JPH08319420A - Polyamide solution composition and production of fibrid and papery sheet made therefrom - Google Patents

Abstract

PURPOSE: To provide a homogeneous solution composition of an aliphatic polyamide such as nylon 6 or 66 or an aliphatic/ aromatic polyamide such as nylon 6I or 6T, to produce a fibrid (pulpy material) from the composition and to produce a synthetic paper from the fibrid. CONSTITUTION: This composition is a solution prepared by dissolving an aliphatic polyamide and/or an aliphatic/aromatic polyamide in N-methyl-2-pyrrolidone(NMP) containing calcium chloride, wherein the rate of the polyamide to NMP is such that 3-25wt.% polyamide and 97-75wt.% NMP are present, and 5-60 pts.wt. calcium chloride is present per 100 pts.wt. polyamide. This composition is made into a fibrid (pulpy material) by precipitating the composition under agitation in a precipitant based on water, and the fibrid can be made into a synthetic paper by forming a mixture of the fibrid with various fibers or natural pulps into paper. The synthetic paper is useful in the production of honeycomb cores, battery separators, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel solution composition of an aliphatic polyamide and / or an aliphatic aromatic polyamide, a method for producing fibrids (pulp-like particles) using the same, and a paper-like sheet using the fibrids. It relates to a manufacturing method. More specifically, a novel solution composition containing an aliphatic polyamide and / or an aliphatic aromatic polyamide, N-methyl-2-pyrrolidone and calcium chloride and suitable for forming into a film, a fiber or a fibrid, and the solution composition The present invention relates to a method for producing a polyamide fibrid having good paper-making property using a product, and a method for producing a paper-like sheet (so-called synthetic paper) using the polyamide fibrid thus obtained.

[0002]

2. Description of the Related Art Aliphatic polyamides such as polycaprolactam (nylon 6) and polyhexamethylene adipamide (nylon 6.6) have a melting point of 210 to 280 ° C. and can be manufactured into fibers, films and the like by melt molding. Is well known. Further, a method is also known in which these polymers are dissolved in concentrated sulfuric acid, formic acid or the like to produce a synthetic pulp-like material called "fibrid" from the solution.

For example, the German patent DE 2056010
(And corresponding US Pat. No. 3,831,317)
Dissolve polycaprolactam (nylon 6) and polyhexamethyleneadipamide (nylon 6.6) in concentrated sulfuric acid,
A method has been proposed in which this is poured into a 1N NaOH aqueous solution to produce a fibrid.

As described above, the aliphatic polyamide is soluble in concentrated sulfuric acid, but the concentrated sulfuric acid solution requires a large amount of sulfuric acid and an alkali hydroxide for neutralizing the concentrated sulfuric acid solution. Also, when trying to remove sulfuric acid by washing with water without using a neutralizing agent, not only a large amount of water must be used, but also the problem of equipment corrosion cannot be avoided. A solution dissolved in concentrated sulfuric acid is hardly a practically preferable polyamide solution composition.

According to Japanese Examined Patent Publication No. 35-11851 (and corresponding British Patent No. 868,651), polyhexamethylene adipamide which is an aliphatic polyamide is used.
The fibrids obtained from polycaproamide copolymers are disclosed to have excellent properties. This copolymer is concentrated sulfuric acid, formic acid, ethylene glycol, N, N-dimethylformamide, N, N-dimethylacetamide, N
-Methyl-2-pyrrolidone, soluble in m-cresol.

However, although these solvents dissolve the polyhexamethylene adipamide-polycaproamide copolymer, homopolyamides such as polycaprolactam (nylon 6) and polyhexamethylene adipamide (nylon 66) do not. , Concentrated sulfuric acid, formic acid and m-cresol, N, N-dimethylformamide, N, N-
It is difficult to dissolve in dimethylacetamide, N-methylpyrrolidone, and ethylene glycol, and it is difficult to prepare a good aliphatic polyamide solution using these solvents.

As described above, phenolic solvents such as phenol and cresol are known as solvents for aliphatic polyamides. The polyamide solution composition prepared using these phenolic solvents is Since it is poorly soluble in water, fibers, films, fibrids, and other molded articles from this solution composition require a specific organic solvent such as the above as a precipitant (coagulation bath solution) in order to obtain molded articles such as fibrids. Not only is the cost high, but there are also problems with environmental hygiene and fire safety.

On the other hand, aliphatic aromatic compounds represented by polyhexamethylene terephthalamide (nylon 6 · T), polyhexamethylene isophthalamide (nylon 6 · I), polyhexamethylene terephthalisophthalamide (nylon 6 · TI), etc. Polyamide dissolves in concentrated sulfuric acid, but if a concentrated sulfuric acid solution is molded using this, a large amount of concentrated sulfuric acid as a solvent and an alkali hydroxide for neutralizing this are required. Moreover, not only is there a problem that a large amount of water must be used when removing residual sulfuric acid by washing with water without using a neutralizing agent, and problems such as equipment corrosion can be avoided. Absent.

Phenol-based solvents such as phenol and cresol are known as solvents for aliphatic aromatic polyamides. Aliphatic-aromatic polyamide solution compositions prepared using these phenol-based solvents are also phenol-based solvents. Since the system solvent is sparingly soluble in water, fibers, films, fibrids and other shaped articles can be obtained from this solution composition by a wet method by using a specific organic solvent such as alcohol or ketone as a precipitant (coagulation bath solution). Need to use.

[0010]

The first object of the present invention is to solve the various problems found in the above-mentioned conventional aliphatic polyamide solution composition and aliphatic aromatic polyamide, and to have high safety. It is an object of the present invention to provide a novel polyamide solution composition which can be favorably molded using an aqueous coagulation bath.

A second object of the present invention is to provide a method for producing fibrids (pulp-like particles) which is industrially advantageous and has good papermaking properties, using the above polyamide liquid composition.

A third object of the present invention is to provide a method for producing a paper-like sheet (synthetic paper) having good mechanical properties using the above fibrids.

Other objects of the present invention will be clarified by the following description.

[0014]

According to the studies made by the present inventors, a specific solvent system containing N-methyl-2-pyrrolidone and calcium chloride is specifically aliphatic polyamide or aliphatic aromatic polyamide. In order to be well dissolved and to be well mixed with water, a solution composition in which the above polyamide is dissolved in this solvent system can be wet-molded using an aqueous coagulation bath, and a good molded product can be obtained by wet molding A new fact has been found that it is possible to obtain, for example, fibrids.

Thus, according to the invention, an aliphatic polyamide and / or an aliphatic aromatic polyamide and N-methyl-
A novel polyamide solution composition containing 2-pyrrolidone and calcium chloride, and specifically, 3 to 25% by weight of an aliphatic polyamide and / or an aliphatic aromatic polyamide and N-methyl-2-pyrrolidone 97 to 75% by weight, and 5 to 60 relative to 100 parts by weight of the above polyamide.
There is provided a novel polyamide solution composition characterized in that it comprises parts by weight of calcium chloride.

Further, according to the present invention, the solution composition of the above-mentioned aliphatic polyamide and / or aliphatic aromatic polyamide is introduced into a precipitant containing water as a main component while stirring to prepare a pulp-like material. Provided is a method for producing a fibrid of an aliphatic polyamide and / or an aliphatic aromatic polyamide, which is characterized in that it is precipitated as fine particles.

Further, according to the present invention, there is provided a method for producing a paper-like sheet by mixing the fibrid of the aliphatic polyamide and / or the aliphatic aromatic polyamide produced by the above method with short fibers or natural pulp. To be done.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an aliphatic polyamide solution composition and a method for preparing the same, an aliphatic aromatic polyamide solution composition and a method for preparing the same according to the present invention, and a fibrid produced using these, Will sequentially describe in detail the method for producing a paper-like sheet using the fibrids.

