarily limited to these. Absent. As the acid anhydride, trimellitic anhydride, ethylene glycol dianhydrotrimellitate,
Propylene glycol dianhydrotrimellitate,
1,4-butanediol dianhydrotrimellitate,
Hexamethylene glycol dianhydrotrimellitate, polyethylene glycol dianhydrotrimellitate, alkylene glycol dianhydrotrimellitate such as polypropylene glycol dianhydrotrimellitate, benzophenone tetracarboxylic dianhydride,
3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, etc. Can be

The polycarboxylic acids include terephthalic acid, isophthalic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-biphenylether dicarboxylic acid,
4'-biphenylsulfone dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, pyromellitic acid, 3,
3 ′, 4,4′-benzophenonetetracarboxylic acid,
3,3 ', 4,4'-biphenylsulfonetetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, dimer acid, stilbene dicarboxylic acid, etc. However, examples of the acid chloride include the acid chlorides of the above-mentioned polycarboxylic acids.

As the isocyanate component, dicyclohexylmethane-4,4′-diisocyanate,
1,3-bis (isocyanatomethyl) cyclohexane,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-
4,4′-diisocyanate, 3,3′-diethyldiphenylmethane-4,4′-diisocyanate, 3,3 ′
-Dichlorodiphenylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyl-4,4'-diisocyanate, 4,4'-diisocyanate-3,3 '
-Dimethylbiphenyl, hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate and the like.

The amine components include 4,4'-diaminodicyclohexylmethane, 1,3-cyclohexanebis (methylamine), orthochloroparaphenylenediamine, paraphenylenediamine, metaphenylenediamine, and 4,4'-diamino. Diphenyl ether, 3,
4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,
4′-diaminodiphenyl sulfone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 2,2′-bis (aminophenyl) propane, 2,
Examples thereof include 4-tolylenediamine, 2,6-tolylenediamine, paraxylylenediamine, isophoronediamine, hexamethylenediamine, p-phenylenediamine, and m-phenylenediamine.

The monomers mentioned as the acid component and the isocyanate (amine) component may be used alone or as a mixture. Depending on the polymer physical properties and polymerizability, it may be one obtained by combining one or more isocyanates with one or more acid anhydrides, or copolymerizing one or more amines with one or more acids or acid chlorides.

The solvent used for synthesizing the polyamideimide and / or polyimide used in the present invention is not particularly limited as long as it is a commonly used solvent. For example, N
Amide solvents such as -methyl-2-pyrrolidone and N, N-dimethylformamide, and high-boiling polar solvents having a dielectric constant of 25 or more with a boiling point of 120 ° C or more, preferably 150 ° C or more, such as γ-butyrolactone, can be used.

The reaction solution (resin composition) comprising the thus synthesized polyamideimide and / or polyimide and a high boiling point polar solvent is used as a dope [gel (filament) in the process of coagulation] for wet spinning. . In order to effectively elute the high boiling point polar solvent from the dope and adjust the elution rate, alcohol solvents such as ethylene glycol and triethylene glycol, hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, and methyl isobutyl Ketone solvents such as ketone, cyclohexanone and isophorone, ether solvents such as dioxane, ethylene glycol dimethyl ether and tetrahydrofuran, methyl acetate, ethyl acetate and acetic acid-n-
An ester solvent such as butyl or cellosolve acetate may be added to the dope.

The lower the polymer concentration of the dope, the lower the residual solvent amount. However, if the concentration is too low, the workability is reduced. Therefore, it is important to balance conditions such as the coagulation bath temperature, the polymer concentration, and the dope composition. That is, the polymer concentration of the dope varies depending on the temperature and composition of the coagulation bath and the temperature and composition of the dope in addition to factors such as the molecular weight and composition of the polyamideimide and / or polyimide.
-80% by weight, preferably 20-70% by weight, more preferably 30-60% by weight.

