Polyimide fiber paper

文档序号:1431892 发布日期:2020-03-17 浏览:46次 中文

阅读说明:本技术 聚酰亚胺纤维纸 (Polyimide fiber paper ) 是由 町田英明 日高正太郎 久野贵治 高桥成彰 植田源 于 2018-08-07 设计创作,主要内容包括:以往的聚酰亚胺原材料由于在聚酰亚胺纤维中利用热塑性的聚酰亚胺,所以有耐热性较低的问题。此外,虽然仅使用耐热性较高的非热塑性聚酰亚胺,但由于是通过将聚酰亚胺的前体溶液纺丝、由高速气流拉取并捕捉到基材上、接着进行聚酰亚胺化的工序得到的,所以有需要特殊的制造装置、难以得到均匀的厚度特别是难以得到宽度较宽的片制品且成为高成本的问题。为了解决上述课题,在本发明中,提供一种聚酰亚胺纤维纸的制造方法,由以下的工序构成:短纤维准备工序,准备非热塑性聚酰亚胺的削出短纤维;以及临时固定纸形成工序,将作为水溶性高分子且作为分解温度比聚酰亚胺的玻化温度低温的材料的水溶性高分子混合,通过进行湿式抄纸,形成临时固定的临时固定纸。(Conventional polyimide materials have a problem of low heat resistance because thermoplastic polyimide is used as the polyimide fibers. Further, although only a non-thermoplastic polyimide having high heat resistance is used, since the polyimide is obtained by a process of spinning a polyimide precursor solution, drawing the solution with a high-speed gas flow, capturing the drawn solution on a substrate, and then imidizing the drawn solution, there are problems that a special production apparatus is required, it is difficult to obtain a uniform thickness, particularly, it is difficult to obtain a sheet product having a wide width, and the cost is high. In order to solve the above problems, the present invention provides a method for producing a polyimide fiber paper, comprising the steps of: a short fiber preparation step of preparing cut short fibers of non-thermoplastic polyimide; and a temporary fixing paper forming step of mixing a water-soluble polymer, which is a water-soluble polymer and is a material having a decomposition temperature lower than the glass transition temperature of the polyimide, and performing wet papermaking to form temporary fixing paper for temporary fixing.)

1. A method for producing polyimide fiber paper is characterized in that,

the method comprises the following steps:

a short fiber preparation step of preparing cut short fibers of non-thermoplastic polyimide; and

and a temporary fixing paper forming step of mixing the cut short fibers with a water-soluble polymer solution which is a water-soluble polymer and is a material having a decomposition temperature lower than the glass transition temperature of the polyimide, and performing wet papermaking to form temporary fixing paper.

2. The method for producing polyimide fiber paper according to claim 1,

and a polyimide precursor dispersing step of dispersing the polyimide precursor in the temporary fixing paper after the temporary fixing paper forming step.

3. The method for producing polyimide fiber paper according to claim 1,

and a polyimide solution dispersing step of dispersing the polyimide solution in the temporary fixing paper after the temporary fixing paper forming step.

4. The method for producing polyimide fiber paper according to any one of claims 1 to 3,

further comprises a water-soluble polymer removing step of removing all the water-soluble polymer by heat treatment after the temporary fixing paper forming step.

5. The method for producing polyimide fiber paper according to any one of claims 1 to 3,

further comprises a water-soluble polymer partial removal step of removing a part of the water-soluble polymer by heat treatment after the temporary fixing paper forming step.

6. The method for producing polyimide fiber paper according to claim 4,

and a polyimide precursor dispersing step of dispersing the polyimide precursor in the temporary fixing paper after the water-soluble polymer removing step.

7. The method for producing polyimide fiber paper according to claim 5,

further comprising a polyimide precursor dispersing step of dispersing the polyimide precursor in the temporary fixing paper after the step of partially removing the water-soluble polymer.

8. The method for producing polyimide fiber paper according to claim 4,

and a polyimide solution dispersing step of dispersing the polyimide solution in the temporary fixing paper after the step of removing all the water-soluble polymer.

9. The method for producing polyimide fiber paper according to claim 5,

further comprises a polyimide solution dispersing step of dispersing the polyimide solution in the temporary fixing paper after the step of partially removing the water-soluble polymer.

10. The method for producing polyimide fiber paper according to claim 6 or 7,

and an imidization step of imidizing the polyimide precursor by heating after the polyimide precursor dispersion step.

11. The method for producing polyimide fiber paper according to claim 8 or 9,

and an imidization step of imidizing the precursor contained in the polyimide solution by heating after the polyimide solution dispersion step.

12. A polyimide fiber paper intermediate structure A characterized in that,

a nonwoven fabric in which short fibers of a non-thermoplastic polyimide are cut out is dispersed as a water-soluble polymer at a decomposition temperature lower than the glass transition temperature of the polyimide.

13. A polyimide fiber paper intermediate structure (B) characterized in that,

a non-woven fabric made of chopped non-thermoplastic polyimide is dispersed with a heat-modified water-soluble polymer which is a water-soluble polymer and has a lower decomposition temperature than the glass transition temperature of the polyimide.

14. A polyimide fiber paper intermediate structure (C) characterized in that,

a non-woven fabric made of chopped non-thermoplastic polyimide is impregnated with a polyimide precursor solution or a polyimide solution by dispersing a heat-modified water-soluble polymer, which is a water-soluble polymer and has a lower decomposition temperature than the glass transition temperature of the polyimide, in the non-woven fabric.

15. The method for producing polyimide fiber paper according to any one of claims 1 to 11,

the water-soluble polymer is contained in an amount of 1 to 50 wt% based on the polyimide.

16. The method for producing polyimide fiber paper according to any one of claims 1 to 11 and 15,

the water-soluble polymer is one or more of starch, alginic acid, carboxymethyl cellulose, casein, vinylon, polyvinyl alcohol, vinyl acetate, polyvinyl acetate, and/or derivatives thereof.

17. The method for producing polyimide fiber paper according to any one of claims 1 to 11, 15 and 16,

the length of the polyimide staple fiber is 1.0mm to 10.0 mm.

18. The method for producing polyimide fiber paper according to claim 17,

the length of the polyimide staple fiber is 2.0mm to 6.0 mm.

19. The method for producing polyimide fiber paper according to any one of claims 1 to 11 and 15 to 18,

the width of the polyimide staple fiber is 1 μm to 50 μm.

20. The method for producing polyimide fiber paper according to claim 19,

the width of the polyimide staple fiber is 3 to 25 μm.

Technical Field

The present invention relates to a paper made of polyimide fibers.

Background

Polyimide films are materials excellent in electrical insulation, heat resistance, cold resistance, heat resistance, chemical resistance, and mechanical properties, and are in high demand in a wide range of fields from aerospace to automobiles and communication devices. However, polyimide films have limitations in terms of heat insulation, gas or liquid permeability, and permeability in terms of the properties possessed by the films, and development of flexible sheet-like products that improve these properties while exhibiting high functionality of polyimide has yet to be carried out. In addition, since a polyimide film generally has a high cost in terms of increasing its thickness and also has a high weight, development of a sheet-like product of polyimide having a low cost, a large thickness and a light weight is required.

As a method for producing a raw material of a polyimide nonwoven fabric using polyimide fibers, there are techniques shown in patent documents 1 and 2, for example.

