Fully aromatic polyamide fibers and method for producing the same

FIELD: process for producing of fully aromatic polyamide fibers comprising filler, in particular, aluminous mineral.

SUBSTANCE: fully aromatic polyamide fiber contains 100 weight parts of fully aromatic polyamide and from 0.05 to 20 weight parts of particles of aluminous mineral having laminated structure, such as hectorite, saponite, stevensite, beidellite, montmorillonite, and swelling mica.

EFFECT: improved mechanical properties of fibers, which may be provided with technological stability at fiber forming stage.

17 cl, 1 dwg, 3 tbl, 7 ex

 

The technical field to which the invention relates.

The present invention relates to wholly aromatic polyamide fibers containing alumina mineral with a layered structure, and the way they are received. More specifically, the present invention relates to wholly aromatic polyamide fibers containing alumina mineral with a layered structure and having improved mechanical properties, especially impact strength, and the way they are received.

Description of the prior art

In recent years, considerable interest is focused on providing high value-added processing of polymers and improve their performance. Multicomponent materials obtained by introducing a filler into the polymer, has been actively developed with the goal of providing high value-added processing of polymers and high performance polymers. In the past, were used fibrous or needle-like fillers as reinforcing fillers to improve mechanical properties and heat resistance of the polymers, and as a result have improved known polymeric materials in terms of tensile strength, modulus of elasticity, tensile strength in bending, thermal dimensional stability and creep properties, and FS is cnym other properties such as an advanced base (resistance to bending), wear resistance, surface hardness, heat resistance and impact resistance.

However, it is known that the strength of a multicomponent material strongly influences not only the strength of the polymer acting as a matrix of multicomponent material, as well as the strength of the actual filler, but also the adhesion at an interface between the filler and polymer, and the quality of the wettability of the polymer with the filler have an impact not only on ease of access, but also on the strength of the final product. Due to these reasons it is not always possible to obtain multi-component material having excellent durability, even if the material is filler, or polymer with high strength and elasticity.

Moreover, it is well known that multi-component material containing a filler, have the disadvantage of low magnitude ultimate elongation.

On the other hand, in a method of producing wholly aromatic polyamide fibers (hereinafter will be referred to as aramid fibers), there is a need for further improvement of process stability and product quality (prevention of breakage of the thread). It is well known that the factor of impact strength (TF) can be generally used in the image quality is as a parameter for assessing industrial aramid fibers. Factor impact strength (TF) is expressed as the product of the tensile strength (T′), which is measured in units of grams/denier, and the square root of ultimate elongation (E %) (TF=T′×E1/2). In the case of fibers having a high factor of toughness, it is known that the number of fibers remaining in the exhaust cylinder in the drawing process, is reduced, and as a result, reduces the breakage of the filaments formed in the fibers, resulting in improved stability of the process of extraction and improvement of the quality of the resulting fiber threads.

Although a well-known example of a method of improving the mechanical strength of the fiber includes improving the degree of orientation of the fibers by extrusion, in the case of using such a method, since it is known that the ultimate elongation decreases with improved tensile strength, it becomes difficult to obtain filaments having a high factor of toughness.

In the past it was assumed that the introduction of a filler in the form of alumina mineral with a layered structure will lead to improved mechanical properties and shape of polyamide fibers (see published patent application of Japan No.. H3-31364, N4-209882 and N8-3818). However, these decisions relate to thermoplastic polyamides, and these documents do not disclose the use of clay is slightly mineral with a layered structure for neuroplasticity polyamides, in the form of wholly aromatic polyamide fibers.

In addition, the estimation methods using aluminous minerals with a layered structure as fillers to improve mechanical properties and heat-resistant wholly aromatic polyamides. For example, in laid the patent application of Japan No. H11-236501 disclosed is a method of obtaining a fully aromatic polyamide multi-component material, which is used as a highly heat-resistant material, by mixing an aqueous solution containing diamino monomer, and a solution in an organic solvent, monomer - acylated dicarboxylic acid, which is soluble in water, and adding alumina mineral water solution or a solution in an organic solvent, in the process of polycondensation of the monomers. In lined with the application for the Japan patent No. H11-255839 disclosed method is effective for obtaining compounds by polymerization in solution fully aromatic polyamide in the solution of alumina mineral with a layered structure in the solvent, able to dissolve specified aluminous mineral with a layered structure, while posted in the patent application of Japan No. H11-256034 method for obtaining a fully aromatic polyamide compounds having improved m the mechanical properties, in which alumina mineral with a layered structure very effectively dispersed in the fully aromatic polyamide, by removing an organic solvent from a solution consisting of wholly aromatic polyamide alumina mineral with a layered structure and an organic solvent.

