JP2019099707A - Organic resin solution and spinning liquid, and, production method of fiber assembly with the spinning liquid and production method of film and composite using the organic resin solution - Google Patents

Abstract

To provide an organic resin solution containing an organic resin containing a nitrogen atom in a chemical structure and having excellent stability and a spinning liquid made of the organic resin solution, and, a method of producing a fiber assembly, a film or a composite having desired aspect.SOLUTION: The present applicants found that by blending a urea-based compound in an organic resin solution containing an organic resin containing nitrogen atoms in a chemical structure, the stability of the organic resin solution can be improved. Therefore, the organic resin solution and the spinning liquid made of the organic resin solution according to the present invention have excellent stability. Then, by using the organic resin solution according to the present invention, films and composites of desired aspect can be produced.SELECTED DRAWING: None

Description

  The present invention relates to a spinning solution comprising an organic resin solution and the organic resin solution, a method for producing a fiber assembly using the spinning solution, a film using the organic resin solution, and a method for producing a composite.

An organic resin solution obtained by dissolving an organic resin in a solvent is a solution capable of preparing materials useful for various industrial applications. For example, a fiber aggregate composed of organic resin fibers can be prepared by spinning using an organic resin solution as a spinning solution, and an organic resin film can be prepared by removing the solvent after developing the organic resin solution into a sheet. After applying the organic resin solution to the object to be coated, it is possible to prepare a composite having an organic resin film on the surface of the object to be coated by removing the solvent. Useful for various industrial applications using the organic resin solution Materials can be prepared.
However, as the applicant continued to study, it was found that there was the following problem. That is, when an organic resin solution is prepared using an organic resin containing nitrogen atoms in the chemical structure, the organic resin solution is denatured such that the organic resin is precipitated in the solution over time, and the stability is poor. Had the problem of And when the organic resin solution inferior to stability was used, it was difficult to prepare a material useful for various industrial applications.

In particular, it has been found that the following problems occur in a spinning solution comprising the organic resin solution.
A fiber assembly (for example, non-woven fabric etc.) consisting of fibers with small average fiber diameter and CV value of fiber diameter has various performances such as separation performance, liquid retention performance, wiping performance, concealment performance, insulation performance, or flexibility. It is known to be excellent.
As a method for producing such a fiber assembly, a method of using a spinning solution obtained by dissolving an organic resin constituting a fiber in a solvent, for example, applying electrostatic force to make the spinning solution smaller in diameter and fiberizing it The collected fibers are collected to produce a fiber assembly, and an accompanying air stream is applied to reduce the diameter of the spinning solution and to form fibers, and the spun fibers are collected to obtain a fiber assembly. Methods (for example, Unexamined-Japanese-Patent No. 2011-012372 etc.) etc. which are manufactured are known.

In order to provide a fiber assembly composed of fibers composed of an organic resin containing a nitrogen atom in the chemical structure in the aspect composed of fibers having a small average fiber diameter or a CV value of the fiber diameter, the applicant of the present application A spinning solution prepared by dissolving in a solvent was prepared, and an attempt was made to produce a fiber assembly using the spinning solution.
However, the prepared spinning solution has a problem that the organic resin is precipitated in the spinning solution with the passage of time, for example, to be denatured and the stability is poor.
And, even if it is intended to produce a fiber assembly using the spinning solution thus modified, the discharge of the spinning solution from the nozzle tip may not be stable at the time of spinning, and the fiber assembly may not be produced. The Alternatively, even if the fiber assembly can be produced, a large number of non-fibers such as shots are present in the produced fiber assembly, and / or the CV value of the average fiber diameter and the fiber diameter in the produced fiber assembly is intended It was not possible to provide a fiber assembly in the desired manner.

When a composite having an organic resin film or an organic resin film on the surface of an object to be coated is produced using an organic resin solution having poor stability, the produced film or composite is precipitated in the organic solution. In the presence of the organic resin, non-uniform portions such as uneven portions and portions having locally different various physical properties such as rigidity are present, and it is not possible to provide a film or a composite of a desired aspect Met.

The present invention manufactures a highly stable organic resin solution containing an organic resin containing a nitrogen atom in the chemical structure, a spinning solution comprising the organic resin solution, and a fiber assembly, film or composite of a desired aspect. The purpose is to provide a method.