The diameter (D) of a nozzle used in a wet spinning type apparatus has a close relationship with the amount of residual solvent. If the spinning speed is constant, the smaller D is, the smaller the amount of residual solvent in the filamentous coagulated material is. Is less. It is usually 1 mm or less, preferably 0.5 mm or less, and desirably 0.3 mm or less. The length (L) of the nozzle is determined in relation to the viscosity characteristics of the dope. The air gap may be provided depending on workability and operability, or a hot air drying device may be employed in the air gap.

The coagulation bath used in the present invention is, for example,
Water, methyl alcohol, ethyl alcohol, ethylene glycol, triethylene glycol, Oh in a poor solvent of the corresponding polyamide-imide and / or polyimide
In addition, those which are miscible with the used high boiling point polar solvent are used, and the above-mentioned alcohols are preferably used.

In the present invention, in order to more effectively elute the solvent from the resin composition and to adjust the elution rate, alcohol solvents such as ethylene glycol and triethylene glycol, and hydrocarbon solvents such as toluene and xylene are used. Solvent, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, ether solvents such as dioxane, ethylene glycol dimethyl ether, tetrahydrofuran, methyl acetate, ethyl acetate, n-butyl acetate, cellosolve acetate, γ-butyrolactone Ester solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and solvents such as dimethylsulfoxide in the coagulation bath to 1 to 40% by weight. It may be e. Among them, N-methyl-2-pyrrolidone, N, N-dimethylacetamide and γ-butyrolactone are preferred.

The relationship between the temperature of the dope and the amount of the residual solvent is such that the higher the temperature of the dope, the smaller the amount of the residual solvent in the filamentous coagulated material. Similarly, the relationship between the temperature of the coagulation bath and the amount of the residual solvent is such that the higher the temperature of the coagulation bath, the smaller the amount of the residual solvent in the coagulated material. Therefore, it is preferable to extrude the resin solution adjusted to 20 ° C. or more into a coagulation bath adjusted to 20 ° C. or more, and more preferably to convert the resin solution adjusted to 40 ° C. or more to a coagulation bath adjusted to 60 ° C. or more. Extrude. As described above, depending on the manufacturing conditions, it is used after being heated.

The coagulation time varies depending on the type of the dope and the temperature of the coagulation bath, etc., and cannot be determined.
It is preferably about 0.2 seconds to 15 minutes.

Before and after the drying step, and during the coagulation step, the filamentous coagulated material is 100 to 1 mm in length, preferably 10 to 1 mm.
By cutting into chips of about 1 mm, the operability in the re-melting step can be improved, and mass productivity can be dramatically improved.

A feature of the present invention is that the dope is formed into a fibrous (filament) shape.
By coagulating to avoid the phenomenon that the coagulation bath as seen in the reprecipitation method becomes turbid and difficult to filter, drying and re-dissolving operations are extremely easy, and the remaining high boiling point polar solvent is extremely reduced. It is possible to make the amount very small. In the case where the fibrous material is formed into a chip shape with a cutter or the like, the above-described effects are particularly enhanced.

Further, when the coagulated material on the yarn or the chips is washed with ion-exchanged water or the like, the remaining amount of the high boiling point polar solvent can be reduced.

The method of drying the solid resin material solidified into a string or chips in the present invention may be vacuum drying or hot air drying. In order to speed up drying, the coagulated material may be washed in advance with a low-boiling solvent such as acetone.

The drying temperature may deteriorate at 180 ° C. in the presence of oxygen, and obviously deteriorate at 200 ° C. Therefore, drying is desirably performed at 160 ° C. or less. In a vacuum or an inert gas atmosphere, although the temperature limit is somewhat relaxed, it is desirable to perform the process at 200 ° C. or lower.

The general-purpose solvent used for re-dissolution in the present invention includes a non-polar solvent and a low-polar solvent. The boiling point of the solvent used for re-dissolving is 160 ° C. or less, and further 120 ° C.
The following are preferable, and the polarity is preferably in a range of less than 25 in dielectric constant. Specifically, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran, 1,4-dioxane and diglyme, hydrocarbon solvents such as toluene, xylene and solvesso, cellosolve acetate and methoxy acetate Ethyl ether solvents such as butyl may be used, and these may be used alone or in combination of two or more depending on the solubility of the resin and the drying process conditions at the time of molding such as a coating film.