Disclosure of Invention

Problems to be solved by the invention

However, the polyimide material disclosed in patent document 1 has a problem of low heat resistance because thermoplastic polyimide is used as the polyimide fibers.

Further, the polyimide material disclosed in patent document 2 is obtained by spinning a polyimide precursor solution, drawing the solution with a high-speed gas flow, capturing the drawn solution on a substrate, and then imidizing the drawn solution, and therefore, there is a problem that a special production apparatus is required, it is difficult to obtain a uniform thickness, and in particular, it is difficult to obtain a sheet product having a wide width, and the cost is high.

Means for solving the problems

In order to solve the above problems, the present invention provides the following polyimide fiber paper and the like. Provided is a method for producing polyimide fiber paper, comprising the following steps: a short fiber preparation step of preparing cut short fibers of non-thermoplastic polyimide; and a temporary fixing paper forming step of mixing a water-soluble polymer, which is a water-soluble polymer and is a material having a decomposition temperature lower than the glass transition temperature of the polyimide, and performing wet papermaking to form temporary fixing paper for temporary fixing.

Next, there is provided a method for producing a polyimide fiber paper, further comprising a polyimide precursor dispersing step of dispersing a polyimide precursor in the temporary fixing paper after the temporary fixing paper forming step.

Next, there is provided a method for producing a polyimide fiber paper, further comprising a polyimide solution dispersing step of dispersing a polyimide solution in the temporary fixing paper after the temporary fixing paper forming step.

Next, there is provided a method for producing a polyimide fiber paper, further comprising a water-soluble polymer removing step of removing all of the water-soluble polymer by heat treatment after the temporary fixing paper forming step.

Next, there is provided a method for producing a polyimide fiber paper, further comprising a water-soluble polymer partial removal step of removing a part of the water-soluble polymer by heat treatment after the temporary fixing paper formation step.

Next, there is provided a method for producing a polyimide fiber paper, further comprising a polyimide precursor dispersing step of dispersing a polyimide precursor in the temporary fixing paper after the step of removing all of the water-soluble polymer.

Next, there is provided a method for producing a polyimide fiber paper, further comprising a polyimide precursor dispersing step of dispersing a polyimide precursor in the temporary fixing paper after the step of partially removing the water-soluble polymer.

Next, there is provided a method for producing a polyimide fiber paper, further comprising a polyimide solution dispersing step of dispersing a polyimide solution in the temporary fixing paper after the step of removing all of the water-soluble polymer.

Next, there is provided a method for producing a polyimide fiber paper, further comprising a polyimide solution dispersing step of dispersing a polyimide solution in the temporary fixing paper after the step of partially removing the water-soluble polymer.

Next, there is provided a method for producing a polyimide fiber paper, further comprising an imidization step of imidizing the polyimide precursor by heating after the polyimide precursor dispersion step.

Next, there is provided a method for producing a polyimide fiber paper, further comprising an imidization step of imidizing a precursor contained in the polyimide solution by heating after the polyimide solution dispersion step.

Next, a polyimide fiber paper intermediate structure a is provided in which a water-soluble polymer, which is a water-soluble polymer and has a decomposition temperature lower than the glass transition temperature of polyimide, is dispersed in a non-woven fabric of non-thermoplastic polyimide from which short fibers have been cut.

Next, a polyimide fiber paper intermediate structure B is provided in which a modified product of a water-soluble polymer, which is a water-soluble polymer and has a decomposition temperature lower than the glass transition temperature of polyimide, is dispersed in a non-thermoplastic polyimide nonwoven fabric from which short fibers have been cut.

Next, a polyimide fiber paper intermediate structure C is provided in which a modified product of a water-soluble polymer, which is a water-soluble polymer and has a decomposition temperature lower than the glass transition temperature of polyimide, is dispersed in a non-thermoplastic polyimide chopped nonwoven fabric, and a polyimide precursor or a polyimide solution is impregnated therein.

Next, a method for producing a polyimide fiber paper is provided, wherein the water-soluble polymer is contained in an amount of 1 to 50% by weight based on the polyimide.

Next, there is provided a method for producing a polyimide fiber paper, wherein the water-soluble polymer is at least one of starch, alginic acid, carboxymethyl cellulose, casein, vinylon, polyvinyl alcohol, vinyl acetate, polyvinyl acetate, and/or derivatives thereof.

Then, a method for producing a polyimide fiber paper is provided, wherein the length of the polyimide staple fiber is 1.0mm to 10.0 mm.

Then, a method for producing a polyimide fiber paper is provided, wherein the length of the polyimide staple fiber is 2.0mm to 6.0 mm.

Then, a method for producing a polyimide fiber paper is provided, wherein the width of the polyimide staple fiber is 1 μm or more and 50 μm or less.

Then, a method for producing a polyimide fiber paper is provided, wherein the width of the polyimide staple fiber is 3 μm or more and 25 μm or less.

Effects of the invention

According to the present invention, a polyimide fiber paper can be produced in which the thermoplastic polyimide component in the constituent material is substantially 100%. A method for producing a raw material which can sufficiently exhibit the inherent properties of a non-thermoplastic polyimide and is excellent in heat resistance, flame retardancy, electrical insulation, heat insulation and lightweight can be provided.

Further, by utilizing the adhesiveness possessed by the intermediate structure, the polyimide fiber paper or the intermediate structure of the present invention can be laminated with other materials, whereby a composite material which can realize reinforcement of characteristics or addition can be provided.

Drawings

Fig. 1 is a flowchart showing an example of a method for producing polyimide fiber paper according to embodiment 1.

Fig. 2 is an enlarged conceptual view of the temporary fixing paper of the present invention.

Fig. 3 is a flowchart showing an example of the method for producing the polyimide fiber paper according to embodiment 2.

Fig. 4 is an enlarged conceptual view of a state where a polyimide precursor solution or a polyimide solution is dispersed in the temporary fixing paper of the present invention.

Fig. 5 is a flowchart showing an example of the method for producing the polyimide fiber paper according to embodiment 3.

Fig. 6 is a flowchart showing an example of the method for producing the polyimide fiber paper according to embodiment 4.

FIG. 7 is an enlarged conceptual view of a state after the step of removing all of the water-soluble polymer in accordance with the present invention.

Fig. 8 is a flowchart showing an example of the method for producing the polyimide fiber paper according to embodiment 5.

FIG. 9 is an enlarged conceptual view of a state after a step of partially removing a water-soluble polymer according to the present invention.

FIG. 10 is an enlarged conceptual view showing a state where a polyimide precursor solution or a polyimide solution is dispersed after the step of removing all of the water-soluble polymer in the present invention.

Fig. 11 is a flowchart showing an example of the method for producing the polyimide fiber paper according to embodiment 6.

FIG. 12 is an enlarged conceptual view showing a state where a polyimide precursor solution or a polyimide solution is dispersed after a step of partially removing a water-soluble polymer according to the present invention.

Fig. 13 is a flowchart showing an example of the method for producing polyimide fiber paper according to embodiment 7.

Fig. 14 is a flowchart showing an example of the method for producing the polyimide fiber paper according to embodiment 8.

Fig. 15 is a flowchart showing an example of the method for producing polyimide fiber paper according to embodiment 9.

Fig. 16 is a flowchart showing an example of the method for producing polyimide fiber paper according to embodiment 10.