The present invention
"[1] An organic resin solution containing an urea resin and an organic resin containing a nitrogen atom in its chemical structure.
[2] A spinning solution comprising the organic resin solution according to claim 1.
[3] A method for producing a fiber assembly, comprising the steps of reducing the diameter of the spinning solution according to claim 2 and forming it into fibers for collection.
[4] A method for producing an organic resin film, comprising the steps of: developing the organic resin solution according to claim 1 into a sheet; and removing the solvent from the organic resin solution developed into the sheet.
[5] An organic resin film is provided on the surface of the object to be coated, including the step of removing the solvent from the organic resin solution applied to the object to be coated after applying the organic resin solution according to claim 1 to the object to be coated Method of producing a complex comprising the "
It is.

As a result of continuing investigations, the applicant of the present application has found that the stability of the organic resin solution can be improved by blending a urea compound in an organic resin solution containing an organic resin containing a nitrogen atom in the chemical structure.
Therefore, the organic resin solution according to the present invention and the spinning solution comprising the organic resin solution are excellent in stability.
Then, in the method for producing a fiber assembly, including the steps of reducing the diameter of the spinning solution and forming and collecting the fiber, the spinning solution from the nozzle tip is used by using the spinning solution having excellent stability according to the present invention. Spinning can be carried out in a stable state, so that a large amount of non-fiber matter such as shot can be prevented and / or the CV value of the average fiber diameter or the fiber diameter unintentionally becomes large Can be produced to produce the fiber assembly of the desired embodiment.
In addition, by using the organic resin solution according to the present invention, it is possible to prevent the presence of nonuniform portions such as uneven portions such as uneven portions and locally different portions of various physical properties such as rigidity, etc. Complexes can be produced.

  The present invention relates to an organic resin solution containing a urea compound and an organic resin containing nitrogen atoms in the chemical structure, and a spinning solution (hereinafter sometimes referred to as an organic resin solution or spinning solution) comprising the organic resin solution For example, various configurations such as the following configurations can be appropriately selected.

  The urea compound as used in the present invention is a compound having a urea skeleton (N-C (O) -N or N-C (S) -N) in its chemical structure, and examples thereof include urea, thiourea and hydroxyurea. , Dimethylolurea, diacetylurea, ethyleneurea, phenylurea, triphenylurea, tetraphenylurea, N-benzoylurea, N, N'-dibenzoylurea, guanylurea phosphate, N, N'-dimethylacetylurea, benzenesulfonyl Urea, p-toluenesulfonylurea, alkylurea having an alkyl group having 1 to 6 carbon atoms (eg, methylurea, dimethylurea, trimethylurea, tetramethylurea, tetraethylurea, ethylurea, diethylurea, etc.), formylurea, etc. Can be used alone or in combination of two or more. In addition, salts (for example, nitrate, hydrochloride, etc.) of these ureas may be used.

  In particular, it can be removed together with the solvent in the step of removing the solvent from the organic resin solution and the reduced diameter spinning solution as described later (for example, the heating step and the step of removing the solvent by immersion in water). It is preferred to use a urea compound. By using an organic resin solution or a spinning solution containing such a urea-based compound, a material (a fiber aggregate consisting of constituent fibers in which the urea-based compound does not exist, or a fiber assembly in which the urea-based compound does not exist) A film or complex in which no urea compound is present, or a material having a small amount of urea compound (a fiber aggregate composed of constituent fibers having a small amount of urea compound, or a urea compound) It is possible to provide a film, a composite, etc. in a small amount. Urea, dimethylurea, phenylurea and the like can be used as such removable urea compounds.

  In addition, it is preferable to use a urea compound having a small molecular weight (low molecular weight compound or monomer) such as urea, dimethylurea and phenylurea. By using an organic resin solution or a spinning solution containing such a urea-based compound, the mass of the urea-based compound to be contained in the organic resin solution or the spinning solution can be further reduced, and finally the urea-based compound does not exist Materials (fiber assembly consisting of constituent fibers in which no urea compound is present, or a film or composite in which no urea compound is present, etc.), or material with a small amount of urea compound (urea compound It is possible to provide a fiber assembly composed of constituent fibers having a small amount of C, or a film or a composite having a small amount of a urea compound.