The means for re-dissolving the dried polymer is not particularly limited, and can be dissolved by an ordinary method. For example, a general-purpose solvent is placed in a container, and while stirring, a dry polymer that has been chipped is added little by little at room temperature or under heating.

[0027]

According to the present invention, since wet spinning is applied,
The high boiling point polar solvent can be efficiently removed. In addition, the solid content can be processed into a chip shape which is extremely easy to handle in terms of workability at the time of re-dissolving, and unnecessary heating such as crosslinking is not required because unnecessary heating is not required during drying of the film.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited by these examples.

The characteristics shown in the examples were evaluated and measured by the following methods.

1. Logarithmic viscosity: 0.5 g of polymer is 10
The solution dissolved in 0 ml of N-methyl-2-pyrrolidone was measured at 30 ° C. using an Ubbelohde type viscosity tube.

2. Viscosity: Measured at 25 ° C. using a B-type viscometer.

3. Residual solvent amount: Measured by a thermogravimetric method at a heating rate of 10 ° C./min. The amount of weight reduction from room temperature to 120 ° C. for 5 minutes is defined as the content of water and the like.
The amount of weight loss until holding at 0 ° C. for 15 minutes was defined as the amount of the high boiling point polar solvent.

Example 1 In a reaction vessel, 536.04 g of trimellitic anhydride,
Chlohexylmethane-4,4'-diisocyanate 58
5.52 g, isophorone diisocyanate 124.04
g, N-methyl-2-pyrrolidone (NMP) 1000
g, sodium methylate (1.507 g) and nitrogen
Raise the temperature from room temperature to 200 ° C over about 2 hours in an atmosphere,
The reaction was carried out at 200 ° C. for 4 hours (logarithmic viscosity of the product: 0.4
3dl ・ g ^-1). After completion of the reaction, the mixture was cooled to 100 ° C.
To the polymer was added 1030.30 g of methyl-2-pyrrolidone.
-Adjust the concentration to 33% by weight and stir well to obtain a dope
Was. Air using D = 0.2mm, L / D = 2 nozzle
At zero gap, back pressure to ion-exchanged water at 22 ° C
1kg / cm^TwoFor coagulation. The obtained filamentous coagulate
Is processed into a chip having a length of 5 mm by an automatic cutter,
It was left overnight at room temperature in a large excess of ion-exchanged water. Obtained
The dried chips were dried in a hot air drier at 80 ° C for 24 hours.
Hexanone / tetrahydrofuran = 1/1 (by volume)
Dissolve in a solvent at room temperature, polymer concentration 20% (17
Iz). The resulting solution is
Coat the dry film to a dry film thickness of 5 μm and dry
did. Drying is performed at normal pressure at 60 ° C. for 3 minutes and then at 140 ° C. for 1 minute.
It took 0 minutes. Coagulation bath temperature is 20 ° C, 40 ° C, 60 ° C,
Perform the same operation as above, changing to 80 ° C and 98 ° C,
Investigate the relationship between the coagulation time by temperature and the amount of residual solvent in the chip
did. The results are shown in FIG. From FIG. 1, the coagulation bath temperature is high
It can be seen that the residual solvent amount decreases as the amount increases. But,
When the coagulation bath temperature exceeds 80 ° C, the amount of residual solvent decreases
Was rarely seen. When the temperature of the coagulation bath is 40
, 60 ° C, 80 ° C, 98 ° C solidification bath composition (coagulation bath
The relationship between the NMP concentration in the
The same operation as that described above was performed. Coagulation bath group by coagulation bath temperature
FIG. 2 shows the relationship between the composition and the amount of residual solvent in the chip. Figure 2
When the NMP concentration in the coagulation bath is 30% by weight or less,
It can be seen that the amount of the existing solvent decreases.