Fig. 17 is a flowchart showing an example of the method for producing polyimide fiber paper according to embodiment 11.

FIG. 18 is an enlarged conceptual view of a polyimide staple fiber of the present invention.

Detailed Description

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the following description, embodiment 1 corresponds to claim 1, embodiment 2 corresponds to claim 2, embodiment 3 corresponds to claim 3, embodiment 4 corresponds to claim 4, embodiment 5 corresponds to claim 5, embodiment 6 corresponds to claim 6, embodiment 7 corresponds to claim 7, embodiment 8 corresponds to claim 8, embodiment 9 corresponds to claim 9, embodiment 10 corresponds to claim 10, embodiment 11 corresponds to claim 11, embodiment 12 corresponds to claim 12, embodiment 13 corresponds to claim 13, embodiment 14 corresponds to claim 14, embodiment 15 corresponds to claim 15, embodiment 16 corresponds to claim 16, embodiment 17 corresponds to claim 18, embodiment 18 corresponds to claim 19, embodiment 19 corresponds to claim 20 and embodiment 20 corresponds to claim 21. The present invention is not limited to these embodiments, and can be implemented in various forms without departing from the spirit thereof.

< embodiment 1>

< brief summary of embodiment 1>

The method for producing a polyimide fiber paper according to the present embodiment can produce a polyimide fiber paper without using a special apparatus by subjecting a polyimide fiber obtained by cutting a polyimide film wound in a cylindrical shape to a wet papermaking method such as that for producing japanese paper and a plurality of heating and pressing steps.

< Structure of embodiment 1>

Fig. 1 is a flowchart showing an example of the method for producing the polyimide fiber paper according to the present embodiment. As shown in the drawing, the method for producing the polyimide fiber paper includes a short fiber preparation step (0101) and a temporary fixing paper formation step (0102).

< description of the structure of embodiment 1>

< embodiment 1 short fiber preparation step >

The "short fiber preparation step" is a step of preparing non-thermoplastic polyimide and cutting short fibers. The polyimide fiber is cut by rotating a roll of a polyimide film wound in a band shape into a cylindrical shape and bringing a blade into contact with a side surface of the rotated polyimide film roll. By rotating the polyimide film roll and abutting the blade, a bundle of very thin polyimide fibers matching the film thickness and the blade fineness was produced. The polyimide staple fibers are produced by cutting the polyimide fiber bundles.

Since the polyimide fiber is obtained by shaving, the fiber has a uniform thickness, and thus the processing is easy in the subsequent process. Further, by adjusting the thickness of the polyimide film constituting the polyimide film roll and the fineness of the tip of the cutting blade, the width of the cut polyimide fiber can be easily varied, and a fiber having a smaller fiber width can be easily produced as compared with a technique using spinning. Further, the fiber length can be freely adjusted by cutting the bundle of the cut fibers.

Since the width and length of the fibers can be freely combined, the width and length of the fibers can be varied according to the use of the polyimide fiber paper, and polyimide fiber paper having various strengths and durability can be manufactured.

< embodiment 1 temporary fixing paper Forming Process >

The "temporary fixing paper forming step" is a step of mixing a water-soluble polymer, which is a water-soluble polymer and has a decomposition temperature lower than the glass transition temperature of polyimide, with cut polyimide short fibers, and forming temporary fixing paper by wet papermaking. In the temporary fixing paper forming process, a composite pulp forming process, a sheeting process and a fusion bonding process are included. Wet papermaking is a process in which a polyimide short fiber and a water-soluble polymer are mixed and a composite slurry dispersed in water is taken up to form a sheet. By performing the temporary fixation, the handling in the next step becomes easy.

The water-soluble polymer is preferably insoluble in water at ordinary temperature, and in this case, the water-soluble polymer in the composite slurry is in the form of fibers or/and powder.

The composite slurry forming step is a step of mixing the polyimide short fibers with a water-soluble polymer which is a water-soluble polymer and is a material having a lower decomposition temperature than the glass transition temperature of the polyimide to form a composite slurry. Although not particularly limited, for example, a dispersion material (for example, TEXANOL PE-10F, manufactured by JIUMINU GmbH, water-soluble polyurethane resin), a defoaming material (for example, FOAMLESS P NEW, manufactured by Minghuai chemical Co., Ltd.), a thickener (for example, a polyacrylamide thickener, manufactured by Minghuai chemical Co., Ltd., MEIPAM), and the like, which are generally used as additives for papermaking, may be added as necessary. The dispersibility of the polyimide staple fibers and the water-soluble polymer is improved by the dispersing material and the thickener, and the defoaming material suppresses the generation of bubbles that cause pinholes. These additives hardly remain as solid components of the temporary fixing paper, and therefore need not be removed.

Although polyimide staple fibers are fibers and therefore can entangle with each other in an aqueous solution, polyimide has inherently high heat resistance and therefore does not have binder fibers that function as a binder to firmly fuse the entangled staple fibers. Therefore, although the entangled fibers are not easily disentangled by the weight of water in a wet state, the entangled fibers are easily disentangled in a dry state, and the state as paper cannot be maintained. Therefore, in order to maintain the entangled polyimide staple fibers, such as fibers of japanese paper, in a dry state even when the fibers are entangled during the paper-making process, a dispersion slurry mixed with a water-soluble polymer is made up. The water-soluble polymer dissolves when heat of a dissolving temperature is applied. At this time, the water-soluble polymer is thermally fused while the polyimide short fibers sandwiched between the water-soluble polymers are sandwiched, and the polyimide short fibers are fixed in a state of being entangled with each other. Alternatively, the water-soluble polymer is bonded to the polyimide short fibers, whereby the polyimide short fibers are fixed in a state of being entangled with each other. The water-soluble polymer is dispersed for the purpose of causing hot melt adhesion. The dispersed water-soluble polymer needs to be a material having a lower temperature at which thermal fusion bonding occurs than the glass transition temperature of polyimide. When the decomposition temperature at which the water-soluble polymer is thermally melt-bonded is higher than the glass transition temperature of the polyimide, the deterioration of the polyimide may progress due to the relationship between the melt-bonding temperature and time.

The sheet forming process is a process of forming a sheet using a known wire (wire) or the like generally used in the production of paper. A sheet formed by filtering a composite pulp with a wire rod or the like (filtering is referred to as "papermaking" in the production process of the present invention) is referred to as a wet paper.

The fusion bonding process is a process of applying heat to a wet paper web formed into a sheet by using a wire material or the like to melt and bond the wet paper web by dissolving a water-soluble polymer.

The water-soluble polymer dissolves when the decomposition temperature is applied. When the water-soluble polymers are dissolved, the water-soluble polymers are thermally fused to each other, and the polyimide short fibers are sandwiched between the thermally fused water-soluble polymers and fixed in a state of being entangled with each other, or the polyimide short fibers are fixed in a state of being entangled with each other by being adhered to the thermally fused water-soluble polymers through the polyimide short fibers, as shown in fig. 2. However, the polyimide staple fibers themselves are not thermally fused, and the fixation by the thermal fusion of the water-soluble polymer is weak to such an extent that the force is weak, the number of fixed portions is small, and the durability is low, and the temporary fixation is weak.

< effect of embodiment 1>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 2>

< brief summary of embodiment 2>

This embodiment is a method for producing a polyimide fiber paper, which is obtained by adding a step of dispersing a polyimide precursor in a temporary fixing paper after the method for producing a polyimide fiber paper of embodiment 1.