(A) Aliphatic Polyamide Solution Composition and Preparation Thereof: The polymer used in the aliphatic polyamide solution composition of the present invention is an aliphatic polyamide. Examples of such an aliphatic polyamide include an aliphatic polyamide having a polymer repeating unit represented by the following general formula [1] or [2].

[0020]

Embedded image

[In the formula, R ¹ is an alkylene group having 2 to 12 carbon atoms (preferably 4 or 8), and R ² is 4 to 10 carbon atoms.
(Preferably 4 or 6) represents a chain or cyclic alkylene group or aralkylene group. ]

[0022]

Embedded image

[In the formula, R ³ represents an alkylene group having 5 carbon atoms. ]

Specific examples of the aliphatic polyamide include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 6.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene sebac In addition to amides (nylon 6/10), polyethylene sebacamide (nylon 2/10) and their copolymers, poly (methylenebis [p-cyclohexylene] adipamide) (PACM-6), polym-xylyleneazide In the present invention, a homopolymer which is not a copolymer is preferable as the aliphatic polyamide in order not to lower the melting point of the polymer (to 180 ° C. or lower) in the present invention.

Suitable aliphatic polyamides in the present invention include polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 6.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene. Although there is sebacamide (nylon 6/10), polycaprolactam (nylon 6) and polyhexamethylene adipamide (nylon 6/6) are particularly useful. These are usually used alone, but if necessary, two or more kinds of polymers may be blended.

As the solvent constituting the aliphatic polyamide solution composition of the present invention, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) or a mixed solvent mainly containing this is used. . Generally, as an amide solvent, N, N-dimethylacetamide other than the above NMP,
N, N-dimethylformamide, etc. are known, and tetramethylurea, N, N-dimethylethyleneurea, etc. are known as urea-based solvents, but any solvent other than NMP can be used in combination with calcium chloride The solubility of the group polyamide is poor and a good solution cannot be prepared.
However, as long as the solubility of polyamide is not impaired, NMP
(Eg, 20% by weight or less thereof, preferably 10% by weight)
It is possible to replace (wt% or less) with another amide solvent (eg, N, N-dimethylacetamide) that is miscible with NMP.

On the other hand, calcium chloride, which is another component of the aliphatic polyamide solution composition of the present invention, may be anhydrous calcium chloride or hydrous calcium chloride. As hydrous calcium chloride, C having 1 to 3 molecules of crystal water
aCl ₂ · nH ₂ O (n = 1 to 3) is preferably used. According to the study of the present inventors, is better this time a small amount of water was present has good solubility, especially CaCl ₂ · 2
It has been found that H ₂ O is optimal.

As described above, according to the present invention, an aliphatic polyamide is dissolved in a solvent system of NMP / CaCl ₂ to obtain a uniform solution, and the above-mentioned specific solvent system is specific to the aliphatic polyamide. It is based on the novel finding that it exhibits good solubility, and such a dissolution behavior is completely unexpected from the conventional findings.

The aliphatic polyamide solution composition of the present invention comprises
As described above, it is a uniform solution composition containing the aliphatic polyamide, NMP and calcium chloride, and the concentration of the aliphatic polyamide and NMP in this composition is Polyamide 3-
25% by weight, preferably 5-20% by weight, NMP 97-
75% by weight, preferably 95-80% by weight, is suitable, and the calcium chloride concentration is 100% by weight of aliphatic polyamide (calcium chloride-free CaCl _2).
5 to 55 parts by weight, preferably 30 to 50 parts by weight.

The aliphatic polyamide (polymer) concentration in the above aliphatic polyamide solution composition must be 3% by weight or more based on the total weight of the aliphatic polyamide and NMP. If the polymer concentration is too low, it is not preferable because it is disadvantageous in solvent recovery and also deteriorates wet molding stability and productivity. On the other hand, if the concentration is too high, it not only takes too long to dissolve the polymer, but in the case of a high concentration, there is a tendency that when the solution composition is cooled to room temperature, the viscosity sharply increases and gels or solidifies, which is disadvantageous in the molding process. Therefore, 25 wt% or less is suitable.

The concentration of calcium chloride in the solution composition is selected according to the amount of the aliphatic polyamide, and the weight of calcium chloride in the solution composition (calculated as an anhydrous salt in the case of hydrous salt) is 100% by weight of the aliphatic polyamide. If it is less than 5 parts by weight per part, the solubility is lowered. Further, even if the amount of calcium chloride is more than 55 parts by weight, the effect does not increase, which is economically undesirable. However, if the composition contains a certain amount of water or more, it may impair the solubility,
It is necessary to keep the amount of water at most 5 times the molar amount of calcium chloride or less.

To prepare the aliphatic polyamide solution composition according to the present invention, a predetermined amount of pellets or pulverized fine powder of the aliphatic polyamide is put in a preparation container together with a predetermined amount of NMP and a predetermined amount of calcium chloride. It is possible to dissolve the polymer by stirring for about 20 minutes to 2 hours at a temperature of not lower than 0 ° C and not higher than the boiling point, preferably at a temperature of about 40 to 200 ° C. When the polymer concentration in the prepared polymer solution composition is low, for example, about 5% by weight, the liquid state is maintained even when cooled to 30 ° C., but the polymer concentration is 1%.
When the amount is about 5% by weight, the viscosity gradually increases depending on the type of the aliphatic polyamide after cooling, and gradually becomes an emulsified state, jelly state or solid state. However, even in this case, when it is heated to, for example, about 50 ° C., it is dissolved again and becomes a low-viscosity liquid.

The aliphatic polyamide solution composition thus obtained is neutral (pH 6-8) and is a device or container as found in solution compositions prepared using concentrated sulfuric acid or formic acid. It does not corrode, etc. and is extremely advantageous for storage and transportation of solutions and wet molding of fibrids, fibers, films and the like.

(B) Aliphatic aromatic polyamide solution composition and its preparation: The polyamide constituting the aliphatic aromatic polyamide solution composition contains 20 mol% or more of either the acid component or the diamine component constituting the polyamide. Of the aromatic dicarboxylic acid or aromatic diamine, preferably 50 mol% or more, and specifically has a polymer repeating unit represented by the following general formula [3] or [4]. Examples thereof include aliphatic aromatic polyamides.

[0035]

Embedded image

[In the formula, Ar ¹ is a p- or m-phenylene group, and the hydrogen moiety of the benzene ring may be substituted with a methyl group or a halogen atom. R ⁴ is an alkylene group having 4 to 10 (preferably 6) carbon atoms. ]

[0037]

[Chemical 4]

[In the formula, Ar ² is a p- or m-phenylene group, and a part of the hydrogen atoms of the benzene ring may be substituted with a methyl group or a halogen atom. Also, R
⁵ is an alkylene group having 4 to 8 carbon atoms. ]

Specific examples of such aliphatic aromatic polyamides include polyhexamethylene terephthalamide (nylon 6 · T), polyhexamethylene isophthalamide (nylon 6 · I), polyhexamethylene terephthalisophthalamide (nylon 6).・ TI), polyhexamethylene terephthaladipamide (nylon 6 ・ T6), polyhexamethylene isophthaladipamide (nylon 6)
-I6), polyhexamethylene terephthalisophthaladipamide (nylon 6 / TI6) and the like, polymetaphenylene adipamide, polytolylene adipamide and the like. Among them, polyhexamethylene terephthalamide (nylon 6 · T), polyhexamethylene terephthalamide (nylon 6 · I), polyhexamethylene terephthalisophthalamide (for which the raw materials are easily available and the heat resistance of the polymer is good) Nylon 6 · TI), polyhexamethylene terephthalisophthaladipamide (nylon 6 · TI6) and the like are preferably used.