However, from the documents of the prior art is not known to improve the mechanical properties of fully aromatic polyamide fibers by introducing alumina mineral with a layered structure as filler, and wholly aromatic polyamide fibers containing alumina mineral with a layered structure as a filler and having a high factor of toughness as a result of this improvement.

Disclosure of inventions

The purpose of the present invention is to provide wholly aromatic polyamide fibers having excellent mechanical properties and high factor toughness, in particular, which can nakativaetsa with satisfactory technological stability of the spinning process, and the means of industrial production of these fibers.

According to research conducted by the authors of the present invention, it was found that elongated and oriented wholly aromatic polyamide fibers obtained by wet the century spinning and extruding a spinning liquid, containing wholly aromatic polyamide and alumina mineral with a layered structure, have excellent mechanical properties and, in particular, a great factor toughness. More unexpectedly, also established by the authors of the present invention that, instead of completely homogeneous dispersion of each layer of alumina mineral with a layered structure in the fibers by the statistical distribution of the set of regions having a relatively high density alumina mineral with a layered structure, in a matrix of aromatic polyamide polymer containing particles may be additionally strengthened the effect of improving the mechanical properties of fibers, in particular factor toughness due to particles of alumina mineral with a layered structure.

Elongated and oriented wholly aromatic polyamide fibers of the present invention includes a resin composition, which contains a matrix consisting of a wholly aromatic polyamide resin and particles of alumina mineral with a layered structure, dispersed and distributed in the matrix in an amount of from 0.05 to 20 wt. parts, per 100 wt. parts of the matrix.

In the wholly aromatic polyamide fibers of the present invention are many areas in which particles glycosaminoglycan with a layered structure is distributed with a relatively high density, preferably statistically distributed in the fully aromatic polyamide matrix.

In the wholly aromatic polyamide fibers of the present invention, when the wholly aromatic polyamide fibers are the shortest path along the axis of the fibers, the resulting profiles of the cross section is observed with an electron microscope with magnification of 100,000, and each profile is the total area S1 of the many areas in which the changing profile of the fiber, due to the influence of alumina particles of the mineral with a layered structure, distributed in the measured field observations S2, equal to 25 μm2the degree of dispersion of Y-alumina particles of the mineral with a layered structure in each fiber, defined by equation (1)

preferably is in the range from 0.1 to 40.

In the wholly aromatic polyamide fibers of the present invention aluminous mineral with a layered structure preferably includes at least one selected from hectorite, saponite, stevensite, beidellite, swelling montmorillonite and mica.

In the wholly aromatic polyamide fibers of the present invention the particles of alumina mineral with a layered structure are particles treated intercalar is the missing agent.

In the wholly aromatic polyamide fibers of the present invention, a layer of alumina particles of the mineral with a layered structure preferably has an average thickness of from 10 to 500 nm.

In the wholly aromatic polyamide fibers of the present invention, the alumina particles of the mineral with a layered structure preferably have a degree of orientation And 50% or more, And is determined according to the equation (2)

In equation (2) w denotes the width of the intensity distribution found by x-ray analysis of the alumina particles of the mineral with a layered structure along the Debye ring of the reflection peak in the plane (001) of the alumina particles of the mineral with a layered structure.

In the wholly aromatic polyamide fibers of the present invention, the ratio (T/M) tensile strength (t) of the wholly aromatic polyamide fibers to the tensile strength (That) comparative wholly aromatic polyamide fibers, identical wholly aromatic polyamide fibers, with the exception of the alumina particles of the mineral with a layered structure (which is missing), is preferably 1.1 or more.

In the wholly aromatic polyamide fibers of the present invention, the ratio (E/EO) ultimate elongation (E) the color of aromatic polyamide fibers to the maximum elongation (SW) comparative wholly aromatic polyamide fibers, identical wholly aromatic polyamide fibers, with the exception of the alumina particles of the mineral with a layered structure (which is missing), is preferably 1.1 or more.

In the wholly aromatic polyamide fibers of the present invention the factor of impact strength (TF) wholly aromatic polyamide fibers is determined according to the equation (3)

In this equation (3) T′ represents the numerical value of the tensile strength, in units of g/1.1 decitex", wholly aromatic polyamide fibers and E′ represents the numerical value of the maximum elongation (%), wholly aromatic polyamide fibers is preferably 30 or more.