< construction of embodiment 2>

Fig. 3 is a flowchart showing an example of the method for producing the polyimide fiber paper according to the present embodiment. As shown in the drawing, the method for producing the polyimide fiber paper of the present embodiment includes a short fiber preparation step (0301), a temporary fixing paper formation step (0302), and a polyimide precursor dispersion step (0303). Hereinafter, the description of the configuration common to embodiment 1 will be omitted, and the characteristic configuration of the present embodiment will be described.

< description of the structure of embodiment 2>

< embodiment 2 polyimide precursor Dispersion step >

The "polyimide precursor dispersion step" is a step of dispersing the polyimide precursor in the temporary fixing paper after the temporary fixing paper formation step. The polyimide precursor is a polyamic acid that becomes a non-thermoplastic polyimide by imidization, and may be dispersed as a polyimide precursor solution in the dispersing step. When the polyimide precursor solution is dispersed, as shown in fig. 4, a film (0402) of the polyimide precursor solution is adhered to the temporary fixing paper so as to cover the whole polyimide short fibers while a water-soluble polymer (0401) for temporarily fixing the polyimide short fibers is contained therein.

Specific examples of the method for dispersing the polyimide precursor include the following methods: the temporary fixing paper is impregnated with a polyimide precursor, excess solvent of the polyimide precursor solution impregnated is removed, the temporary fixing paper impregnated with the polyimide precursor is dried, and only the polyimide precursor from which the excess solvent has been removed and the water-soluble polymer to which the polyimide short fibers have been fixed are left on the temporary fixing paper and added. As described above, the step of adding the polyimide precursor, which is a component for main-bonding the temporary fixing paper, to the temporary fixing paper is a polyimide precursor dispersing step.

In the process of drying the impregnated polyimide precursor solution, imidization reaction of the polyimide precursor reaction does not occur.

< effect of the invention in embodiment 2>

The method for producing polyimide fiber paper according to the present embodiment can produce polyimide fiber paper having a uniform thickness and polyimide fiber paper having a wide sheet shape having a uniform thickness without using a special apparatus.

< embodiment 3>

< brief summary of embodiment 3>

This embodiment is a method for producing a polyimide fiber paper, in which a step of dispersing a polyimide solution is added after a temporary fixing paper forming step in the production step of a polyimide fiber paper described in embodiment 1 or embodiment 2.

< construction of embodiment 3>

Fig. 5 is a flowchart showing an example of a method for producing the most basic polyimide fiber paper of the present embodiment. As shown in the drawing, the method for producing the polyimide fiber paper of the present embodiment includes a short fiber preparation step (0501), a temporary fixing paper formation step (0502), and a polyimide dispersion step (0503). Hereinafter, the description of the configuration common to embodiment 1 or embodiment 2 will be omitted, and the characteristic configuration of the present embodiment will be described.

< description of the structure of embodiment 3>

< embodiment 3 polyimide Dispersion step >

The "polyimide dispersion step" is a step of dispersing the polyimide solution in the temporary fixing paper after the temporary fixing paper formation step. When the polyimide solution is dispersed, a film containing a water-soluble polymer in which polyimide short fibers are fixed and a polyimide solution is attached so as to cover the polyimide short fibers is used, as in the case of dispersing the polyimide precursor solution shown in fig. 4.

As a specific example of the method of dispersing the polyimide, a method of impregnating the temporary fixing paper with a solution of polyimide and adding the solution to the temporary fixing paper may be considered. The step of adding polyimide to the temporary fixing paper, which is a component for permanently bonding the temporary fixing paper, is a polyimide dispersion step.

< effect of embodiment 3>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 4>

< brief summary of embodiment 4>

This embodiment is a method for producing a polyimide fiber paper, which includes a step of removing all of the water-soluble polymer after the temporary fixing paper forming step in the polyimide fiber paper production step of any one of embodiments 1 to 3.

< construction of embodiment 4>

Fig. 6 is a flowchart showing an example of the method for producing the polyimide fiber paper according to the present embodiment. As shown in the drawing, the method for producing the polyimide fiber paper of the present embodiment includes a short fiber preparation step (0601), a temporary fixed paper formation step (0602), and a water-soluble polymer removal step (0603). Hereinafter, a description of a configuration common to any one of embodiments 1 to 3 is omitted, and a characteristic configuration of the present embodiment will be described.

< description of the structure of embodiment 4>

< embodiment 4 Process for removing Water-soluble Polymer from the substrate >

The "water-soluble polymer total removal step" is a step of removing all of the water-soluble polymer by heat treatment after the temporary fixing paper formation step. For example, the temporary fixing paper is sandwiched between two heat rolls, and heat is applied to decompose the water-soluble polymer. A processing method called a so-called calender process.

The heat of the heat roll for the step of removing all of the water-soluble polymer is set to 190 to 250 degrees. The temperature at which the water-soluble polymer is reliably decomposed is required to be a temperature at which the imidization reaction does not occur in the impregnated polyimide precursor in the case of embodiment 2, or a temperature at which the imidization reaction does not occur in the polyimide precursor of the impregnated polyimide solution in the case of embodiment 3.

In the process of removing the water-soluble polymer by heat treatment, the water-soluble polymer is almost removed, and a part of the water-soluble polymer is thermally modified and remains in the temporary fixing paper. The remaining water-soluble polymer thermal modifier prevents the temporary fixing paper from being dispersed after the removal of the water-soluble polymer, and maintains the state in which the polyimide fibers in the temporary fixing paper are entangled. FIG. 7 is a view showing the state of the polyimide fiber paper after the step of removing all of the water-soluble polymer. The portion surrounded by the dotted line in the figure is a process portion for temporarily fixing the polyimide short fibers of the water-soluble polymer in the paper. The part indicated by the solid line inside the dotted line is a thermally modified product of the water-soluble polymer remaining on the polyimide fiber paper after the water-soluble polymer is completely removed. As shown in the figure, even if the water-soluble polymer is completely removed in a state where imidization does not occur, the temporary fixing paper is not dispersed because the polyimide short fibers are fixed by the thermal modification product of the water-soluble polymer. Furthermore, the temporary fixing paper after the step of removing all the water-soluble polymer exhibits the viscosity of the thermally modified water-soluble polymer, and therefore can be thermally fused to another material having thermal fusion viscosity.

< effect of embodiment 4>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 5>

< brief summary of embodiment 5>

The invention according to this embodiment relates to a method for producing a polyimide fiber paper, in which only a part of the water-soluble polymer is removed after the temporary fixing paper forming step in the polyimide fiber paper production step described in any one of embodiments 1 to 3, and a part of the water-soluble polymer is left on the temporary fixing paper.

< construction of embodiment 5>

Fig. 8 is a flowchart showing an example of a method for producing the most basic polyimide fiber paper of the present embodiment. As shown in the drawing, the method for producing the polyimide fiber paper of the present embodiment includes a short fiber preparation step (0801), a temporary fixing paper formation step (0802), and a water-soluble polymer partial removal step (0803). Hereinafter, description of a configuration common to any one of embodiments 1 to 4 will be omitted, and a characteristic point of the present embodiment will be described.