Further, the solvent constituting the solution composition of the aliphatic aromatic polyamide used in the present invention is exclusively N 2
-Methyl-2-pyrrolidone (NMP) or a mixed solvent mainly containing this, and used as a solvent system in which calcium chloride is mixed with this.

In general, N, N-dimethylacetamide, N, N-dimethylformamide and the like are known as amide solvents other than the above NMP, and tetramethylurea, N, N- as urea solvents. Although there are dimethyl ethylene urea and the like, even if calcium chloride is added to any of these solvents other than NMP, the solubility of the aliphatic aromatic polyamide is poor and a good solution cannot be prepared. However, as long as the solubility of the aliphatic aromatic polyamide is not impaired, NMP
-Part (for example, 20% by weight or less, preferably 10% by weight)
Hereinafter, more preferably 5% by weight or less) may be replaced with another amide solvent (eg, dimethylacetamide) that is miscible with NMP.

On the other hand, the component calcium chloride constituting the solution composition used in the present invention may be anhydrous calcium chloride or hydrous calcium chloride. As hydrous calcium chloride, Ca having 1 to 3 molecules of crystal water
Cl ₂ · nH ₂ O (n = 1 to 3) is preferably used.
According to the research conducted by the present inventors, the solubility is better when a small amount of water is present, and especially Ca containing two molecules of water of crystallization is found.
Cl ₂ · 2H ₂ O is most suitable.

The ratio of the aliphatic aromatic polyamide and NMP in this solution composition is 3 to 25% by weight (preferably 5 to 20% by weight) of aliphatic aromatic polyamide and NMP.
97 to 75% by weight (preferably 95 to 80% by weight) is suitable, and the calcium chloride concentration is 5 to 60 parts by weight, especially 20 to 5 parts by weight per 100 parts by weight of the aliphatic aromatic polyamide.
5 parts by weight is suitable.

The concentration of the polymer (aliphatic aromatic polyamide) in the solution composition is preferably 3% by weight or more based on the total weight of the polymer and NMP. If the concentration is too low, it is disadvantageous in solvent recovery, and the stability and productivity of the production of fibrids by wet molding are deteriorated. Therefore, the polymer concentration is suitably 3% by weight or more, preferably 5% by weight or more. On the other hand, if the concentration is too high, it not only takes too long to dissolve the polymer but also requires high temperature heating, and in the case of a high concentration, when the solution composition is cooled to room temperature, the viscosity sharply increases and tends to gel or solidify. However, the polymer concentration is 25 because it is disadvantageous in the fibrid molding process.
A suitable amount is not more than 20% by weight, more preferably not more than 20% by weight.

The calcium chloride concentration in the solution composition is selected according to the amount of the aliphatic aromatic polyamide, and if the calcium chloride concentration is lower than the above range based on the amount of the aliphatic aromatic polyamide, the solubility will decrease. . Further, even if the concentration of calcium chloride is higher than the above range, the effect does not increase, which is economically unfavorable. Further, when the solution composition contains a certain amount or more of water, the solubility may be impaired, and therefore the amount of water needs to be suppressed to 5 times or less the molar amount of calcium chloride at the maximum.

As described above, the present invention is most characterized by using a novel solution composition which is prepared by dissolving an aliphatic aromatic polyamide in a solvent system of NMP / CaCl _2. The present invention is based on a new finding that the present inventors have never expected in the past that the above-mentioned specific solvent system shows a specifically good solubility in aliphatic aromatic polyamide.

As a method for preparing this aliphatic aromatic polyamide solution composition, a predetermined amount of aliphatic aromatic polyamide pellets or pulverized fine powder is placed in a preparation container with a predetermined amount of NMP and a predetermined amount of calcium chloride. Then, a method of dissolving the polymer by stirring at a temperature of 30 ° C. or higher and lower than the boiling point, preferably about 50 to 200 ° C. for about 20 minutes to 2 hours is adopted.

When the polymer concentration in the prepared polymer solution composition is low, for example, about 5% by weight, 30
Although it remains liquid even after cooling to ℃, depending on the type of aliphatic aromatic polyamide, when the polymer concentration reaches about 15% by weight, the viscosity gradually increases due to cooling and gradually becomes an emulsified, jelly-like or solid state. Become a state. However, even in this case, when it is heated to, for example, about 50 ° C., it is dissolved again and becomes a low-viscosity liquid.

The aliphatic-aromatic polyamide solution composition thus obtained is neutral (pH 6-8) and is a container as found in solution compositions prepared using concentrated sulfuric acid or formic acid. It does not corrode or the equipment, and is extremely advantageous for storage / transportation of solutions and production of fibrids, films, fibers, etc. by wet molding.

The above-mentioned (a) aliphatic polyamide solution composition and (b) aliphatic-aromatic polyamide solution composition are essentially the above-mentioned three components, that is, the above-mentioned polyamide, NMP and chloride. It is composed of calcium, but can contain additives such as stabilizers, flame retardants, release agents, colorants, matting agents, antistatic agents, fillers, etc., if necessary.

In the present invention, it is also possible to use an aliphatic polyamide and an aliphatic aromatic polyamide in combination as the polyamide. For example, as the polyamide, nylon 6
A blend of 6 with nylon 6.6 IT may be used. In this case, the total amount of both polyamides in the solution composition should fall within the above-mentioned blending ratio range.

(C) Production of Aliphatic Polyamide Fibrid According to the present invention, a fibrid is produced using the novel aliphatic polyamide solution composition described above. A method in which the precipitating agent is dropped into a bath containing a precipitating agent containing water as a main component while stirring at high speed to precipitate / precipitate the aliphatic polyamide as pulp-like particles is adopted.

As such a precipitant, it is possible to use not only water but also another precipitant or a coagulation regulator mixed with water. An amide-based solvent is used as the coagulation regulator, and NMP can be mentioned as a preferred example of the amide-based solvent. There is no particular restriction on the mixing amount of the amide-based solvent, but if the mixing amount is too large, the pulp-like substances produced will coagulate and weld, and the mechanical properties of the sheet-like product obtained by processing this pulp-like substance In addition, the electrical properties and the thermal properties are deteriorated, and the papermaking property is deteriorated, which is not preferable. Therefore, the mixing amount of the amide-based solvent is preferably suppressed to 30% by weight or less in the coagulation bath.

The temperature of the solution composition at the time of precipitation is 30 to 80 ° C.
Is preferred. The coagulation bath temperature is also one of the important factors for obtaining a pulp-like material having good papermaking properties and a good shape, and is usually 5 to 70 ° C, preferably 10 to 50 ° C.

In order to obtain a good fibrid, it is preferable to remove the solvent from the solution composition dropped and introduced into the coagulation bath consisting of the precipitant which is being stirred at high speed, and at the same time, to operate so as to give a shearing or beating action. The amount of the precipitant used in the aliphatic polyamide solution composition is 5/1 by weight.
To 200/1 are preferable, and in particular 10/1 to 100 /
1 is preferred.

In this way, an aliphatic polyamide fibrid (pulp-like material) having good paper-making properties is obtained.

As a precipitation device, Japanese Patent Laid-Open No. 52-15621
An apparatus combining a stator and a rotor described in No. 10 is preferably used.