In the wholly aromatic polyamide fibers of the present invention, the ratio (TF/TFo) factor impact strength (TF) wholly aromatic polyamide fibers to the factor of adhesion (TFo) comparative wholly aromatic polyamide fibers, identical wholly aromatic polyamide fibers, with the exception of the alumina particles of the mineral with a layered structure (which is missing), is preferably 1.1 or more.

In the wholly aromatic polyamide fibers of the present invention, the alumina particles of the mineral with a layered is the structure preferably contain organic onevia ions, located between the layers of the mineral.

In the wholly aromatic polyamide fibers of the present invention preferably wholly aromatic polyamide resin selected from fully meta-aromatic polyamide resin.

The method of the present invention for receiving elongated and oriented wholly aromatic polyamide fibers includes the selection of the spinning liquid, solvent, and wholly aromatic polyamide resin, and particles of alumina mineral with a layered structure in an amount of from 0.05 to 20 wt. parts per 100 wt. parts of the wholly aromatic polyamide resin through a multichannel mouthpiece with the formation of filamentary streams of the spinning liquid;

introduction filamentary streams of the spinning liquid in an aqueous coagulating bath to coagulate filamentary streams of the spinning liquid;

pulling obtained devicenote threads in a humidified atmosphere and

drying heat treatment of the obtained extruded threads.

In the method of the present invention to obtain a wholly aromatic polyamide fibers preferably the spinning liquid is prepared by mixing solution a, which includes part of the solvent, part of the wholly aromatic polyamide resin and particles of alumina mineral with a layered article is octoroi in an amount of from 30 to 300 wt. parts per 100 wt. parts of the wholly aromatic polyamide resin with a solution containing the remainder of the solvent, the rest of the wholly aromatic polyamide resin, and satisfies the requirements (1) and (2):

(1) the viscosity of the solution (A) at the shear rate of 0.1 sec-1in 15-80 times greater than the viscosity of the solution And at a shear rate of 10 sec-1and

(2) the viscosity of the solution (A) at the shear rate of 0.1 sec-14-20 times greater than the viscosity of the solution (C) at the shear rate of 0.1 sec-1.

In the method of the present invention to obtain a wholly aromatic polyamide fibers preferably the concentration of the wholly aromatic polyamide resin in the spinning solution is from 0.1 to 30 wt.%.

In the method of the present invention to obtain a wholly aromatic polyamide fibers, the degree of stretching devicenote threads in a humidified atmosphere preferably is in the range from 30 to 60% of the maximum stretching devicenote threads.

In the method of the present invention to obtain a wholly aromatic polyamide fibers preferably the solvent is selected from polar amide solvents.

In the method of the present invention to obtain a wholly aromatic polyamide fibers are preferably wholly aromatic polyamide resin you who eraut from fully meta-aromatic polyamide resin.

Brief description of drawing

The drawing represents an electron micrograph of the cross section of one example of a wholly aromatic polyamide fibers of the present invention.

The best option of carrying out the invention

In the fully aromatic polyamide used in the present invention, an aromatic ring, which forms the main chain of recurring units fully aromatic polyamide, linked together by an amide bonds, and fully aromatic polyamide preferably chosen from meta fully-aromatic polyamides. Usually this type wholly aromatic polyamides obtained by low temperature polymerization in solution or polymerization at the interface of dihalogenide aromatic dicarboxylic acid and aromatic diamine in their solution.

Although diamino component used in the present invention preferably contains one or more types, for example, para-phenylenediamine, 2-chloro-para-phenylenediamine, 2,5-dichloro-para-phenylenediamine, 2,6-dichloro-para-phenylenediamine, meta-phenylenediamine, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone or 3.3′-diaminodiphenylsulfone, it is not limited to these diamines. Among these diamino the s compounds are preferably used para-phenylenediamine, meta-phenylenediamine and 3,4′-diaminodiphenyl ether.

In addition, although dihalogenide component of the aromatic dicarboxylic acid used in the present invention preferably contains one or more types, for example, dichloride visitorial acid dichloride, terephthalic acid dichloride, 2-chloraseptic acid dichloride, 2,5-dichloracetic acid dichloride, 2,6-dichloracetic acid or dichloride, 2,6-naphthaleneboronic acid, they are not limited to the above. Among these dihalogenide aromatic dicarboxylic acid dichloride, terephthalic acid and/or isophthalic acid dichloride are used preferably.

Among the above wholly aromatic polyamides are preferably used poly-meta-phenylenedimaleimide and copoly-para-phenylene-3,4′-deoxidation-terephthalamide, although particularly preferably used poly-meta-phenylene-isophthalamide.