< description of the construction of embodiment 5>

< embodiment 5 Process for partially removing Water-soluble Polymer >

The "water-soluble polymer partially removing step" is a step of removing a part of the water-soluble polymer by heat treatment after the temporary fixing paper forming step. In the step of removing a part of the water-soluble polymer, as in the case of the step of removing the whole water-soluble polymer, a so-called calender process may be considered in which a temporary fixing paper is sandwiched between two heat rolls, heat is applied, and the water-soluble polymer is decomposed.

The heat of the heat roll for the water-soluble polymer-complete-removing step is set to 190 to 250 degrees, as in the case of the water-soluble polymer-complete-removing step described above. The temperature at which the water-soluble polymer is reliably decomposed is required to be a temperature at which the imidization reaction does not occur in the impregnated polyimide precursor in the case of embodiment 2, or a temperature at which the imidization reaction does not occur in the polyimide precursor of the impregnated polyimide solution in the case of embodiment 3.

When the water-soluble polymer is partially removed by heat treatment, the water-soluble polymer is decomposed and the water-soluble polymer is modified simultaneously in the partial removal step. Therefore, the water-soluble polymer that has not been removed and the water-soluble polymer that has been modified by the heat treatment remain on the temporary fixing paper after a part of the removal step. FIG. 9 is a view showing the state of the polyimide fiber paper after the step of partially removing the water-soluble polymer. The portion surrounded by the dotted line in the figure is a process portion for temporarily fixing the polyimide short fibers of the water-soluble polymer in the paper. The portions indicated by the solid lines inside the dotted lines are the water-soluble polymer and the thermally modified water-soluble polymer remaining on the polyimide fiber paper after the water-soluble polymer is partially removed. As shown in the figure, even if the water-soluble polymer is partially removed in a state where the imidization reaction does not occur, the temporary fixing paper does not disperse because the water-soluble polymer and the thermal modification product of the water-soluble polymer fix the polyimide short fibers. In the figure, the part of the thermal-modified water-soluble polymer shown by the solid line in fig. 9, which is a conceptual diagram showing the state after the step of partially removing the water-soluble polymer, is larger than the part of the thermal-modified water-soluble polymer shown by the solid line in fig. 8, which is a conceptual diagram showing the state after the step of completely removing the water-soluble polymer. This is because the removal step is performed to remove only a part of the water-soluble polymer, and therefore the amount of the water-soluble polymer to be removed is small compared to the total water-soluble polymer removal step.

The polyimide staple fiber after the step of removing a part of the water-soluble polymer can be thermally fused with other thermally fusible materials because the water-soluble polymer and the modified water-soluble polymer have adhesiveness.

< effect of the invention in embodiment 5>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 6>

< brief summary of embodiment 6>

The polyimide fiber paper of the present embodiment is an invention relating to a method for producing a polyimide fiber paper by dispersing a polyimide precursor not before the step of removing all of the water-soluble polymer in the method for producing a polyimide fiber paper of embodiment 4 but after the step of removing all of the water-soluble polymer. If the polyimide precursor is dispersed after the water-soluble all-removing step, as shown in fig. 10, the polyimide short fibers are wrapped and the water-soluble polymer thermally modified substance (1001) fixed to the polyimide short fibers is wrapped, and the film (1002) is adhered so that the polyimide short fibers are wrapped with the polyimide precursor.

< construction of embodiment 6>

Fig. 11 is a flowchart showing an example of a method for producing the most basic polyimide fiber paper of the present embodiment. As shown in the drawing, the method for producing the polyimide fiber paper of the present embodiment includes a short fiber preparation step (1101), a temporary fixing paper formation step (1102), a water-soluble polymer total removal step (1103), and a polyimide precursor dispersion step (1104). Description of the structure common to any one of embodiments 1 to 5 is omitted.

As described above, if the polyimide precursor is dispersed after the step of removing all of the water-soluble polymer, as shown in fig. 10, the polyimide short fibers are wrapped and the water-soluble polymer thermally modified product fixed to the polyimide short fibers is wrapped, and the film is adhered so that the polyimide short fibers are wrapped with the polyimide precursor. After the step of removing all the water-soluble polymer, only the thermally modified water-soluble polymer is fixed to the short polyimide fibers. Therefore, the force for fixing the polyimide short fibers becomes weak. Since the polyimide staple fibers are unwound from the state of being entangled with the polyimide precursor before the imidization reaction between the polyimide staple fibers and the polyimide precursor is carried out after the step of removing all the water-soluble polymer, the cut polyimide staple fibers of embodiment 6 are preferably made of a fiber length and a fiber width that are easy to entangle with themselves. Polyimide staple fibers tend to entangle when the fiber length is relatively long and the width of the fiber is relatively thin. For example, a short polyimide fiber having a fiber length of 5mm or more and a fiber width of 25 μm or less is suitable for the production of the polyimide fiber paper of embodiment 6.

< effect of the invention in embodiment 6>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 7>

< brief summary of embodiment 7>

The polyimide fiber paper of the present embodiment is prepared by dispersing a polyimide precursor not before the step of partially removing the water-soluble polymer but after the step of partially removing the water-soluble polymer in the method for producing a polyimide fiber paper of embodiment 5. After the step of removing a part of the water-soluble polymer, if the polyimide solution is dispersed, as shown in fig. 12, the polyimide short fibers are wrapped and the water-soluble polymer thermal-modified product (1201) fixed to the polyimide short fibers are wrapped, and the film (1202) is adhered so that the polyimide short fibers are wrapped with the polyimide precursor.

< construction of embodiment 7>

Fig. 13 is a flowchart showing an example of a method for producing the most basic polyimide fiber paper of the present embodiment. As shown in the drawing, the method for producing a polyimide fiber paper according to the present embodiment includes a short fiber preparation step (1301), a temporary fixing paper formation step (1302), a water-soluble polymer partial removal step (1303), and a polyimide precursor dispersion step (1304). Description of a structure common to any one of embodiments 1 to 6 is omitted.

As described above, if the polyimide solution is dispersed after the step of partially removing the water-soluble polymer, the film is adhered to the polyimide short fiber by wrapping the polyimide short fiber, and wrapping the water-soluble polymer and the heat-modified water-soluble polymer that are fixed to the polyimide short fiber, and wrapping the polyimide short fiber with the polyimide precursor, as shown in fig. 12. In the case where a part of the water-soluble polymer is removed, unlike the case of embodiment 6 where the whole water-soluble polymer is removed, the polyimide short fibers are fixed not only by the thermal modification product of the water-soluble polymer but by both of the water-soluble polymer and the thermal modification product of the water-soluble polymer. Therefore, the mass of the water-soluble polymer and the water-soluble polymer thermally-modified product to be fixed becomes larger than that of the water-soluble polymer thermally-modified product alone. Further, the area of the polyimide short fibers fixed with the water-soluble polymer and the thermal modification product of the water-soluble polymer is larger than the area of the polyimide short fibers fixed with only the thermal modification product of the water-soluble polymer. Therefore, the fixation of the polyimide short fibers after the step of partially removing the water-soluble polymer is relatively strong. After the step of removing a part of the water-soluble polymer, the risk of entanglement and unraveling of the short polyimide fibers before imidization after the step of dispersing the polyimide precursor is relatively small, and even if the cut short polyimide fibers are relatively short and thick, the short polyimide fibers are not unraveled. For example, a polyimide staple fiber having a fiber length of 5mm or less and a fiber width of 25 μm or more is suitable for the production of the polyimide fiber paper of embodiment 7.