Example 2 A dope was prepared in the same manner as in Example 1, and was spun and solidified in a coagulation bath having an NMP concentration of 20% by weight and a bath temperature of 80 ° C. with no air gap. After being left in the coagulation bath for 2 hours and 40 minutes, it was immersed (washed with water) in a large excess of 80 ° C. ion-exchanged water for 6 hours. The amount of residual solvent in the chip was 2.6% by weight. NMP concentration of 10% by weight, 30% by weight, 40% by weight
The time of immersion (washing) in ion-exchanged water at 80 ° C.
The amount of the residual solvent in the chip was measured by changing the time to 2 hours, 10 minutes, and 4 hours, respectively, and the relationship between the composition of the coagulation bath and the amount of the residual solvent in the chip was examined. The results are shown in FIG. From FIG.
It can be seen that washing with water after coagulating the polymer reduces the amount of residual solvent.

Example 3 A dope was prepared in the same manner as in Example 1, and was spun and coagulated in a coagulation bath having an NMP concentration of 20% by weight and a bath temperature of 80 ° C. with no air gap. After leaving in the coagulation bath for 2 hours and 10 minutes, 20
It was immersed in a large excess of ion-exchanged water at 6 ° C. for 6 hours. The amount of residual solvent in the chip was 2.4% by weight. The temperature of the ion-exchanged water (coagulation bath) was changed to 40 ° C., 60 ° C., and 80 ° C., and the relationship between the temperature of the ion-exchanged water (coagulation bath) and the amount of residual solvent in the chip was examined. FIG. 4 shows the results. From FIG. 4, when the standing time is fixed, as the coagulation bath temperature increases,
It can be seen that the residual solvent amount decreases.

Example 4 The operation was carried out in the same manner as in Example 1, and the nozzle was coagulated with ion-exchanged water at 60 ° C. for 2 hours while varying the value of the diameter D of the nozzle. Fig. 5 shows the relationship between the diameter of the yarn and the amount of residual solvent in the chip.
Shown in FIG. 5 shows that the smaller the diameter of the nozzle, the smaller the amount of the remaining solvent.

Example 5 The operation was carried out in the same manner as in Example 1, except that the doping temperature was 20 ° C.
The temperature was changed to 0 ° C. and 60 ° C., and the mixture was coagulated with ion exchanged water for 2 hours. FIG. 6 shows the relationship between the doping temperature and the amount of residual solvent in the chip. From FIG. 6, it can be seen that the higher the doping temperature, the higher the mobility, possibly due to a decrease in the amount of residual solvent.

Example 6 The same operation as in Example 1 was carried out, and the coagulation bath temperature was 60 ° C. and the coagulation time was 30 minutes or 120 minutes. The solvent amount was measured. FIG. 7 shows the relationship between the dope concentration and the amount of residual solvent in the chip. From FIG. 7, it can be seen that since the polymer / solvent easily moves during the coagulation process, the amount of the residual solvent decreases as the polymer concentration decreases.

Example 7 In a reaction vessel, 536.04 g of trimellitic anhydride and dicyclohexylmethane-4,4'-diisocyanate 58 were added.
5.52 g, isophorone diisocyanate 124.04
g, N-methyl-2-pyrrolidone (1000 g) and sodium methylate (1.507 g) were charged under nitrogen atmosphere.
The temperature is raised from room temperature to 200 ° C. over a period of 4 hours at 200 ° C.
(The logarithmic viscosity of the reaction solution was 0.43 dl · g.)
^-1 ). After the completion of the reaction, the mixture was cooled to 100 ° C., and 304.5 g of ethylene glycol (EG) and 725.5 g of N-methyl-2-pyrrolidone were added to adjust the polymer concentration to 33% by weight, and sufficiently stirred to obtain a dope. D = 0.2mm, L /
D = 2 nozzle and water temperature 60 with zero air gap
° C, NMP / EG = 8.5 / 1.5 in 13% aqueous solution,
Spin coagulation was performed at a back pressure of 1 kg / cm ² . The chip was processed into a chip having a length of 3 mm, solidified for 2 hours, and left overnight at room temperature in the presence of a large excess of ion-exchanged water. The residual solvent amount of the chip was 3.7% by weight. After drying at 80 ° C. for 24 hours using a hot air drier, cyclohexanone / tetrahydrofuran = 1/1
(Volume ratio) in a solvent at room temperature.
% By weight (17 poise). The obtained solution was coated on a polyester film so as to have a dry film thickness of 5 μm, and dried. Drying took 3 minutes at 60 ° C. and then 10 minutes at 140 ° C. under normal pressure.