Upon receipt of the spinning fluid through polymerizati fully aromatic polyamide is used, at least one type of solvent, examples of which include (but are not limited to these organic polar solvents based on amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and N-methylcaprolactam, water-soluble ether compounds is of, such as tetrahydrofuran and dioxane, water-soluble alcohol compounds such as methanol, ethanol and ethylene glycol, water-soluble ketone compounds such as acetone and methyl ethyl ketone, and water-soluble nitrile compounds such as acetonitrile and propionitrile. In addition, the above solvents may be a mixture of two or more types of compounds mentioned above. Preferably in the method of the present invention is used dehydrated solvent.

In this case, the polymerization mixture may be added a suitable amount of traditionally known inorganic salts, before polymerization, during polymerization or after polymerization, with the aim of increasing the solubility. Examples of such inorganic salts include lithium chloride and calcium chloride.

In addition, upon receipt of a fully aromatic polyamide of the above diamino component and the above halide acid component, the molar ratio diamino component to the halide acid component preferably regulate in the range from 0.90 to 1.10 is and more preferably from 0.95 to 1.05.

End group of the molecule fully aromatic polyamide used in the present invention, can be blocked. In the case of use with this purpose, agent, block the end of the tank group, the examples used blocking agent include chloride and phthalic acid and its substituted form, while examples of the amine component include aniline and its substituted form.

In General, aliphatic amine, aromatic amine salt and Quaternary ammonium can be used in combination in order to bind the acid, such as halomonadaceae formed by the interaction between the halides of acids and diamines.

After the above polymerization reaction in the reaction mixture can be added to the basic inorganic compound such as sodium hydroxide, potassium hydroxide, calcium hydroxide or calcium oxide, which is necessary to neutralize the reaction mixture.

There are no special restrictions on the reaction conditions, upon receipt of a fully aromatic polyamide of the present invention. Typically, the interaction between the acid halide and diamine occurs rapidly, and the typical reaction temperature is from -25 to 100°and preferably -10 to 80°C.

Wholly aromatic polyamide polymer, thus obtained, can be extracted in the form of flocculent suspensions, by downloading and immersion of the polymer in nerastvorim fluid such as water or alcohol. Although the flakes of polymer can be dissolved in the solvent,and the resulting solution can be used for wet spinning, the solution resulting from the polymerization reaction, can also be used as a spinning liquid. Although there are no particular restrictions on the solvent used when re-dissolving the formed polymer flakes and the wholly aromatic polyamide is dissolved, preferably is the same solvent as in the polymerization of the above wholly aromatic polyamide.

In the following are preferably used aluminous mineral with a layered structure used in the present invention, which has the ability to cation exchange and demonstrates the property of swelling as a result of introduction of water between the layers of the mineral, and smectitic aluminous mineral and swelling mica. Specific examples of the alumina mineral with a layered structure include smectite aluminous minerals such as hectorite, saponite, stevensite, Badelt and montmorillonite (including their natural and chemically synthesized form), as well as substituted forms, derivatives, or mixtures thereof. In addition, examples of the swelling mica include synthetic swelling mica, which is synthesized chemically and contains ions of Li and Na between layers of mica and their substituted forms, derivatives or mixture.

In the present invention the particles of alumina mi is erala with a layered structure, treated with surface-active substance containing organic onevia ions (intercalating agent), preferably used as particles above alumina mineral with a layered structure. Processing these organic onievymi ions improves the dispersion of the wholly aromatic polyamide of the particulate alumina mineral with a layered structure in the matrix and improves formemost yarns and factor in the impact strength of the resulting fibers.

Preferably organic viewy ion used in the above surface treatment, selected from Quaternary ammonium ions having a chemical structure represented by the following formula (1):

(in which R1, R2, R3and R4respectively and independently mean alkyl group having from 1 to 30 carbon atoms or hydroxytrimethylene group represented as - (CH2CH2O)nH). Among the alkyl groups having from 1 to 30 carbon atoms, represented as R1, R2, R3and R4here are the preferred alkyl group having from 1 to 18 carbon atoms. Preferred examples of Quaternary ammonium compounds include (but are not limited to dodecyldimethyl unilorin, tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, realtimeisuniversal, didodecyldimethylammonium, detraditionalisation, dihexadecylnaphthalene, dioxidecontaining, mileydeminiley, didecyldimethylammoniumchloride, tetradecyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, realtimedesigner, trioctyltrimellitate, gidroksipropilmetilzelluloza, hydroxytamoxifen-didecyldimethylammoniumchloride, hydroxyperoxyeicosatetraenoates, hydroxyperoxyeicosatetraenoates, hydroxyperoxyeicosatetraenoates, hydroxyperoxyeicosatetraenoates, dihydroxydiphenylmethane, bis(hydroxytamoxifen)tetradecyltrimethylammonium, bis(hydroxytamoxifen)hexadecyltrimethylammonium, bis(hydroxytamoxifen)octadecyltrimethylammonium and bis(hydroxytamoxifen)oleilethanolamid.