(D) Production of Aliphatic Aromatic Polyamide Fibrids: The solution composition used for producing the aliphatic aromatic fibrids in the present invention is a novel composition containing the above-mentioned aliphatic aromatic polyamide, NMP and calcium chloride. Solution composition.

To produce fibrids using this solution composition, the aliphatic aromatic polyamide solution composition is treated with a precipitant containing water as a main component, as in the case of the aliphatic polyamide fibrids described above. A method is employed in which a precipitating agent is dropped into the following bath with stirring to precipitate / precipitate as pulp-like particles.

As such a precipitating agent, it is possible to use not only water but also other precipitating agents and precipitation regulators in admixture with water. Examples of such precipitation regulators include NM
An amide solvent such as P is used. The mixing amount of the amide solvent in the precipitant is preferably suppressed to 30% by weight or less in the precipitant. The temperature of the precipitating agent is also an important factor for obtaining a pulp-like material having good papermaking properties and good shape,
It is usually 10 to 70 ° C, preferably 15 to 50 ° C.

It is preferable that the precipitant is subjected to high-speed agitation and operated so as to remove the solvent from the solution composition added dropwise and introduced, and at the same time exert a shearing or beating action. The amount of the precipitant used in the aromatic-aliphatic polyamide solution composition is preferably 5/1 to 200/1 in weight ratio, and particularly preferably 10/1 to 100/1.

Also in the case of an aliphatic aromatic polyamide, a device combining a stator and a rotor described in JP-A-52-15621 is preferably used as a precipitation device.

Thus, a fibrid (pulp-like material) made of an aliphatic polyamide or an aliphatic aromatic polyamide and having good paper-making properties can be economically produced by using an aqueous precipitant.

(E) Production of sheet-like material: In the present invention, the fibrid of the aliphatic polyamide or the aliphatic aromatic polyamide (these may be collectively referred to as "polyamide" hereinafter) produced as described above. By mixing with short fibers or natural pulp and making a paper, a sheet material (synthetic paper) having excellent heat resistance and good mechanical properties can be obtained. At this time, the amount of polyamide fibrids in the sheet-like material can be arbitrarily changed according to the application,
It is preferably in the range of 5% by weight, particularly preferably 20 to 80% by weight.

Therefore, when paper is made from the polyamide fibrids obtained by the present invention and the short fibers, the polyamide fibrids / short fibers ratio is 80 by weight.
/ 20 to 20/80 is preferable.

In the present invention, various fibers can be applied as the short fibers used when the sheet-like material is produced from the polyamide fibrids and the short fibers. Specific examples include polyethylene terephthalate fiber, polyester fiber such as polybutylene terephthalate fiber,
Aliphatic polyamide fibers such as nylon 6 and nylon 6.6 fibers, wholly aromatic polyamide fibers such as polymetaphenylene isophthalamide fibers, polyparaphenylene terephthalamide fibers, polyolefin fibers such as polyethylene fibers and polypropylene fibers Examples thereof include fibers, polyacrylonitrile fibers, polycarbonate fibers and the like. Also, glass fiber, ceramic fiber,
Carbon fiber, asbestos, metal fiber, potassium titanate fiber and the like are also applicable.

The thickness of the short fibers (single yarn fineness) used in the present invention varies depending on the intended use of the sheet-like material, but is usually 0.1 to improve dispersibility with the pulp-like material. Finer fibers of ~ 5 denier are preferably used. The length of the short fibers is not particularly limited, but is usually 1 to 30 mm, preferably 2 to 15
mm.

The mixed papermaking of polyamide fibrids and short fibers in the present invention is carried out by a wet method using a Fourdrinier type, cylinder type or the like papermaking machine, as in the case of making paper from conventional wood pulp. Good. In this case, if necessary, a surfactant, a dispersant, a thickener and other additives may be added.

The polyamide fibrids of the present invention can be satisfactorily mixed and made into paper in the same manner as natural pulp produced from wood. Also in this case, fibrids /
The ratio of natural pulp is 80/20 to 20/80 by weight
Is preferred.

In the method of the present invention, it is possible to use two or more kinds of fibrids as the polyamide fibrids in a mixture. For example, a fibrid of an aliphatic polyamide such as nylon 6.6 and a fat of nylon 6 • I can be used. Mixtures of fibrids of aromatic aromatic polyamides can be used. In this case, the total amount of polyamide fibrids should be in the above range.

In the present invention, when a sheet-like material is made from fibrids and short fibers and / or natural pulp,
If necessary, it is possible to mix and use a pulp-like substance from another polymer (for example, wholly aromatic polyamide fibrids, polyolefin-based pulp-like substance, etc.). Also,
It is also possible to mix a small proportion of mica, kaolin, talc, glass flakes, etc., for example, 50% or less of the paper weight to make paper.

The sheet-like material obtained as described above can be used as it is after drying, but excellent performance can be imparted by heating and pressurizing it by means such as a hot press or a hot roll. . The temperature adopted in such heating and pressurization is the type of polyamide used, the type of short fibers,
Although it varies depending on the content of fibrids present in the sheet, it is usually 50 to 350 ° C., preferably 100 to 30.
0 ° C is suitable. The pressure also varies depending on the type of polyamide forming the fibrid, the type of short fibers, the content of the fibrid in the sheet, the use of the sheet, etc., but is usually 400 Kgf / cm ² or less, especially 10 to 3
00 Kgf / cm ² is preferable.

[0073]

Industrial Applicability The solution composition of the aliphatic polyamide and / or the aliphatic aromatic polyamide according to the present invention has excellent uniformity and stability, and is excellent in fibrid content using an aqueous precipitant,
It can be wet-molded into a film, fiber or the like.

The polyamide fibrid (pulp-like material) obtained from the solution composition by the method of the present invention has a good paper-making property, and is used to produce a sheet-like material (synthetic paper) having excellent properties. be able to. And, the sheet-like material containing this fibrid does not contain concentrated sulfuric acid or formic acid in the product at all, so that there is no corrosion of the device, jig or the like in various fields of use, and further does not cause deterioration in quality in the use environment, It is extremely advantageous.

Further, in the method of the present invention, since water or an aqueous precipitant is used as the precipitant during the production of the fibrids, it is advantageous in terms of cost, and it is also suitable in terms of safety, equipment and environment.

Moreover, according to the method of the present invention, a good and low-cost sheet-like material (synthetic paper) can be produced from inexpensive aliphatic polyamide or fibrid of aromatic aliphatic polyamide having relatively good heat resistance.

The sheet-like material is an electrically insulating paper,
Industrial fields such as battery / separator of electrolyte solution, electric / electronic materials such as diaphragms, packaging materials for heavy bags, interior materials for interior and automobiles, maps, securities paper, speaker cone paper, honeycomb core materials, etc. It can be effectively used for consumer use.

For example, an unexpanded honeycomb core obtained by applying an adhesive in a predetermined pattern to a sheet-like material obtained by mixing and making a paper of polyamide fibrids and short fibers according to the method of the present invention and spreading the resin is applied. By impregnating and fixing by heating and curing, a lightweight and high-strength honeycomb core can be manufactured. Further, a honeycomb panel in which the honeycomb core is used as a core material and a surface plate such as an FRP plate is bonded to one or both surfaces of the core material via an adhesive layer may be used. This honeycomb core is cheaper than an aramid honeycomb core, yet has a higher strength than conventional kraft paper and is a lightweight structural material, fireproof and heat resistant structural material, sound insulating material, heat insulating material, fluid rectifying material, etc. It is suitable for.