  The organic resin containing a nitrogen atom in the chemical structure in the present invention refers to a compound having a nitrogen atom in the chemical structure, and in particular, a resin having a heterocyclic structure is preferable because of its excellent heat resistance. For example, polyazole resins (eg, polybenzimidazole, polybenzoxazole, polybenzothiazole, polypyrrole, polycarbazole, etc.), polyimide resins (eg, aliphatic polyimide, aromatic polyimide, polymaleimide, etc.), polyamic acid, polypyridine And polyquinoxaline can be used singly or in combination of two or more.

The type of the organic resin containing nitrogen atoms in the chemical structure is appropriately selected depending on the physical properties required for the material to be provided (for example, a fiber assembly, a film, a composite, etc.). Although it is preferable to use polybenzimidazole, it is possible to provide a material having excellent heat resistance.
In addition, although a polybenzimidazole is not specifically limited, For example, it can be an organic resin which has a repeating unit represented by following formula (I) or (II).

In formula (II), Y is a substituted element selected from O and S, or a carbon-carbon bond (for example, a divalent group such as -O-, -CO-, -SO _2- ). Furthermore, the Y moiety may be a σ bond that combines the repeating units represented by the above-mentioned formula (I).
And Z is a divalent C1-C10 alkanediyl, a divalent C2-C10 alkenediyl, a divalent C6-C15 aryl, a divalent C5-C15 heteroaryl, a divalent C5-C15 heterocyclyl, a divalent C6-C19 aryl sulfone, and Preferred is a divalent group selected from the group consisting of divalent C6-C19 aryl ethers and having at least one aromatic ring. For example, a functional group having a group as described in the following formula is preferable.

  The kind of the solvent constituting the organic resin solution and the spinning solution according to the present invention can be appropriately selected as long as it is a solvent capable of dissolving at least the urea compound and the organic resin containing nitrogen atom in the chemical structure. For example, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl methyl ketone, ethanol, sulfuric acid, polyphosphoric acid, an alkali solution and the like can be used as a single or a plurality of mixed solvents.

  The mass of the urea-based compound contained in the organic resin solution or the spinning solution is appropriately selected so as to provide the desired material according to the mass of the organic resin containing nitrogen atoms in the chemical structure contained in the organic resin solution or the spinning solution. is there. However, if the mass of the urea-based compound contained in the organic resin solution or the spinning solution is too small, there is a risk that the effect of improving the stability of the organic resin solution or the spinning solution may not be sufficiently exhibited. If the mass of the urea compound contained in the liquid is too large, it may be difficult to produce the material.

  Therefore, the mass of the urea-based compound contained in the organic resin solution or the spinning solution is 0.01 to 0.01 when the mass of the organic resin containing nitrogen atoms in the chemical structure contained in the organic resin solution or the spinning solution is 100 parts. The amount is preferably 100 parts by mass, more preferably 0.1 to 50 parts by mass, and most preferably 1 to 20 parts by mass.

  The mass of the organic resin containing a nitrogen atom in the chemical structure contained in the organic resin solution or the spinning solution is appropriately selected in accordance with the use conditions of the organic resin solution and the like so as to provide the desired material. Specifically, when the mass of the solvent is 100 parts, it is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 75 parts by mass, and 0.1 to 50 parts by mass Is most preferred.

  Although the reason why the organic resin solution or spinning solution of the present invention is excellent in stability is not completely understood, the amide of the urea compound with respect to the chemical structure part in which the reactive nitrogen atom is present in the organic resin It is considered that the structure portion having affinity makes it difficult for an undesired reaction (such as insolubilization in a solvent) which leads to a decrease in stability such as self-crosslinking of the organic resin in a solvent to progress. .

  In particular, this effect has many nitrogen atoms in the chemical structure (because it has many nitrogen atoms in the chemical structure, it is thought that an undesired reaction that leads to a decrease in stability such as self-crosslinking is likely to progress) polybenzimidazole In organic resin solutions and spinning solutions containing organic resins such as In addition, this effect is due to the organic resin solution or spinning that contains a urea-based compound such as urea, which has a small molecular weight (it is considered to have a higher affinity to the chemical structure part comprising the nitrogen atom of the organic resin due to the smaller molecular structure). The liquid is effectively exhibited.