An example of a method of processing particles of alumina mineral with a layered structure of an organic onievymi ions usually involves mixing 1 wt. part of the cha is TIC aluminous mineral with a layered structure and from 1 to 10 wt. parts organic niewyk ions in water, followed by drying the mixture. The amount of water used is preferably in the range of 1-100 times the amount of aluminous minerals with a layered structure. In addition, the temperature during mixing is preferably from 30 to 70°S, and the mixing time is preferably from 0.5 to 2 hours. The preferred conditions of the drying means drying under normal pressure for 3 days at a temperature of 70-100°and then vacuum drying for 2 days.

Preferably, the average thickness of the layer of alumina particles of the mineral with a layered structure in the wholly aromatic polyamide fibers of the present invention is 500 nm or less and more preferably 200 nm or less. In addition, as mentioned here, the average thickness of the layer of alumina mineral with a layered structure means the average thickness of the layer which is defined for all particles of alumina mineral with a layered structure, in cross-sectional area of 25 μm2when measured with an electron microscope (magnification: 100000×) longitudinal cross-section fibers. If the average thickness of the layer of alumina mineral with a layered structure is greater than 500 nm, there may be difficulties in ensuring the stability of the formation during spinning education is the standing of the resin composition. On the other hand, if you try to increase the dispersion of alumina particles of the mineral with a layered structure down to the molecular level, it is necessary to reduce the concentration of the spinning liquid, in order to ensure the effects of density and particle size distribution of alumina mineral with a layered structure that, in combination with a decrease in the production efficiency of the spinning process also reduces the effect of improving the impact strength of the resulting fibers. Therefore, the average thickness of the layer of alumina particles of the mineral with a layered structure is preferably 10 nm or more and more preferably 12 nm or more. In addition, the preferred vertical and horizontal sizes of the particles of alumina mineral with a layered structure used in the present invention, is equal to (50-1000 nm)×(50-1000 nm), and more preferably 100-500 nm)×(100-500 nm).

Moreover, when the total surface area S1 is measured in a multitude of areas in which state changes occur cross-section of the fibers due to the influence of alumina particles of the mineral with a layered structure, the observed cross-sectional area S2, equal to 25 μm2by cutting wholly aromatic polyamide fibers along the fiber axis and the examination of a longitudinal section in e the main objective of the microscope with magnification of 100,000 times the degree of dispersion of Y within each of the alumina particles of the mineral with a layered structure, which is determined by the following formula (1):

preferably is in the range from 0.1 to 40% and more preferably in the range of from 0.5 to 30%. If the degree of dispersion of Y is less than 0.1, the improvement factor toughness is small, whereas if the degree of dispersion of Y exceeds 40 becomes low transparency of the spinning liquid derived from wholly aromatic polyamide particles of alumina mineral with a layered structure and solvent, and reduced plasticity.

In the above microscopic examination of changes of state of the fibers observed in the cross section of the fibers, called distributed in these areas cross-alumina particles of the mineral with a layered structure, which are common with high distribution density compared to other areas. In the present invention discovered that the factor of impact strength of the resulting fibers can be increased thus, due to the statistical distribution of areas with relatively high density of particles of alumina mineral with a layered structure in the matrix fibers, wholly aromatic polyamide what about the polymer. It is advisable diffuse distribution of areas with relatively high density of particles of alumina mineral with a layered structure can be achieved by adjusting the degree of dispersion of Y-alumina particles of the mineral with a layered structure within the range from 0.1 to 40,

The drawing shows a cross section of an extruded sample of wholly aromatic polyamide fibers of the present invention. In the drawing, there are many areas with a high density alumina mineral with a layered structure, which are statistically distributed in the form of staple fibers in the cross section of the fiber. These areas are like staple fibers are elongated along the direction of the fiber axis.

Although not fully explained the reasons for the better factor the impact strength of the resulting fibers in the statistical distribution of areas with relatively high density of particles of alumina mineral with a layered structure in the fibers, as described above, when pulled these areas containing particles of alumina mineral with a layered structure with high-density distribution, it is assumed that the mesh structure is formed of alumina particles of the mineral with a layered structure and molecules wholly aromatic polyamide the first polymer, this lattice structure is oriented along the direction of the axis of the fibers by extrusion. The authors suggest that the formation of this mesh structure, oriented between the particles of alumina mineral with a layered structure and a polymer, gives the main contribution to the improvement factor impact strength, even at relatively low content of alumina particles of the mineral with a layered structure.