< effect of embodiment 7>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 8>

< brief summary of embodiment 8>

The invention of the present embodiment relates to a method for producing a polyimide fiber paper in which a polyimide solution is dispersed not before the step of removing all of the water-soluble polymer but after the step of removing all of the water-soluble polymer in the method for producing a polyimide fiber paper of embodiment 4. Similarly to fig. 10 showing the state where the polyimide precursor is dispersed after the water-soluble polymer complete removal step, if the polyimide solution is dispersed after the water-soluble polymer complete removal step, the polyimide short fibers are wrapped and the water-soluble polymer thermally modified substance fixed to the polyimide short fibers is wrapped, and the film is adhered so that the polyimide short fibers are wrapped with the polyimide solution.

< construction of embodiment 8>

Fig. 14 is a flowchart showing an example of a method for producing the most basic polyimide fiber paper of the present embodiment. As shown in the drawing, the method for producing the polyimide fiber paper of the present embodiment includes a short fiber preparation step (1401), a temporary fixing paper formation step (1402), a water-soluble polymer total removal step (1403), and a polyimide solution dispersion step (1404). Description of a structure common to any one of embodiments 1 to 7 is omitted.

As described above, if the polyimide solution is dispersed after the step of removing all the water-soluble polymer, the polyimide short fibers are wrapped and the water-soluble polymer thermally modified product fixed to the polyimide short fibers is wrapped, and the film is adhered so that the polyimide short fibers are wrapped with the polyimide solution. After the step of removing all the water-soluble polymer, only the thermally modified water-soluble polymer is fixed to the short polyimide fibers. Therefore, the force for fixing the polyimide short fibers becomes weak. Since the polyimide fiber paper cannot be produced if the polyimide staple fibers are unwound before the polyimide and the polyimide staple fibers are imidized after the step of removing all the water-soluble polymer and the step of dispersing the polyimide, the cut polyimide staple fibers of embodiment 8 are preferably made of a fiber length and a fiber width that are easily entangled with themselves, as in embodiment 6. Polyimide staple fibers tend to entangle when the fiber length is relatively long and the width of the fiber is relatively thin. For example, a short polyimide fiber having a fiber length of 5mm or more and a fiber width of 25 μm or less is also suitable for the production of the polyimide fiber paper of embodiment 8.

< effect of the invention in embodiment 8>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 9>

< brief summary of embodiment 9>

The polyimide fiber paper of the present embodiment is a method for producing a polyimide fiber paper in which a polyimide solution is dispersed not before the step of partially removing the water-soluble polymer of embodiment 5 but after the step of partially removing the water-soluble polymer. Similarly to fig. 12 showing the state where the polyimide precursor is dispersed after the step of removing a part of the water-soluble polymer, if the polyimide solution is dispersed after the step of removing a part of the water-soluble polymer, the water-soluble polymer and the heat-modified water-soluble polymer that are fixed to the polyimide short fibers are wrapped with the polyimide short fibers, and the film is adhered so that the polyimide short fibers are wrapped with the polyimide solution.

< construction of embodiment 9>

Fig. 15 is a flowchart showing an example of a method for producing the most basic polyimide fiber paper of the present embodiment. As shown in the drawing, the method for producing a polyimide fiber paper of the present embodiment includes a short fiber preparation step (1501), a temporary fixing paper formation step (1502), a water-soluble polymer partial removal step (1503), and a polyimide solution dispersion step (1504). Description of a structure common to any one of embodiments 1 to 8 is omitted.

As described above, similarly to fig. 12 showing the state where the polyimide precursor is dispersed after the step of removing a part of the water-soluble polymer, if the polyimide solution is dispersed after the step of removing a part of the water-soluble polymer, the water-soluble polymer and the heat-modified water-soluble polymer which are fixed to the polyimide short fibers are wrapped with the polyimide short fibers, and the film is adhered so that the polyimide short fibers are wrapped with the polyimide solution. When a part of the water-soluble polymer is removed, the short polyimide fibers are fixed by both the water-soluble polymer and the heat-modified water-soluble polymer, as in embodiment 7, instead of being fixed by only the heat-modified water-soluble polymer alone. Therefore, the mass of the water-soluble polymer and the water-soluble polymer thermally-modified product to be fixed becomes larger than that of the water-soluble polymer thermally-modified product alone. Further, the area of the polyimide short fibers fixed with the water-soluble polymer and the thermal modification product of the water-soluble polymer is larger than the area of the polyimide short fibers fixed with only the thermal modification product of the water-soluble polymer. Therefore, the fixation of the polyimide short fibers after the step of partially removing the water-soluble polymer is relatively strong. After the step of removing a part of the water-soluble polymer, there is relatively little risk that the polyimide short fibers are entangled and disentangled before imidization after the polyimide dispersion step, and even if the polyimide short fibers are relatively short and thick, the polyimide short fibers are not disentangled. For example, a short polyimide fiber having a fiber length of 5mm or less and a fiber width of 25 μm or more is suitable for the production of the polyimide fiber paper of embodiment 9.

< effect of the invention in embodiment 9>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 10>

< brief summary of embodiment 10>

The polyimide fiber paper of the present embodiment relates to the invention of the method for producing polyimide fiber paper, which further includes a step of performing a heat treatment after the polyimide precursor dispersion step in the method for producing polyimide fiber paper described in embodiment 6 or embodiment 7.

< construction of embodiment 10>

Fig. 16 is a flowchart showing an example of a method for producing the most basic polyimide fiber paper of the present embodiment. As shown in the drawing, the method for producing a polyimide fiber paper according to the present embodiment includes a short fiber preparation step (1601), a temporary fixed paper formation step (1602), a water-soluble polymer total removal step (1603), a polyimide precursor dispersion step (1604), and an imidization step (1605). Hereinafter, a description of a configuration common to any one of embodiments 1 to 9 will be omitted, and a characteristic point of the present embodiment will be described.

< description of the structure of embodiment 10>

< embodiment 10 Imidization step >

The "imidization step" is a step of imidizing the polyimide precursor by heating after the polyimide precursor dispersion step. The polyimide fiber temporary fixing paper is a polyimide fiber paper in which fibers are fixed to each other by imidization. In the imidization step, similarly to the case of the above-described step of removing all of the water-soluble polymer, for example, a machine commonly called a calender machine is used, and the temporary fixing paper is sandwiched between two hot rolls to apply heat to imidize the polyimide precursor, thereby fixing the polyimide fibers to each other.

The heat of the heat roll for the imidization is set to 300 degrees or more, unlike the case of the water-soluble polymer removing step. The temperature is a temperature at which the polyimide precursor is imidized and fixed to the polyimide constituting the polyimide fiber paper.

< embodiment 10 otherwise >

In the present embodiment, the temporary fixing paper is sandwiched between the heat roll and the heat roll twice across the step of removing all or a part of the water-soluble polymer and the imidization step. The paper is temporarily fixed by being sandwiched between heat rollers, pressed, and thinned by the pressing, to have a thickness as common paper. Further, the thickness and surface shape of the paper may be changed depending on the degree of pressing and the shape of the heating roller.

Further, the porosity per unit thickness can also be increased by passing the sheet through a heating furnace of 300 ℃ or higher in a non-pressurized state without using a heat roll and expanding the sheet in the thickness direction.