The organic resin solution and the spinning solution according to the present invention may contain other organic resins and various additives, as required.
Although the type of other organic resin can be selected appropriately, for example, polyolefin resin (eg, polyethylene, polypropylene, polymethylpentene, polyolefin having a structure in which a part of hydrocarbon is substituted with a cyano group or halogen such as fluorine or chlorine) Resins, etc.), styrene resins, polyvinyl alcohol resins, polyether resins (eg, polyether ether ketone, polyacetal, modified polyphenylene ether, aromatic polyether ketone, etc.), polyester resins (eg, polyethylene terephthalate, poly Trimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate, polyarylate, wholly aromatic polyester resin, etc., polyimide resin Polyamide imide resin, polyamide resin (for example, aromatic polyamide resin, aromatic polyether amide resin, nylon resin, etc.), resin having a tolyl group (for example, polyacrylonitrile, etc.), urethane resin, epoxy resin, polysulfone Base resin (eg, polysulfone, polyether sulfone, etc.), fluorine resin (eg, polytetrafluoroethylene, polyvinylidene fluoride, etc.), cellulose resin, polybenzimidazole resin, acrylic resin (eg, acrylic ester or methacryl resin) A known organic resin such as polyacrylonitrile resin obtained by copolymerizing acid ester or the like, moda acrylic resin obtained by copolymerizing acrylonitrile and vinyl chloride or vinylidene chloride, etc.) or the like is used alone or as a mixture of plural kinds Kill.
The mass of the organic resin solution or the other organic resin contained in the spinning solution can be appropriately selected in accordance with the preparation conditions of the material such as the spinning conditions so as to provide the desired material.

  Further, the type of various additives can be appropriately selected, but for example, flame retardants, fragrances, pigments, antibacterial agents, anti-globes, photocatalyst particles, emulsifiers, dispersants, thickeners, anti-foaming agents such as alumina and silica, etc. Inorganic particles and inorganic fillers, activated carbon and charcoal black, spinning stabilizers and the like can be added. The kind of the spinning stabilizer can be appropriately selected, and for example, metal salts such as calcium chloride and lithium chloride, salts comprising an organic acid and a nitrogen compound as disclosed in JP 2012-46844 A, etc. It can be used alone or in combination of two or more.

  Further, the mass of various additives contained in the organic resin solution and the spinning solution is appropriately selected in accordance with the preparation conditions of the material such as the spinning conditions so as to provide the desired material. Specifically, when the mass of the organic resin solution and the spinning solution is 100 parts, it can be present in an amount of 0.01 to 30 parts by mass, can be present in an amount of 0.1 to 20 parts by mass, and 1 to 10 Parts by weight can be present.

  The temperature and viscosity of the organic resin solution and the spinning solution are appropriately selected in accordance with the preparation conditions of the material such as the spinning conditions so as to provide the desired material. Specifically, the temperature of the organic resin solution or the spinning solution can be 0 to 165 ° C., can be 10 to 160 ° C., and can be 20 to 150 ° C. The viscosity of the organic resin solution or the spinning solution can be 10 to 30,000 mPa · s at 25 ° C., can be 100 to 20,000 mPa · s, and can be 1,000 to 10,000 mPa · s.

  Next, a method for producing a fiber assembly using the spinning solution according to the present invention will be illustrated and described. Description of the same items as the items already described will be omitted.

The method for producing the fiber assembly can be appropriately selected, but for example, a method of spinning by the action of a gas as disclosed in the electrostatic spinning method, JP 2009-287138 A, JP 2011-32593 JP In addition to the action of the electric field as described above, it is possible to use a method of spinning by applying a shearing force of gas, centrifugal spinning method or the like. Then, it is possible to use a method for producing a fiber assembly including the steps of reducing the diameter of the spinning solution and forming it into fibers by using these production methods and collecting them on a collection body such as a drum or a net.
Among these, it is easy to spin an ultrafine fiber having an average fiber diameter of 2 μm or less by using an electrostatic spinning method or a method of spinning by a gas shearing action as disclosed in JP 2009-287138 A, The fiber diameter is uniform, and it is preferable because it is easy to manufacture a fiber assembly consisting of continuous microfibers.