Example 8 536.04 g of trimellitic anhydride and dicyclohexylmethane-4,4'-diisocyanate 58 were placed in a reaction vessel.
5.52 g, isophorone diisocyanate 124.04
g, N-methyl-2-pyrrolidone (1000 g) and sodium methylate (1.507 g) were charged under nitrogen atmosphere.
The temperature is raised from room temperature to 200 ° C. over a period of 4 hours at 200 ° C.
(The logarithmic viscosity of the reaction solution was 0.43 dl · g.)
^-1 ). After completion of the reaction, the mixture was cooled to 100 ° C., 304.5 g of triethylene glycol (TEG) and 725.5 g of N-methyl-2-pyrrolidone were added, the polymer concentration was adjusted to 33% by weight, and the mixture was sufficiently stirred to obtain a dope. . D = 0.2m
m, L / D = 2, no air gap, water temperature 60 ° C., NMP / TEG = 8.5 / 1.5 1
The solution was coagulated into a 3% aqueous solution by spinning at a back pressure of 1 kg / cm ² .
The chip was processed into a chip having a length of 5 mm, solidified for 2 hours, and left overnight at room temperature in the presence of a large excess of ion-exchanged water. The residual solvent amount was 2.7% by weight. 80 ℃ 24 with hot air dryer
After drying for an hour, cyclohexanone / tetrahydrofuran =
It was dissolved in a 1/1 (volume ratio) solvent at room temperature, and the solid content concentration was adjusted to 20% by weight (17 poise). The obtained solution was coated on a polyester film so as to have a dry film thickness of 5 μm, and dried. Dry at 60 ° C under normal pressure for 3
Followed by 10 minutes at 140 ° C.

Example 9 632.11 g of trimellitic anhydride, 1,1,
3-bis (isocyanatomethyl) cyclohexane 51
1.24 g, 146.27 isophorone diisocyanate
g, N-methyl-2-pyrrolidone (1000 g) and sodium methylate (1.507 g) were charged under nitrogen atmosphere.
The temperature is raised from room temperature to 200 ° C. over a period of 4 hours at 200 ° C.
(The logarithmic viscosity of the reaction mixture was 0.41 dl.
g ^-1 ). After completion of the reaction, the mixture was cooled to 100 ° C.
1030.30 g of 2-pyrrolidone was added, the polymer concentration was adjusted to 33% by weight, and the mixture was sufficiently stirred to obtain a dope. D
= 0.2 mm, L / D = 2 nozzle, ion pressure water at 22 ° C with zero air gap, back pressure 1kg / c
It was spun coagulated in m ^2. Processed into 5mm long chips,
It was left overnight at room temperature in the presence of a large excess of ion-exchanged water. The residual solvent amount was 2.7% by weight. 80 ℃ with hot air dryer
It was dried for 24 hours, dissolved in a solvent of cyclohexanone / tetrahydrofuran = 1/1 (volume ratio) at room temperature, and adjusted to a solid concentration of 20% by weight (17 poise). The obtained solution was coated on a polyester film so as to have a dry film thickness of 5 μm, and dried. 60 ° C under normal pressure for drying
It took 3 minutes followed by 10 minutes at 140 ° C.