< effect of the invention in embodiment 10>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 11>

< brief summary of embodiment 11>

The polyimide fiber paper of the present embodiment relates to the invention of the method for producing polyimide fiber paper having an imidization step after the polyimide solution dispersion step in the method for producing polyimide fiber paper described in embodiment 8 or embodiment 9.

< construction of embodiment 11>

Fig. 17 is a flowchart showing an example of a method for producing the most basic polyimide fiber paper of the present embodiment. As shown in the drawing, the method for producing the polyimide fiber paper of the present embodiment includes a short fiber preparation step (1701), a temporary fixing paper formation step (1702), a water-soluble polymer total removal step (1703), a polyimide solution dispersion step (1704), and an imidization step (1705). Hereinafter, a description of a configuration common to any one of embodiments 1 to 10 is omitted, and a characteristic point of the present embodiment will be described.

< embodiment 11 Imidization step >

In the imidization step of the present embodiment, the polyimide precursor in the polyimide solution undergoes imidization. Thus, the polyimide fibers in the temporarily fixed state are bonded and fixed to each other to form a polyimide fiber paper. In the imidization step, similarly to the case of embodiment 10 using the polyimide precursor, for example, a machine generally called a calender machine is used to fix the polyimide fiber papers to each other by applying heat of 300 degrees or more to the temporarily fixed paper sandwiched between two heat rolls to imidize the polyimide precursor in the polyimide solution.

< embodiment 11 otherwise >

In this embodiment, as in embodiment 10, the thickness of the temporarily fixed paper is set to be as thick as a general paper by pressing the temporarily fixed paper in the step of removing all or part of the water-soluble polymer and the step of imidizing.

Further, the thickness and surface shape of the paper may be changed depending on the degree of pressing and the shape of the heating roller.

Further, the porosity per unit thickness can also be increased by passing the sheet through a heating furnace of 300 ℃ or higher in a non-pressurized state without using a heat roll and expanding the sheet in the thickness direction.

< effect of the invention in embodiment 11>

The method for producing a polyimide fiber paper of the present embodiment can produce a polyimide fiber paper having a uniform thickness and a wide sheet-like polyimide fiber paper having a uniform thickness without using a special apparatus.

< embodiment 12>

< brief summary of embodiment 12>

The invention of the present embodiment is produced in an intermediate stage of producing the polyimide fiber paper.

< construction of embodiment 12>

The invention of embodiment 12 is a polyimide fiber paper intermediate structure a that is a nonwoven fabric made of chopped non-thermoplastic polyimide. The polyimide fiber paper intermediate structure a is a nonwoven fabric in which a water-soluble polymer having a decomposition temperature lower than the glass transition temperature of polyimide is dispersed. The water-soluble polymer has a thermal fusion viscosity different from that of the non-thermoplastic polyimide, and can be fused to another substance by thermal fusion bonding of the water-soluble polymer in the polyimide fiber paper intermediate structure a. Therefore, the polyimide fiber paper intermediate structure a has adhesiveness.

< effect of the invention in embodiment 12>

The invention according to the present embodiment can provide a paper-like material containing polyimide as a main component, which is not only polyimide that is not thermoplastic but also has a tackiness that enables fusion bonding with other substances.

< embodiment 13>

< brief summary of embodiment 13>

The invention of the present embodiment is produced in an intermediate stage of producing the polyimide fiber paper.

< construction of embodiment 13>

The invention of the present embodiment is a polyimide fiber paper intermediate structure B which is a non-heating polyimide nonwoven fabric in which short fibers are cut out. The polyimide fiber paper intermediate structure B is obtained by dispersing a modified product of a water-soluble polymer, which is a water-soluble polymer and has a lower decomposition temperature than the glass transition temperature of polyimide, in a nonwoven fabric. When the water-soluble polymer is heated, both reactions of decomposition and modification occur, the water-soluble polymer having undergone the decomposition reaction is removed from the nonwoven fabric, and the heat-modified product of the modified water-soluble polymer remains in the nonwoven fabric. The heat-denatured product of the water-soluble polymer has a property of being thermally fused in the same manner as the water-soluble polymer before the heat-denaturation. Therefore, the heat-denatured product of the water-soluble polymer exhibits viscosity when heated, and can be melt-adhered to other substances. Therefore, the polyimide fiber paper intermediate structure B has melt adhesiveness.

< effect of the invention in embodiment 13>

The invention of the present embodiment can provide a polyimide fiber paper having a uniform thickness and having a tackiness enabling fusion bonding with another substance, and a wide sheet-shaped polyimide fiber paper having a uniform thickness and having a tackiness enabling fusion bonding with another substance, without using a special apparatus.

< embodiment 14>

< brief summary of embodiment 14>

The invention of the present embodiment is produced in an intermediate stage of producing the polyimide fiber paper.

< construction of embodiment 14>

The invention of the present embodiment is a polyimide fiber paper intermediate structure C which is a non-woven fabric of non-thermoplastic polyimide from which short fibers are cut. The polyimide fiber paper intermediate structure C is obtained by dispersing a modified product of a water-soluble polymer, which is a water-soluble polymer and has a decomposition temperature lower than the glass transition temperature of polyimide, in a nonwoven fabric, impregnating the nonwoven fabric with a polyimide precursor and/or a polyimide solution, and drying the impregnated polyimide precursor and/or polyimide solution. The thermally modified product of the water-soluble polymer can be thermally fused and bonded, and the properties thereof are not lost even when impregnated with a polyimide precursor and/or a polyimide solution. Therefore, the polyimide fiber paper intermediate structure C has adhesiveness, and if heat is applied, it can be thermally fused with another substance having adhesiveness.

< effect of the invention in embodiment 14>

The invention of the present embodiment can provide a polyimide fiber paper having a uniform thickness and having a tackiness enabling fusion bonding with another substance, and a wide sheet-shaped polyimide fiber paper having a uniform thickness and having a tackiness enabling fusion bonding with another substance, without using a special apparatus.

< embodiment 15>

The invention of this embodiment represents the optimum range of the weight of the water-soluble polymer in the method for producing polyimide fiber paper described in any one of embodiments 1 to 11. The weight of the water-soluble polymer is preferably in the range of 1 to 50% by weight based on the weight of the polyimide. If the amount of the water-soluble polymer is too large, the portion where the water-soluble polymer exists is too hydrophobic when the water-soluble polymer is removed, and the strength and effect as a polyimide fiber paper become insufficient. On the other hand, when the amount of the water-soluble polymer is too small, the force for temporarily fixing the polyimide by fusion bonding of the water-soluble polymer becomes too weak, and the temporary fixation is no longer possible. Therefore, there is an optimum range in the weight of the water-soluble polymer.

< embodiment 16>

The invention according to the present embodiment represents the optimum type for the water-soluble polymer in the method for producing polyimide fiber paper according to any one of embodiments 1 to 11 and claim 15. The most preferable water-soluble polymer for producing the polyimide fiber paper is one or more of starch, alginic acid, carboxymethyl cellulose, casein, vinylon, polyvinyl alcohol, vinyl acetate, polyvinyl acetate, and/or derivatives thereof. There are many water-soluble polymers, but depending on the type, the strength of hot melt adhesion or the degree of thermal modification by the removal step varies, and any one or more of the above-mentioned water-soluble polymers may be used as the most suitable water-soluble polymer for producing the polyimide fiber paper.