The method for reducing the diameter of the spinning solution can be appropriately selected, but for example, the discharged spinning solution is directed to the counter electrode by applying an electric force to the spinning solution discharged from the nozzle or slit based on the electrostatic spinning method. A method of flying to reduce the diameter, a method of causing the discharged spinning solution to fly toward the collection body such as a mesh by making the force of gas act on the spinning solution discharged from the nozzle or slit, etc. It can be adopted.
And a fiber web is formed on a collection object by collecting on a collection object, such as a mesh and a belt conveyor, the spinning solution which carried out diameter reduction (fiberization) as mentioned above, for example.

The fiber web thus produced may be used as it is as a fiber assembly, but may be subjected to a heating device to remove the solvent and the urea compound from the fiber web. The type of heating device can be appropriately selected, and for example, a device for heating or heating and pressing with a roll, an oven dryer, a far infrared heater, a dry heat dryer, a hot air dryer, a device capable of irradiating with infrared light and the like can be used. The heating temperature of the fiber web by the heating device is appropriately selected, but it is possible to volatilize or decompose and volatilize the solvent or the urea compound and to remove it, and to be a temperature at which the component such as constituent fibers do not unintentionally decompose or denature Adjust as appropriate.
If necessary, the organic resin contained in the constituent fibers may be self-crosslinked or crosslinked by heating the heating device. Specifically, a fiber aggregate having excellent solvent resistance can be provided by heating a fiber web provided with constituent fibers containing polybenzimidazole at a temperature of 350 ° C. or higher.

Alternatively, the fiber web or fiber assembly produced as described above may be removed by immersing in water or the like to elute the solvent or urea compound remaining in the constituent fibers.
Furthermore, the fiber web or fiber assembly produced as described above may be subjected to a pressure treatment process such as a reliable press treatment to make the surface smooth.

  The fiber assembly produced in this way may be used as it is for various applications, but the step of forming a composite with a resin film, or lamination of another porous member, film, foam, etc. Through various secondary processes such as the process of manufacturing the body, and the process of punching and processing the shape according to the use and usage mode, a material provided with a fiber assembly usable as various industrial materials is prepared. May be

  Further, a film or a composite having an organic resin containing a nitrogen atom in the chemical structure can be produced by applying an organic resin solution to a conventionally known method for producing a film or a composite.

  Specifically, after the organic resin solution according to the present invention is developed into a sheet, a method for producing a film may be employed, including the step of removing the solvent from the organic resin solution developed into the sheet. The thickness of the film to be produced can be selected appropriately according to the needs, and it may be a film having no air permeability or a film having air permeability. Alternatively, it may be a foam film.

Further, after applying the organic resin solution according to the present invention to the object to be coated, an organic resin film is provided on the surface of the object to be coated, including the step of removing the solvent from the organic resin solution applied to the object to be coated A method of producing a composite can be employed. The type of the object to be coated and the thickness of the organic resin film in the composite can be appropriately selected according to the request.
The solvent and the urea compound remaining from the film or the composite can be removed in the same manner as the method for removing the solvent and the urea compound remaining from the fiber assembly described above.

Similarly, the produced film or composite may be used as it is in various applications as it is, but it is a step of forming a composite with a resin film, or a laminate by laminating other structural members such as a porous body, a film and a foam. Through various secondary processes such as the process of manufacturing shapes, and the process of punching and processing the shapes according to the application and usage mode, to prepare materials provided with films and composites that can be used as various industrial materials May be

  Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.

(Comparative example 1)
After mixing 75 parts by mass of dimethylacetamide and 25 parts by mass of polybenzimidazole (manufactured by Perfomance Products, model number: CELAZOLE (registered trademark), PBI 100 Mesh Polymer), the mixture is heated to 150 ° C. The benzimidazole was dissolved to prepare a solution.
The prepared solution was cooled to 25 ° C., passed through a glass filter with a pore size of 1 μm (Advantec, model number: GA-100), and filtered to prepare an organic resin solution.