Comparative Example 1 In a reaction vessel, 536.04 g of trimellitic anhydride, 58 mg of dicyclohexylmethane-4,4'-diisocyanate were added.
5.52 g, isophorone diisocyanate 124.04
g, N-methyl-2-pyrrolidone (1000 g) and sodium methylate (1.507 g) were charged under nitrogen atmosphere.
The temperature is raised from room temperature to 200 ° C. over time,
(The logarithmic viscosity of the reaction mixture was 0.43 dl.
g ^-1 ). After completion of the reaction, the mixture was cooled to 100 ° C.
1679.6 g of 2-pyrrolidone was added, and the solid content
The mixture was adjusted to 0% by weight and stirred sufficiently. The obtained resin solution is
The film was coated on a PET film so as to have a dry film thickness of 20 μm, and dried. 3mmHg for drying, 200 ℃ 2
It took four hours. The amount of residual solvent in the obtained film is about 1
However, it was found by Soxhlet extraction that it was partially crosslinked and gelled.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the coagulation time (minutes) and the amount of solvent remaining in a chip (% by weight) for each temperature of a coagulation bath.
Indicates that the coagulation bath temperature is 20 ° C., 、 indicates 40 ° C., □ indicates 60 ° C., Δ indicates 80 ° C., and Δ indicates 98 ° C.

FIG. 2 shows the composition of the coagulation bath according to the temperature of the coagulation bath (NM in the coagulation bath)
P is a graph showing the relationship between the concentration of the solvent (% by weight) and the amount of the residual solvent in the chip (% by weight), where Δ indicates a case where the coagulation bath temperature is 40 ° C., □ indicates a case where the temperature is 60 ° C., and ○ indicates a case where the temperature is 80 ° C. , ◇ is 98
It shows the case of ° C.

FIG. 3 is a graph showing the effect of post-washing after coagulation at 80 ° C.
Is a graph showing the relationship between the composition of the coagulation bath (NMP concentration in the coagulation bath, wt%) and the amount of the residual solvent in the chip (wt%) according to the immersion time in a large excess of ion-exchanged water. When not treated with exchanged water, △ is when treated with ion-exchanged water for 2 hours and 10 minutes, □ is when treated for 4 hours, and ▽ is 6
Shows the case of time processing.

FIG. 4 shows the coagulation bath temperature and the amount of residual solvent in the chip (% by weight).
6 is a graph showing the relationship of.

FIG. 5 is a graph showing the relationship between the diameter of a filamentous coagulated product and the amount of residual solvent (% by weight) in a chip.

FIG. 6 is a graph showing the relationship between the doping temperature (° C.) and the amount of residual solvent in the chip (% by weight).

FIG. 7 is a graph showing the relationship between the polymer concentration of the dope (% by weight) and the amount of residual solvent in the chip (% by weight).

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09D 179/08 C09D 179/08 AB C09J 179/08 C09J 179/08 BZ // C08L 79:08 C08L 79:08 (72 ) Inventor Tadashi Inukai 2-1-1 Katata, Otsu-shi, Shiga Toyo Boseki Co., Ltd. (56) References JP-A-2-28215 (JP, A) JP-A-2-41319 (JP, A) JP-A-6-345867 (JP, A) JP-A-7-10993 (JP, A) JP-A-7-18075 (JP, A) JP-A-7-173289 (JP, A) JP-A-5-179200 (JP, A) JP-A-2-104721 (JP, A) JP-A-1-95155 (JP, A) JP-A-2-277814 (JP, A) JP-A-5-222612 (JP, A) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 73/00-73/26 C08L 79/00-7 9/08

Claims (3)

(57) [Claims] 1. A polyamideimide or / and polyimide solution dissolved in a high-boiling-point polar solvent having a boiling point of 120 ° C. or higher is coagulated in a coagulation bath comprising a poor solvent into a thread form, dried, and then reused in another solvent. A method for producing a polyamideimide and / or polyimide resin solution, characterized by dissolving. 2. The process for producing a polyamideimide and / or polyimide resin solution according to claim 1, wherein the filamentous coagulated material is cut into chips by cutting. 3. The method according to claim 1, wherein the polyamideimide and / or the polyimide are synthesized using cyclohexylmethane-4,4′-diisocyanate or 4,4′-diaminodicyclohexylmethane as an essential component. Polyamideimide according to 2 or /
And a method for producing a polyimide resin solution.