In the present invention can be used fillers different from aluminous mineral with a layered structure, in combination with the wholly aromatic polyamide polymer, provided that they do not impair the physical properties or technological stability during spinning. Although as a filler can be used fibrous or fibrous fillers, such as flaky, scaly, granular fillers with incorrect form or crushed fillers, especially preferred are fibrous fillers. Specific examples of fillers include whiskers of potassium titanate, whiskers titanate palladium, whiskers of aluminum borate, whiskers of silicon nitride, mica, talc, kaolin, silicon dioxide, calcium carbonate, glass beads, glass flakes, glass microspheres, alumina, dis is hid molybdenum, the wollastonite, titanium dioxide, zinc oxide, calcium polyphosphate, graphite, metal powder, metal flakes, metal tape, metal oxides, carbon powder, graphite, carbon flakes and scaly carbon. Moreover, in the case of a high degree of pulping monofilaments of a wholly aromatic polyamide fibers may be used glass fibers, carbon fibers such as polyacrylonitrile and bituminous fiber, metal fiber, such as fiber, stainless steel, aluminum fiber, brass fiber, organic fiber, such as wholly aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, fibers, Zirconia fibers of aluminum oxide, fibers of silica, fibers of titanium dioxide, fiber silicon carbide, slag wool, or metal tape. Additionally, there may be used two or more types of these additives in combination.

Moreover, the above fillers can also be used after treatment of their surface known binders (such as a binding agent based on silane or binder based on titanate) or other material for surface treatment.

In the wholly aromatic polyamide fibers of the present image is etenia necessary to the content of aluminous minerals with a layered structure was in the range of from 0.05 to 20 wt. parts, preferably from 0.1 to 10 wt. parts and more preferably from 0.5 to 5 wt. parts, relative to 100 wt. parts of the wholly aromatic polyamide. If the content of alumina mineral with a layered structure is less than 0.05 wt. parts relative to 100 wt. parts specified fully aromatic polyamide, that is not observed improvement factor toughness, though, if the content of this mineral is greater than 20 wt. parts, it becomes a low transparency and reduced plasticity of the spinning liquid, consisting of aluminous minerals with a layered structure, fully aromatic polyamide and a solvent therefore, such compositions are undesirable.

In addition, if the degree of orientation And alumina mineral with a layered structure in the fibers is 50% or more, preferably 70% or more and more preferably 80% or more, the improved mechanical properties (factor toughness) and various physical properties such as thermal dimensional stability, therefore, this orientation is preferred.

In addition, the degree of orientation And the alumina particles of the mineral with a layered structure is determined according to the following formula of intensive the STI distribution, measured along the Debye ring of the reflection peak in the plane (001) of the alumina particles of the mineral with a layered structure and defined by x-ray analysis.

In this formula, w indicates the width (in degrees) of the intensity distribution measured along the Debye ring of the reflection peak.

Wholly aromatic polyamide fibers of the present invention have a tensile strength which is better by 10% or more, and ultimate elongation (E), which is better by 10% or more, compared with the wholly aromatic polyamide portages, which are completely identical to the above wholly aromatic polyamide fibers, with the exception of the alumina particles of the mineral with a layered structure (which is missing). In addition, the wholly aromatic polyamide fibers of the present invention have the factor of toughness (TF), which is better by 10% or more, especially better by 20% or more and preferably better by 30% or more, compared with the wholly aromatic polyamide fibers. Moreover, the above mentioned factors impact strength (TF) is defined as the product of the tensile strength (T′), which is measured in units of grams/denier, and ultimate elongation (E), which is measured in percent, namely TF=′ ×(E)1/2.

Thus, if the factor of impact strength is improved by 30% or more when improving the strength of the fibers, there are fewer yarn breaks in the fibers, even if it increases the degree of stretching (better quality), and reduces the number of fibers remaining in the exhaust cylinder and the like in the drawing process (improves stability). In particular, the improvement factor toughness by 10% or more is preferable, as it becomes more the effect of stabilization in the process of drawing.

In addition, the wholly aromatic polyamide fibers of the present invention can also contain additives, such as antioxidants, heat stabilizers, agents that increase the weather resistance, dyes, antistatic agents, flame retardant agents, or agents that increase the conductivity, in such amount that does not impair the useful effect of the invention.