Example 1
After mixing 75 parts by mass of dimethylacetamide and 25 parts by mass of polybenzimidazole (manufactured by Perfomance Products, model number: CELAZOLE (registered trademark), PBI 100 Mesh Polymer), the mixture is heated to 150 ° C. The benzimidazole was dissolved to prepare a solution.
The prepared solution is cooled to 80 ° C., and 0.25 parts by mass of urea (manufactured by Tokyo Chemical Industry Co., Ltd.) is mixed and dissolved, and then the solution is cooled to 25 ° C., and a glass filter with a pore diameter of 1 μm ( The organic resin solution was prepared by permeating to Advantec Co., Ltd., model number: GA-100, and filtering.

(Example 2)
An organic resin solution was prepared in the same manner as in Example 1 except that the mass of urea to be dissolved was changed to 0.5 parts by mass.

(Example 3)
An organic resin solution was prepared in the same manner as in Example 1 except that the mass of urea to be dissolved was changed to 0.75 parts by mass.

(Example 4)
An organic resin solution was prepared in the same manner as in Example 1 except that the mass of urea to be dissolved was changed to 1.25 parts by mass.

(Example 5)
An organic resin solution was prepared in the same manner as in Example 3, except that the urea compound to be dissolved was changed to 0.75 parts by mass of dimethylurea.

(Example 6)
An organic resin solution was prepared in the same manner as Example 3, except that the urea compound to be dissolved was changed to 0.75 parts by mass of phenylurea.

  The stability of each organic resin solution was evaluated by using each organic resin solution prepared as mentioned above to the following measuring method.

(Confirmation of stability of organic resin solution)
Each organic resin solution prepared as described above was allowed to stand in a 25 ° C. environment for 7 days. Then, the number of days until polybenzimidazole was precipitated in the organic resin solution was confirmed visually.
As a result of confirmation, when the organic resin solution of Comparative Example 1 was allowed to stand for 2 days, precipitation of polybenzimidazole was observed in the organic resin solution. On the other hand, no precipitation of polybenzimidazole was observed in the organic resin solution when the organic resin solution of Example 1 was allowed to stand for 2 days, and precipitation of polybenzimidazole was observed in the organic resin solution after standing for 4 days. It was done. In addition, when the organic resin solution of Example 2-6 was allowed to stand for 2 days, no precipitation of polybenzimidazole was observed in the organic resin solution, and even after standing for 7 days, polybenzimidazole was not added to the organic resin solution. No precipitation of benzimidazole was observed.

(Spinning solution and method for producing non-woven fabric using the spinning solution)
After leaving each organic resin solution of Comparative Example 1 and Example 1-4 in a 25 ° C. environment for 2 days, each organic resin solution (only the organic resin solution of Comparative Example 1 in the polybenzimidazole in the organic resin solution) Precipitation was recognized as spinning solution, and it spins by providing to the electrostatic spinning apparatus of the following conditions, and tried manufacture of the nonwoven fabric which is a fiber assembly.
The grounded power supply was connected to a metal nozzle with an inner diameter of 0.44 mm. A grounded collector (glass cloth impregnated with polytetrafluoroethylene and conductive particles and fired) was provided to face the opening of the nozzle tip. At this time, the shortest distance between the nozzle tip and the collector was adjusted to 7 cm. The nozzle was applied at 5-15 kV with a power supply to create an electric field between the nozzle and the collector.
The spinning solution is discharged from the opening of the nozzle such that the amount of discharge is 1 cc / hour, and the spinning solution is guided to an electric field to fly the spinning solution from the opening at the tip of the nozzle to the collector and to reduce the diameter. The fiber was formed and collected on a collector to prepare a fiber web. The spinning environment in this step was a temperature of 25 ° C. and a humidity of 40% RH.
The fiber web thus obtained is heat treated at 180 ° C. for 30 minutes using an electric furnace (PHH 200 manufactured by TABAI) to volatilize dimethylacetamide remaining in the fibers constituting the fiber web. The resultant was removed (as well as the urea compound was volatilized if the urea compound remained on the fiber web) to produce a non-woven fabric.