[0079]

EXAMPLES Hereinafter, the method of the present invention will be described more specifically with reference to Examples and Comparative Examples. However, these Examples and Comparative Examples are for helping understanding of the present invention, and the scope of the present invention is not limited by these descriptions. All "parts" and "%" in Examples and Comparative Examples are based on weight unless otherwise specified, and all quantitative ratios are weight ratios.

Further, the tensile strength of paper (sheet-like material),
The tensile elongation was measured on a sample of 5 cm according to JIS P8133-1976 "Paper and paper board tensile strength test method".

[Example 1] This example shows a solution composition of polycaprolactam (nylon 6) and an example of producing a fibrid (pulp-like material) using the solution composition.

The dried polycaprolactam pellets were ground into a fine powder with a grinder. 30 parts of this fine powder
It was put in a three-necked flask together with 170 parts of MP and 15 parts of anhydrous calcium chloride, heated under stirring in a nitrogen atmosphere at 150 ° C., and stirred at that temperature for 5 hours to dissolve polycaprolactam fine powder. After that, 180 ° C
The temperature was raised to and the remaining fine particles were dissolved to prepare a transparent polycaprolactam solution composition.

When this solution composition was cooled to 20 ° C., it became a viscous starch syrup. When this was heated again to 50 ° C., it dissolved and became liquid.

This solution composition was gradually dropped on the surface of water to form a thin film, which was thoroughly washed with water to obtain a polycaprolactam thin film (film-like product).

Further, this polycaprolactam solution composition was dropped into an aqueous solution of water / NMP (weight ratio) = 9/1 at 20 ° C. with stirring with a blender to obtain a polycaprolactam fibrid.

Comparative Example 1 The same polycaprolactam as in Example 1 was used, except that various solvents (a single solvent and a solvent system containing calcium chloride) other than the solvent system consisting of NMP and calcium chloride were used. An attempt was made to dissolve by heating and stirring under the conditions. The results are summarized in Table 1 below. The abbreviations of the solvents in Table 1 are as follows.

DMF: N, N-dimethylformamide DMAC: N, N-dimethylacetamide DMI: N, N-dimethylimidazolidinone TMU: tetramethylurea DMSO: dimethylsulfoxide EG: ethylene glycol

[0088]

[Table 1]

As shown in Table 1 above, when various amide organic solvents and urea organic solvents were used alone (Experiment N
o.1-1 to 1-7) or a solvent system in which calcium chloride is added to a solvent other than NMP (Experiment No. 1-8 to 1-1)
In any of 3), polycaprolactam (nylon 6) was not dissolved, and the intended solution composition could not be obtained.

Example 2 This example shows an example of preparing a polycaprolactam (nylon 6) solution composition, and using the composition to produce fibrids and paper-like sheets.

As in Example 1, dried polycaprolactam (nylon 6) pellets were pulverized into a fine powder by a pulverizer. 30 parts of this fine powder together with 170 parts of N-methyl-2-pyrrolidone (NMP) and 15 parts of anhydrous calcium chloride were placed in a three-necked flask and placed under a nitrogen atmosphere for 15
The temperature was raised with stirring at 0 ° C, and stirring was continued for 5 hours at that temperature to dissolve polycaprolactam, and then 180 ° C.
The temperature was raised to and the remaining fine particles were dissolved to prepare a transparent polycaprolactam solution composition.

After the above solution composition was cooled to 50 ° C., it was added dropwise to a large excess amount of a water / NMP system mixed aqueous solution (NMP content 5%) cooled to 20 ° C. with stirring to give a poly A fibrid precipitate of caprolactam was obtained. This fibrid precipitate was repeatedly washed with a large amount of water,
Residual calcium chloride and NMP were removed. The target fibrid of polycaprolactam (pulp-like material) was obtained by drying the hydrous fibrids in a steam dryer at 120 ° C.

Water-containing fibrids of polycaprolactam (50 parts by weight of solid content) produced as described above and 50 parts of nylon 6 short fibers having a fiber length of 3 mm and a thickness of 1.5 denier were dispersed in a large amount of water, When paper was made from this aqueous dispersion using a tappy standard sheet machine, a sheet-like material having good drainage from the papermaking wire mesh, good papermaking properties, and good texture was obtained.

After drying this sheet material at 70 ° C. for 3 hours,
Hot pressing under the conditions of 180 ° C. and 50 Kgf / cm ² ,
A nylon 6 synthetic paper having a thickness of about 125 μm and a basis weight of 60 g / m ² was obtained. The tensile strength of this synthetic paper is 1.7 Kgf /
It was 5 cm and the tensile elongation was 3.0%.

Example 3 This example relates to the preparation of fibrids from polycaprolactam (nylon 6) and the production of paper-like sheets using the fibrids.

An aqueous dispersion containing 50 parts of polycaprolactam fibrids (as solid content weight) produced in the same manner as in Example 2 and 50 parts of nylon 6.6 short fibers having a fiber length of 3 mm and a thickness of 1.5 denier. Paper using a tappy standard sheet machine, then heated and dried in a steam heating drum dryer at 110 ° C to a thickness of 125μ.
m, sheet weight 60 g / m ² (nylon 6/6
6 synthetic paper) was obtained.

Example 4 Polycaprolactam (nylon 6) fibrids produced in Example 2 and a thickness of 0.3
Denier and ultrafine polyethylene terephthalate (PET) short fibers having a fiber length of 3 mm were mixed at a dry weight ratio of 50/50 and dispersed in a large excess of water. When this dispersion was paper-made using a paper machine in the same manner as in Example 2, the dispersibility was good and a homogeneous sheet-like product was obtained. The thickness of the synthetic paper obtained by calendering this is 120μ.
m, basis weight is 60 g / m ² , and tensile strength is 1.8.
The Kgf / 5 cm and the tensile elongation were 2.5%.

[Example 5] This example relates to an example of preparing a solution composition of polyhexamethylene adipamide (nylon 6.6).

22 parts of fine powder of dried polyhexamethylene adipamide, 178 parts of NMP and 15 parts of calcium chloride (CaCl ₂ .2H ₂ O) containing 2 molecules of water of crystallization were placed in a three-necked flask. , Stirring under nitrogen atmosphere 15
The temperature was raised to 0 ° C., and stirring was continued for 7 hours at that temperature to dissolve polyhexamethylene adipamide, and then 180 ° C.
The temperature was raised to and stirred for 2 hours. Thus, polyhexamethylene adipamide was completely dissolved and a uniform solution composition was obtained. After cooling this solution composition to 50 ° C., a film-like material and fibrids were produced in the same manner as in Example 1.

[Example 6] In this example, preparation of a solution composition of polyhexamethylene adipamide (nylon 6.6) and production of fibrids and sheets using the same will be described.

Similar to Example 5, 22 parts of dried polyhexamethylene adipamide fine powder and 178 parts of NMP and calcium chloride (CaCl ₂ ·.
(2H ₂ O) (15 parts) was placed in a three-necked flask, the temperature was raised to 150 ° C. with stirring under a nitrogen atmosphere, and stirring was continued at that temperature for 7 hours to dissolve polyhexamethylene adipamide. Furthermore, this solution was heated to 180 ° C. and stirred for 2 hours. Thus, the polyhexamethylene adipamide was completely dissolved and a homogeneous solution composition was obtained.

The above polyhexamethylene adipamide solution composition was cooled to 50 ° C., and then dropped into a large excess amount of water kept at 20 ° C. with stirring to give a polyhexamethylene adipamide fibrid form. A precipitate was obtained. This fibrid-like precipitate was repeatedly washed with water to remove calcium chloride and NMP remaining in the precipitate. This water-containing fibrid was dried using a hot air drier to obtain the desired dried polyhexamethylene adipamide (nylon 6.6) fibrid.