< embodiment 17>

The invention of the present embodiment represents the optimum types for the polyimide precursor and the polyimide solution in the method for producing polyimide fiber paper described in any one of embodiments 1 to 11 and claim 16.

The polyimide precursor is a non-thermoplastic polyimide precursor obtained by polymerizing an aromatic diamine component and an aromatic acid anhydride component in an organic solvent, or a non-thermoplastic polyimide precursor which is substituted with a different solvent from that used in the polymerization after polycondensation.

The aromatic diamine component contained in the polyimide precursor is 1 or more selected from the group consisting of p-phenylenediamine, 1, 3-bis (4-aminophenoxy) benzene, 4 '-diaminodiphenyl ether and 3, 4' -diaminodiphenyl ether, but may contain other aromatic diamine components than these components.

The aromatic acid anhydride component contained in the polyimide precursor is 1 or more selected from the group consisting of 4, 4' -oxydiphthalic anhydride, pyromellitic dianhydride, and 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride, but may contain an aromatic acid anhydride component other than these components.

Examples of the organic solvent used for forming the polyamic acid solution containing the polyimide precursor include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol solvents such as phenol, o-, m-or p-cresol, xylenol, halogenated phenol and catechol, aprotic polar solvents such as hexamethylphosphoramide and γ -butyrolactone, and xylene, toluene, acetone and water can also be used.

The polyimide solution is a solution containing a precursor component to be a non-thermoplastic polyimide and a non-thermoplastic polyimide component at least by an imidization reaction.

The non-thermoplastic polyimide contained in the polyimide solution is not specified, but is preferably a polyimide obtained from a polyimide precursor composed of an aromatic diamine and an aromatic acid anhydride.

The precursor component contained in the polyimide solution and to be a non-thermoplastic polyimide by imidization is not specified, but polyimide precursors such as those obtained in 0134 to 0136 described above and the like can be given as examples.

The solvent used in the polyimide solution is not particularly limited, and examples thereof include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol solvents such as phenol, o-, m-or p-cresol, xylenol, halogenated phenol and catechol, aprotic polar solvents such as hexamethylphosphoramide and γ -butyrolactone, and xylene, toluene, acetone and water can be used.

< embodiment 18>

The invention according to this embodiment is an invention that indicates an appropriate length of the polyimide staple fibers in the method for producing polyimide fiber paper according to any one of embodiments 1 to 11 and claims 15 to 17. The polyimide staple fiber is suitably 1.0mm to 10.0mm long. If the polyimide staple fiber is too short, the polyimide fibers are not sufficiently entangled with each other in the slurry, and even if the polyimide fibers are taken up, they cannot be sufficiently entangled with each other as a nonwoven fabric. Therefore, even when a water-soluble polymer is used, temporary fixation is difficult. On the other hand, if the polyimide staple fibers are too long, the fibers are entangled with each other in a complicated manner, and even if heat and pressure are applied, the surface is not smooth, and the finished state as paper is insufficient. Thus, there is an appropriate value in terms of the length of the polyimide staple fiber.

If the length is within the appropriate range, the finished state of the paper becomes sufficient, but the polyimide density per unit area differs depending on the length of the fiber length, and therefore, there may be a case where some difference occurs in the degree of expression of the characteristics such as heat resistance and mechanical strength possessed by the polyimide. Therefore, it is preferable to form the polyimide staple fiber by selecting one or more lengths from appropriate lengths according to the purpose.

< embodiment 19>

The invention of the present embodiment represents the optimum length of the polyimide short fibers in the method for producing a polyimide fiber paper described in embodiment 18. The optimal length of the polyimide short fiber is more than 2.0mm and less than 6.0 mm. It has been explained that the difference in the manufacturing process and the completion condition occurs depending on the length of the polyimide short fiber. In embodiment 18, although it is pointed out that the length is appropriately long depending on the production process and the completion state, the length of the polyimide short fibers is optimally long, which satisfies all the conditions of the stability of the production process, the completion state of the paper, the effects of the completed polyimide fiber paper and the intermediate structure thereof.

< embodiment 20>

The invention of this embodiment represents values of an appropriate region of the width of the polyimide staple fibers in the polyimide fiber paper production method described in any one of embodiments 1 to 11 and 15 to 19. Fig. 18 is a conceptual diagram of polyimide staple fibers. The length indicated by a solid line in the figure is the width (1801) of the polyimide short fiber, and the length indicated by a broken line in the figure is the height (1802) of the polyimide short fiber. The width of the polyimide staple fibers and the height of the polyimide staple fibers may be longer than each other, or both may have the same length.

The polyimide staple fiber preferably has a width of 1 μm or more and 50 μm or less. The polyimide staple fibers have different flexibility depending on the width of the polyimide staple fibers. The thicker one is hard to bend, and the thinner one is soft to bend. Therefore, the complexity of intertwining the polyimide short fibers, and the water-soluble polymer with each other varies depending on the width of the polyimide short fibers. In the case of the simple winding method, the polyimide short fibers may be unwound from the wound state by a slight impact, and the strength of the finished paper may be weakened. On the other hand, if the winding is too complicated, the intertwined portions overlap to have a thickness, and therefore the finished paper is not smooth, and the degree of finish as paper becomes insufficient. Therefore, the polyimide staple fibers have a suitable width as described above.

As described above, the polyimide short fibers are cut by abutting a blade against the side surface of the roll of polyimide film. The height of the polyimide short fibers is determined by the thickness of the polyimide film, and the width of the polyimide short fibers is adjusted by a blade that is cut from the side surface. The polyimide film having a thickness of 1 μm or more and 50 μm or less is suitable as a roll of a polyimide film cut out of polyimide short fibers when producing a polyimide fiber paper. Further, a polyimide film having a thickness of 3 μm or more and 25 μm or less is preferable as a roll of a polyimide film from which polyimide short fibers are cut when a polyimide fiber paper is produced.

< embodiment 21>

The invention of the present embodiment represents the optimum width of the polyimide short fibers in the method for producing a polyimide fiber paper described in embodiment 20. The polyimide staple fiber has an optimum width of 3 to 25 μm. It has been explained that a difference occurs in the manufacturing process, the completion condition depending on the width of the polyimide short fiber. In embodiment 19, although it is pointed out that the width is appropriate for the production process and the completion state, the width of the polyimide staple fiber which is further in the condition of optimally satisfying all the effects of the stability of the production process, the completion state of the paper, the completed polyimide fiber paper and the intermediate structure thereof is the optimum width.

< others >

In embodiments 15 to 21, suitable conditions or optimum conditions in the case of producing a polyimide fiber paper by the present polyimide fiber paper production method are shown. The weight of the water-soluble polymer, the type of the water-soluble polymer, the length of the polyimide short fibers, and the width of the polyimide short fibers are factors that affect each other, and therefore the state of completion and properties of the finished paper are determined by the above factors being compositely related to each other. Therefore, it is necessary to make an optimum combination in consideration of the purpose of use of the manufactured paper and the heating conditions of the heating process required in the manufacturing process.

Industrial applicability

The polyimide fiber paper of the present invention can be used as a circuit board material, a heat-resistant and heat-insulating material, a sound-absorbing material, an insulating material for motors and generators, and a heat-resistant filter.

Description of the reference numerals

0101 short fiber preparation process

0102 temporarily fixing the paper forming process.

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