(Comparative example 2)
In the polybenzimidazole non-woven fabric manufactured using the organic resin solution of Comparative Example 1 as a spinning solution after standing for 2 days in a 25 ° C. environment, many non-fibers such as shot are present, and the average fiber is The diameter (500 nm) and the CV value (0.5) of the fiber diameter were unintentionally large. In addition, discharge of the spinning solution from the tip of the nozzle was not stable during spinning, and it was difficult to produce a nonwoven fabric.

(Examples 7-10)
In the polybenzimidazole non-woven fabric produced using each organic resin solution of Example 1-4 as a spinning solution after standing for 2 days in a 25 ° C. environment, the presence of non-fiber matter such as shot The average fiber diameter (400 nm) and the CV value (0.2) of the fiber diameter were small. Moreover, it was able to spin in the state which discharge of the spinning solution from the nozzle tip was stable.

  From the above, the organic resin solution according to the present invention and the spinning solution comprising the organic resin solution are excellent in stability, and by using the spinning solution, it is possible to produce a fiber assembly of a desired embodiment.

(Comparative example 3)
Using the coater (slit width: 200 μm) on a glass plate, the organic resin solution of Comparative Example 1 (the precipitation of polybenzimidazole was observed in the organic resin solution) after standing for 2 days in a 25 ° C. environment It was applied by developing into a sheet form. Thereafter, the organic resin solution developed on the glass plate is provided to the oven (heating temperature: 140 ° C.) together with the glass plate, thereby removing dimethylacetamide from the organic resin solution developed in the form of a sheet, on the surface of the glass plate. A composite (polybenzimidazole film thickness: 20 μm) with a polybenzimidazole film was prepared. And the polybenzimidazole film (thickness: 20 micrometers) was manufactured by peeling a polybenzimidazole film from a glass plate.
As a result of visually confirming the main surface of the polybenzimidazole film and the main surface of the film in the composite produced in this manner, a portion with asperities appeared and the appearance was poor.

(Example 11)
The coater (slit width: 200 μm) was placed on a glass plate with the organic resin solution of Example 1 (no precipitation of polybenzimidazole was not observed in the organic resin solution) after standing for 2 days in a 25 ° C. environment. It was applied by developing into a sheet shape. Thereafter, the organic resin solution developed on the glass plate is provided to the oven (heating temperature: 140 ° C.) together with the glass plate to remove dimethylacetamide and urea from the organic resin solution developed in the form of a sheet, thereby the glass plate A composite (polybenzimidazole film thickness: 20 μm) having a polybenzimidazole film on the surface was produced. And the polybenzimidazole film (thickness: 20 micrometers) was manufactured by peeling a polybenzimidazole film from a glass plate.
When the main surface of the polybenzimidazole film in the composite produced in this manner and the main surface of the film were visually confirmed, no irregularities were found and the appearance was good.

From the above, by using the organic resin solution according to the present invention, it is possible to prevent the presence of non-uniform portions such as uneven portions such as uneven portions and locally different portions of various physical properties such as rigidity, etc. And complexes can be manufactured.

  Depending on the method of producing an organic resin solution and a spinning solution of the present invention, a fiber assembly using the spinning solution, a film using the organic resin solution, and a method of producing a composite, for example, an air filter, liquid filter, alkali Separators for electrochemical devices such as batteries, lithium batteries or capacitors, water treatment membranes, gas separation membranes, electrolyte membranes, supports for various membranes such as the above-mentioned membranes, gas diffusers, masks and substrates for patches, etc. We can provide materials that can be used as various industrial materials such as sanitary materials and sound absorbing materials.

Claims (5)

An organic resin solution containing a urea compound and an organic resin containing nitrogen atom in the chemical structure. A spinning solution comprising the organic resin solution according to claim 1. A method for producing a fiber assembly, comprising the steps of reducing the diameter of the spinning solution according to claim 2 and forming it into fibers for collection. The manufacturing method of the organic resin film provided with the process of removing a solvent from the organic resin solution which expand | deployed in the said sheet form, after expand | deploying the organic resin solution of Claim 1 in sheet form. An organic resin film is provided on the surface of the object to be coated, including the step of removing the solvent from the organic resin solution applied to the object to be coated after applying the organic resin solution according to claim 1 to the object to be coated Method of manufacturing a complex.