The above fibrids and short fibers obtained by cutting nylon 6.6 fibers having a thickness of 1.5 denier into 5 mm were mixed at a dry weight ratio of 50/50 and dispersed in a large amount of water. Paper was made in the same manner as in Example 2, and polyhexamethylene adipamide fibrids and nylon 6 were used.
-A sheet-like material was prepared from 6 fibers.

The sheet-like material was dried and heated and pressed in the same manner as in Example 2 to obtain synthetic paper. The obtained synthetic paper had a thickness of 130 μm, a basis weight of 65 g / m ² , a tensile strength of 1.8 Kgf / 5 cm, and a tensile elongation of 5.5%. Further, the dispersibility of each component in the above papermaking operation is good, and the papermaking can be smoothly carried out and a homogeneous sheet material (nylon 6
* 6 synthetic paper) was obtained.

Example 7 This example relates to the preparation of a solution composition of polyhexamethylene terephthalisophthaladipamide (nylon 6 / TI6 copolymer) which is an aliphatic aromatic polyamide.

Pellets of a nylon 6 / TI6 copolymer having a melting point of 279 to 282 ° C. copolymerized with a composition ratio of 100 mol of hexamethylenediamine, 65 mol of terephthalic acid, 25 mol of isophthalic acid and 10 mol of adipic acid were pulverized with a grinder. Crushed to a fine powder. 45 parts of the obtained nylon 6 / TI6 copolymer fine powder was placed in a three-necked flask together with 330 parts of NMP and 49 parts of calcium chloride and heated to 180 ° C. with stirring under a nitrogen atmosphere, and the temperature was increased. After stirring for 5 hours to dissolve the polymer, the temperature was further raised to 200 ° C. and stirring was continued to completely dissolve the remaining fine particles to obtain a transparent solution composition of nylon 6 · TI6.

Comparative Example 2 The same polyhexamethylene terephthalisophthaladipamide (nylon 6 as in Example 7)
-TI6 copolymer) is heated and stirred under the same conditions as in Example 7 using various solvents (homologous solvent and solvent system containing calcium chloride) other than the solvent system consisting of NMP and calcium chloride to dissolve. I tried. The results are shown in Table 2 below.
Are shown together. The abbreviations of the solvents in Table 2 are shown in Table 1.
Is the same as

[0108]

[Table 2]

As shown in Table 2 above, when various amide organic solvents and urea organic solvents were used alone (Experiment N
o.2-1 to 2-7) or a solvent system (Experiment No. 2-8 to 2-13) in which calcium chloride is added to a solvent other than NMP, polyhexamethylene terephthalisophthaladipamide (nylon) 6 * TI6 copolymer) was not dissolved, and the intended solution composition could not be obtained.

Example 8 The solution composition of polyhexamethylene terephthalisophthaladipamide (nylon 6 / TI6 copolymer) prepared in Example 7 was cooled to 50 C and then cooled to 20 ° C. in a large excess amount. Was dropped into the water / NMP-based mixed aqueous solution (NMP content: 5%) under stirring to obtain a nylon 6 / TI6 fibrid precipitate.

The fibrid precipitate was repeatedly washed with a large amount of water to remove calcium chloride and NMP remaining in the fibrid. The target fibrous aliphatic aromatic polyamide fibrid was obtained by drying this hydrous fibrid in a steam dryer at 120 ° C.

Water-containing fibrids (50 parts by weight of solid content) of this nylon 6 / TI6 copolymer, fiber length 3 mm,
50 parts of nylon 6 short fibers with a thickness of 1.5 denier were dispersed in a large amount of water, and paper was made from this dispersion using a Tappy Standard Sheet Machine. A sheet-like material having a good texture was obtained.

After drying this sheet material at 70 ° C. for 3 hours,
Heat-pressed by a flat plate press at a temperature of 180 ° C. and a pressure of 60 Kgf / cm ² , a thickness of about 130 μm and a basis weight of 6
0 g / m ² of synthetic paper was obtained. The synthetic paper had a tensile strength of 1.9 Kgf / 5 cm and a tensile elongation of 3.0%.

[Example 9] This example relates to preparation of a solution composition of polyhexamethylene terephthalisophthalamide (nylon 6 / TI copolymer) which is an aliphatic aromatic polyamide.

Pellets of nylon 6 / TI copolymer copolymerized in a composition ratio of 100 mol of hexamethylenediamine, 78 mol of terephthalic acid and 22 mol of isophthalic acid were pulverized into a fine powder by a pulverizer. Calcium chloride (CaCl ₂ .2H ₂ O) 20 containing 23 parts of Nylon 6 · TI copolymer fine powder, 177 parts of NMP and 2 molecules of water of crystallization obtained
Parts were placed in a three-necked flask, the temperature was raised to 170 ° C. with stirring under a nitrogen atmosphere, and the stirring was continued for 7 hours at that temperature to dissolve the nylon 6 / TI copolymer. Furthermore, this solution was heated to 190 ° C. and stirred for 2 hours. Thus, the copolymer was completely dissolved and a homogeneous solution composition was obtained.

[Example 10] This example is an example of producing fibrids and paper-like sheets using the solution composition of polyhexamethylene terephthalisophthalamide (nylon 6 / TI copolymer) prepared in Example 9. Is.

The solution composition of the nylon 6 / TI copolymer prepared in Example 9 was cooled to 50 ° C. and then added dropwise to the large excess amount of water kept at 20 ° C. under stirring.
A fibrous precipitate of nylon 6 / TI copolymer was obtained. This fibrid-like precipitate was repeatedly washed with water to remove residual calcium chloride and NMP. The hydrous fibrids were dried using a hot air drier to give nylon 6
A TI copolymer fibrid was obtained.

Nylon 6 · TI thus obtained
Copolymer water-containing fibrids, fiber length 3 mm, thickness 1.
5 denier nylon 6.6 short fibers were mixed so as to have a dry weight ratio of 50/50 and dispersed in a large amount of water, and then nylon 6 • TI copolymer / A sheet of nylon 6.6 was prepared. A homogenous sheet-like material (synthetic paper) was obtained with good dispersibility in the above papermaking operation.

Further, the synthetic paper obtained by hot pressing under the same conditions as in Example 8 had a thickness of 125 μm, a basis weight of 65 g / m ² , and a tensile strength of 2.0 Kgf.
/ 5 cm, and the tensile elongation was 5.0%.

Example 11 15 parts of polyhexamethylene terephthalamide (nylon 6 · T) obtained by solution polymerization of hexamethylene diamine and terephthalic acid chloride in equimolar ratios in NMP solvent was added to 100 parts of NMP. Part and 15 parts of calcium chloride (CaCl ₂ ) were placed in a three-necked flask, and the temperature was raised to 180 ° C. with stirring under a nitrogen atmosphere, and the stirring was continued for 5 hours at that temperature.
The temperature was raised to 0 ° C. and the mixture was stirred, and the remaining fine powder was dissolved to prepare a polyhexamethylene terephthalamide (nylon 6 · T) solution composition.

The solution composition is cooled to 50 ° C.,
Nylon 6 by adding dropwise to a water / NMP-based aqueous solution (NMP content is 5% by weight) kept at ℃ with stirring.
A T fibrid precipitate was obtained. This precipitate was repeatedly washed with a large amount of water to remove NMP and calcium chloride remaining in the fibrid precipitate to obtain a hydrous fibrid.