Wholly aromatic polyamide fibers of the present invention can be obtained, for example, by using a method similar to that described below. Namely, wholly aromatic polyamide fibers of the present invention can be obtained, for example, by using a method that includes the steps: (1) preparation of the spinning liquid (spinning solution), consisting of all the romantic polyamide, alumina mineral with a layered structure and a solvent, (2) coagulation of the spinning liquid by introducing streams of the spinning liquid in an aqueous coagulating bath, (3) pulling the coagulated filaments in a humidified atmosphere, and (4) drying the heat-treated extruded filaments. The ratio of alumina mineral with a layered structure to a fully aromatic polyamide in the spinning liquid in the mixture is adjusted in the range from 0.05 to 20 wt. parts, preferably from 0.1 to 10 wt. parts and particularly preferably from 0.5 to 5 wt. parts per 100 wt. parts of the wholly aromatic polyamide. In addition, the concentration of polymer in the spinning liquid is preferably from 0.1 to 30 wt.%, more preferably from 1 to 25 wt.%, and even more preferably from 15 to 25 wt.%. Moreover, the opacity of the spinning liquid is preferably brought to 10 or less and more preferably 5 or less.

In addition, there are no restrictions on the method of obtaining the spinning liquid. Examples of methods that may be used include: (a) method in which alumina mineral with a layered structure added to a solution of fully aromatic polyamide (B) the manner in which the solution of a wholly aromatic polyamide and the dispersion of alumina mineral with a layered structure of the Pach is with each other, and (C) the way in which a fully aromatic polyamide added to a solution of alumina mineral with a layered structure.

Upon receipt of the spinning fluid from the wholly aromatic polyamide polymer, particles of alumina mineral with a layered structure and solvent preferably spinning liquid used in the present invention, is obtained by preparation of a solution a, which includes part of the solvent, part of the wholly aromatic polyamide polymer and from 30 to 300 wt. parts of alumina particles of the mineral with a layered structure per 100 wt. parts of this wholly aromatic polyamide polymer, a separate solution, comprising the solvent and the remainder of the wholly aromatic polyamide polymer, and mixing solution a and solution In such a way that the solvent a and the solvent simultaneously satisfy the following conditions:

(1) the viscosity of the solution And at a shear rate of 0.1 sec-1in 15-80 times greater than its viscosity at the shear rate of 10 sec-1and

(2) the viscosity of the solution And at a shear rate of 0.1 sec-14-20 times higher solution viscosity At shear rate of 0.1 sec-1.

As a result of this cooking area having a relatively high density of particles of aluminous minerals with layered the structure, can be uniformly dispersed and distributed in the spinning liquid, which, along with stabilization of the spinning process, allows to adjust the degree of dispersion of Y-alumina particles of the mineral with a layered structure formed in the fibers at the desired level, thereby increasing the effect of improving the factor of impact strength of the resulting fibers.

Here, if the ratio of alumina mineral with a layered structure to a fully aromatic polyamide in solution And is less than 30 wt. parts and decreases the difference in the viscosity of solution, aluminous mineral with a layered structure is easier and more uniformly distributed in the resulting spinning liquid, and reduces the effect of the improvement factor toughness. On the other hand, if this ratio exceeds 300 wt. parts, then the distribution density of the alumina mineral with a layered structure becomes significantly less uniform, and as a result, the stability of the spinning process may be reduced.

In addition, if the viscosity of the solution And at a shear rate of 0.1 sec-1less than 4 times the viscosity of the solution at a shear rate of 0.1 sec-1then aluminous mineral with a layered structure easily and evenly distributed, resulting in slowing down the formation of regions having a relatively substantial the density distribution of particles of alumina mineral with a layered structure, and decreases the effect of improving factor toughness. On the other hand, if the viscosity is more than 20 times, the formation of areas with relatively high density of particles of alumina mineral with a layered structure in the spinning liquid in the spinning process, becomes excessive, resulting in increasing pressure packing and the like and process stability may decrease. In addition, if the viscosity of the solution And at a shear rate of 0.1 sec-1less than 15 times differs from the viscosity at the shear rate of 10 sec-1, aluminous mineral with a layered structure easily and evenly distributed in the fibers, it reduces the formation of regions having a relatively greater density distribution of the alumina particles of the mineral with a layered structure, and reduces the effect of the improvement factor toughness. On the other hand, if the viscosity is more than 20 times, the formation of areas with relatively high density of particles of alumina mineral with a layered structure in the spinning liquid in the spinning process, becomes excessive and as a result, the stability may decrease.