The thus obtained nylon 6 · T fibrids (60 parts by dry weight), polyethylene terephthalate (PE) having a thickness of 0.3 denier and a fiber length of 3 mm
T) Extra fine fibers (40 parts) were mixed and dispersed in a large amount of water in the same manner as in Example 2 to make a paper. The papermaking property of this fibrid was good.

The sheet-like material thus obtained was dried and further hot-pressed under the conditions of 180 ° C. and 60 Kgf / cm ² to obtain a nylon 6 · T / PET-based synthetic paper which was homogeneous and had a thickness of 120 μm. The basis weight was 58 g / m ² , the tensile strength was 2.0 Kgf / 5 cm, and the tensile elongation was 3.0%.

[Example 12] This example shows an example of manufacturing a honeycomb core using the polycaprolactam (nylon 6) paper-like sheet manufactured according to the present invention.

(1) Coating and Laminating of Adhesive: On one side of the polycaprolactam (nylon 6) paper-like sheet obtained in Example 2, an epoxy resin adhesive (manufactured by Yuka Shell Co., Ltd .:
"Epicoat 828" / "Epicoat 871" / "Epicure Z" = 50/50/20) was applied in a 7 mm width stripe pattern at a pitch of 28 mm and then laminated while shifting the coated surface by half a pitch. Then, using a press which heats this laminate at 140 ° C., 20 Kgf / cm ² (gauge pressure)
By heating and adhering for 20 minutes under pressure, an unexpanded honeycomb core was obtained. The coating amount of the adhesive was 55.0% by weight with respect to the sheet-shaped material as the base material.

(2) Spreading, resin impregnation and curing: The unstretched honeycomb core obtained by the above method was cut in a width of 7 mm (corresponding to the thickness of the honeycomb core) in the direction perpendicular to the stripes of the adhesive. The cut unexpanded honeycomb core was expanded to form a honeycomb shape, and an epoxy resin solution prepared in advance with the shape fixed (Yukaka Shell Co., Ltd .: “Epicoat 828” /
"Epicure Z" / acetone = 100/20/180)
Impregnated in. Then, after removing the acetone by air drying,
It was cured by heating at 5 ° C. for 2 hours and then at 120 ° C. for 4 hours.

(3) Performance of honeycomb core: The cured honeycomb core thus obtained has an apparent specific gravity of 0.0
25 g / cm ³ and compressive strength (cell size: 7 m
m, core thickness: 7 mm) was as good as 5.5 Kgf / cm ² .

[Example 13] 22 parts of fine powder of polyhexamethylene adipamide (nylon 6.6) and NMP1
Calcium chloride containing 78 parts and 2 molecules of water of crystallization (CaC
After the Hitoshiｰsolution l ₂ · 2H ₂ O) was heated and dissolved and 15 parts, in the same manner as in Example 6, was prepared fibrids of polyhexamethylene adipamide (nylon 6.6).

From 50 parts of this fibrid and 50 parts of nylon 6.6 short fiber having a thickness of 1.5 denier and a fiber length of 5 mm, wet papermaking was carried out to a thickness of 130 μm and a basis weight of 65 g /
A sheet of m ² was obtained.

Using this sheet material, adhesive coating, lamination, pressure bonding, and expansion were carried out to obtain an expanded honeycomb core. This expanded honeycomb core (cell size: 7 mm, cell thickness: 7 m
m) is a phenolic resin solution (made by Cemedine: No. 11)
(0; methyl ethyl ketone solution), air-dried, and then heated in a hot air dryer at 100 C for 2 hours and then at 160 ° C. for 2 hours to give an apparent specific gravity of 0.052 g /
A honeycomb core of cm ³ was obtained. The compressive strength of the obtained phenol resin-impregnated honeycomb core is 18.5 Kgf / cm ^2.
And was good.

[Example 14] 60 parts of the polyhexamethylene adipamide (nylon 6.6) fibrid obtained in Example 13 was copolymerized with paraphenylenediamine / 3,4-diaminodiphenyl ether and terephthalic acid. A sheet-like material was prepared from 40 parts of short fibers (fiber length: 3 mm) of fibers (made by Teijin: "Technora") from group polyamide.

On this sheet material, an epoxy resin adhesive was applied, laminated and spread in the same manner as in Example 12 to obtain a expanded honeycomb core, which was further impregnated with epoxy resin, heat-cured and fixed, An epoxy resin-impregnated honeycomb core was obtained. The apparent specific gravity of this honeycomb core is 0.048 g /
cm ³ , and the compressive strength was good at 16.5 Kgf / cm ² .

Example 15 Hexamethylenediamine 1
Fine powder 45 of aliphatic aromatic polyamide (nylon 6 / TI6 copolymer) obtained from 00 mol, 65 mol of terephthalic acid, 25 mol of isophthalic acid and 10 mol of adipic acid
Parts, 330 parts of NMP and 40 parts of calcium chloride are heated and dissolved under stirring, cooled to 50 ° C., and this solution is added dropwise to a water / NMP (NMP content is 5%) aqueous solution at 20 ° C. under stirring. , The above-mentioned aliphatic aromatic polyamide (nylon 6
Fibrids of (TI6 copolymer) were obtained.

A thickness of 130 parts was obtained in the same manner as in Example 8 from 50 parts of the fibrids thus obtained and 50 parts of nylon 6 short fibers (fiber length 3 mm, thickness 1.5 denier).
A sheet-shaped product having a micrometer and a basis weight of 60 g / m ² was produced.

On this sheet material, an epoxy resin adhesive was applied, laminated and spread in the same manner as in Example 12 to prepare a spread honeycomb core. Then, in the same manner as in Example 12, the epoxy resin impregnation, heat curing, and fixation were performed to obtain an epoxy resin-impregnated honeycomb core. The apparent specific gravity of this honeycomb core is 0.050 g / cm ³ , and the compressive strength is 1.
It was as good as 8.0 Kgf / cm ² .

Film-like epoxy adhesive (made by Kasei Fiberlight Co., Ltd .: MX
F-7303) is set, and the glass fiber woven fabric reinforced epoxy resin laminate prepared separately is stacked on both sides thereof, vacuum bagging is performed, and then adhesive curing is performed by using an autoclave molding machine prepared at 125 ° C. to make a honeycomb core.・ I got a panel. The honeycomb core panel thus obtained had a compressive strength of 35.0 Kgf / cm ² .

Example 16 This example shows an example of manufacturing a honeycomb panel from a honeycomb core.

On the surface of the sheet-like material obtained in Example 4,
Coating with an epoxy resin adhesive in the same manner as in Example 12,
An unexpanded honeycomb core was obtained by laminating. Furthermore, Example 1
In the same manner as in 2, spreading, epoxy resin impregnation, heat curing,
Fixing was performed to obtain an expanded honeycomb core. The apparent specific gravity of the obtained honeycomb core was 0.036 g / cm ³ , and the compressive strength was 7.5 Kgf / cm ² .

Subsequently, using this honeycomb core, the following steps (1), (2) and (3) were sequentially carried out to manufacture a honeycomb panel.

(1) Preparation of Glass Fiber Woven Fabric Reinforced Epoxy Resin Laminate: Glass Fiber Woven Fabric (Nitto Boseki: WE13P1)
04; thickness 0.11 mm) to "Epicoat 828" /
Explosion-proof hot air that was immersed and impregnated in epoxy resin consisting of "Epicure Z series" (100/20), then squeezed the resin through a pair of free rollers with a clearance of 0.2 mm and heated to 90 ° C. A glass / epoxy prepreg was prepared by holding it in a dryer for 20 minutes. 5 sheets of this prepreg are stacked and a 0.5 mm spacer is used, temperature: 160 ° C., pressure: 30 Kgf
/ Cm ² for 20 minutes and then held in a hot air circulation type drying oven at 160 ° C. for 2 hours to prepare a glass fiber woven fabric reinforced epoxy resin laminate having a thickness of 0.5 mm.

(2) Manufacture of honeycomb panel: Film type epoxy adhesive (resin film adhesive: MXF-7303 manufactured by Kasei Fiberlight Co., Ltd.) was set on the upper and lower surfaces of the honeycomb core obtained as described above. Then, the glass fiber woven fabric reinforced epoxy resin laminate of the above (1) was superposed on it and adhesively cured using a press heated to 120 ° C. to obtain a honeycomb panel. The compressive strength of the obtained honeycomb panel is 32.5 Kgf / cm ^2.
And was good.

Example 17 Hexamethylenediamine 1
00 mol, terephthalic acid 78 mol and isophthalic acid 22
Aliphatic aromatic polyamide (nylon 6
23 parts of fine powder of (TI), 177 parts of NMP and calcium chloride (CaCl ₂ .2H ₂ O) 2 containing 2 molecules of water of crystallization
After dissolving with 0 parts by heating and cooling the resulting solution to 50 C, it was dropped into water / NMP-based aqueous solution in the same manner as in Example 8 to obtain the above aliphatic aromatic polyamide (nylon 6 · TI).
Got the fibrids of.

50 parts of the thus-obtained fibrids and 50 parts of nylon 6.6 fiber short fibers (fiber length 3 mm, thickness 1.5 denier) were mixed and paper-made in the same manner as in Example 9. Heat pressed to a thickness of 125 μm, basis weight 65 g /
A sheet of m ² was obtained.

Using this sheet material, adhesive coating, lamination, pressure bonding and expansion were carried out in the same manner as in Example 12 to obtain a expanded honeycomb core. This expanded honeycomb core was used in Example 13.
Phenolic resin (made by Cemedine: No. 1)
After impregnating with 10) and air-drying, keep the temperature at 120 ° C and then at 160 ° C for 1 hour each to give an apparent specific gravity of 0.048 g / c.
A honeycomb core of m ³ was obtained. The compressive strength of this phenol resin-impregnated honeycomb core was as good as 18.5 Kgf / cm ² .

Example 18 A sheet-like material obtained from the nylon 6 • TI fibrids prepared in Example 10 and nylon 6.6 fibers was dried at 70 ° C. for 3 hours, then at a temperature of 180 ° C. and a pressure of 60 Kgf.・ Heat-pressed by a flat plate press under the condition of cm ² and the thickness is about 125 μmm and the basis weight is 60 g.
A synthetic paper of / cm ² was obtained. The tensile strength of this synthetic paper was 1.95 Kgf / 5 cm, and the tensile elongation was 3.5%.

The air permeability of this synthetic paper (JIS P8117)
Was 30 seconds / 100 ml, and could be effectively used as a separator of a sealed secondary battery.

[Example 19] 1.6 parts (dry basis weight) of the nylon 6 fibrids prepared in the same manner as in Example 2 was added to about 800 ml of ion-exchanged water under high-speed stirring to uniformly disperse. It was On the other hand, 1.6 parts (dry basis weight) of the natural pulp used for the filter paper for chemical analysis was homogeneously dispersed in about 800 ml of ion-exchanged water in the same manner as above.

The above nylon 6 fibrid dispersion and the natural pulp dispersion were mixed and further vigorously stirred to obtain a homogeneous dispersion, and then a tappy standard sheet machine was used to obtain a sheet with a width of 25 cm each. When the paper was made into a sheet, the water was well drained from the paper mesh and the paper-making property was good.

After drying this sheet at 70 ° C. for 3 hours,
180 ℃ and pressure 50Kgf · cm ²Heat press under the conditions of
, Thickness about 128μmm, basis weight 60g / cm²Nairo
6 / natural pulp mixed paper was obtained. Pulling this mixed paper
Strength is 1.15 Kgf / 5 cm, tensile elongation is 1.8%
Met.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 7-44250 (32) Priority date Hei 7 (1995) March 3 (33) Country of priority claim Japan (JP) (31) Priority Claim number Japanese patent application No. 7-64127 (32) Priority date Hei 7 (1995) March 23 (33) Priority claiming country Japan (JP) (72) Inventor Yuzo Aito 2-1, Hinodemachi, Iwakuni-shi, Yamaguchi Prefecture Teijin Limited Iwakuni Research Center

Claims (11)

[Claims] 1. An N-methyl-containing aliphatic chloride and / or an aliphatic aromatic polyamide containing calcium chloride.
A solution composition dissolved in 2-pyrrolidone, wherein the ratio of the polyamide and N-methyl-2-pyrrolidone in the solution composition is N-methyl-2-pyrrolidone 97 to 25% by weight of the polyamide. 75% by weight,
And the polyamide solution composition characterized by containing 5-60 weight part calcium chloride with respect to 100 weight part of said polyamide. 2. The aliphatic polyamide is polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 6.6), polytetramethylene adipamide (nylon 4.6) and polyhexamethylene sebacamide (nylon). 6.10) and at least one polyamide selected from these copolyamides, and the polyamide solution composition according to claim 1. 3. The polyamide solution composition, wherein the proportion of the aliphatic polyamide and N-methyl-2-pyrrolidone is 95 to 80% by weight of N-methyl-2-pyrrolidone with respect to 5 to 20% by weight of the polyamide, and Polyamide 100
The polyamide solution composition according to claim 1 or 2, which contains 5 to 55 parts by weight of calcium chloride with respect to parts by weight. 4. The aliphatic aromatic polyamide is polyhexamethylene terephthalamide (nylon 6 · T), polyhexamethylene isophthalamide (nylon 6 · I), polyhexamethylene terephthalisophthalamide (nylon 6 · TI), polyhexa. The polyamide solution composition according to claim 1, which is at least one polyamide selected from methylene terephthalisophthaladipamide (nylon 6 · TI6) and copolyamides thereof. 5. The ratio of the aliphatic aromatic polyamide and N-methyl-2-pyrrolidone in the polyamide solution composition is 5 to 20% by weight of the polyamide and N-methyl-2.
Polyamide solution composition according to claim 1 or 4, characterized in that it contains 95 to 80% by weight of pyrrolidone and 5 to 55 parts by weight of calcium chloride per 100 parts by weight of the polyamide. 6. The polyamide solution composition according to claim 1, which is introduced into a precipitant containing water as a main component while stirring the precipitant to precipitate as pulp-like fine particles. Manufacturing method of polyamide fibrid. 7. The aliphatic polyamide solution composition according to claim 2 is introduced into a precipitant containing water as a main component while stirring the precipitant to precipitate as fine pulp-like particles. To produce aliphatic polyamide fibrids. 8. The aliphatic aromatic polyamide solution composition according to claim 4 is introduced into a precipitant having water as a main component while the precipitant is stirred to precipitate as fine pulp-like particles. A process for producing an aliphatic aromatic polyamide fibrid, which comprises: 9. The method for producing a polyamide fibrid according to claim 6, wherein the precipitant is water or an aqueous solution of N-methyl-2-pyrrolidone. 10. A paper sheet is prepared by mixing the polyamide fibrids produced by the method according to any one of claims 6 to 9 and short fibers to make paper, and further heating and pressurizing as necessary. A method for producing synthetic paper, which is characterized in that 11. A paper sheet is prepared by mixing the polyamide fibrids produced by the method according to any one of claims 6 to 9 and a natural pulp to make a paper, and further heating and pressing the paper if necessary. A method for producing a polyamide / natural pulp mixed paper, which is characterized in that