Although the solvent used for preparation of the spinning liquid is arbitrary, provided that it fully rest who shall aromatic polyamide, preferred are those that contain mostly polar solvent-based amide, specific examples of which include aprotic organic solvent-based amide, such as N-methyl-2-pyrrolidone (NRM), N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, dimethylformamide, tetramethylrhodamine, hexamethylphosphoramide and N-methylbutyrate. Although the temperature of the spinning liquid is expedient should be installed in accordance with the solubility of fully aromatic polyamide, preferably it is set in the range from 50 to 90°Since, from the point of view of the spinning capacity in the case polymethacrylamide.

In the method of the present invention filamentary streams of the spinning liquid is introduced, for example, directly in the aqueous coagulating bath of multi-channel mouthpiece, which usually has 10 to 30,000 outlets in order to coagulate filamentary stream with the formation of devicenote fibers. There are no specific limitations to the composition of the aqueous coagulating bath used according to the invention, although it is advisable composition should be selected in accordance with the types used wholly aromatic polyamide and a solvent can be used traditionally known aqueous coagulating bath containing an inorganic salt and/or Rast ritel. More specifically, if fully aromatic polyamide is polymethylpentene and the solvent is N-methyl-2-pyrrolidone (NRM), a preferred example, the aqueous solution has a concentration of calcium chloride from 34 to 42 wt.% and the concentration of the NRM from 3 to 10 wt.%. In this case, a suitable temperature aqueous coagulating bath is in the range from 80 to 95°With the time of immersion of the fibers in the coagulating bath is advisable in the range from 1 to 11 seconds.

Since a significant amount of solvent remains on devicenote fibers removed from the coagulating bath, preferably devicenote fiber is washed in order to remove and to remove the residual solvent. Examples of methods used include transmission devicenote fibres through water bath, after their removal from the coagulating bath, and splashing water on devicenote fiber. Preferably, the solvent content in the fibres after washing is regulated at the level of 30 wt.% or less, and at a higher water content, it can penetrate into the fibers in the subsequent process of drawing and can easily be formed cavities, which will reduce the strength of the fiber.

Washed devicenote fiber pull in a humidified atmosphere, preferably in a bath of warm water, at the same time, by rinsing galayda residual solvent and inorganic salt, such as calcium chloride, which are used in combination, if necessary. The temperature at which is above the pulling, it is installed in accordance with the amount of solvent remaining in devicenote fibers. For example, in the case where the amount of residual solvent is 50% or more relative to the weight of the polymer, preferably the temperature of the extrusion adjust from 0 to 50°With, although in the case when the amount of residual solvent is less than 50% relative to the weight of the polymer, preferably the temperature of the extrusion adjust from 50 to 100°C. furthermore, preferably the degree of stretching regulate from 0.3 to 0.6 times, more preferably to 1.05 times or more, even more preferably up to 1.10 times or more from the maximum degree of stretching devicenote fibers (degree of stretching, which begins to occur the destruction of threads, pulling in identical conditions).

The resulting elongated fiber is usually dried at a temperature of 100°With or higher, followed by hot stretching, if necessary, and further heat treatment using a heating roller or heating tile.

Then thus obtained wholly aromatic polyamide fibers are placed in the drum, by the tea needed twist or served directly to further processing, or after corrugation, if necessary, cut, and they do in any subsequent desired processing in the form of short fibers.

EXAMPLES

A more detailed explanation of the present invention is provided with the following examples.

In these examples, specific properties are defined using the following tests.

(Characteristic viscosity XB)

The test polymer is dissolved in N-methyl-2-pyrrolidone at a concentration of 0.5 g/100 ml, and the viscosity of this solution is measured at 30°using Ostwald viscometer, and then, using the measured value of viscosity, calculate the characteristic viscosity.

(Viscosity)

The viscosity of the spinning liquid is measured at 70°using viscometer manufactured by Rheometric Scientific (brand Rheomat 115).

(The degree of pulping)

The degree of pulping measured in accordance with the standard of Japan JIS-L-1015.

(Tensile strength, ultimate elongation)

The tensile strength and ultimate elongation is measured in accordance with JIS-L-1015, using a sample length of 20 mm, the initial load of 0.05 g/decitex and the speed of the pulling rate of 20 mm/min

(The degree of orientation And alumina mineral with a layered structure)

Step the new orientation is measured using an x-ray source (Rigaku Denki, RU-200B) in the conditions: radiation CuKα target, a voltage of 45 kV and a current of 70 mA. Incident x-ray radiation covergirls and turns into a monochromatic radiation with the help of a mirror with a multilayer structure produced by Osmic, in subsequent measurements of samples of fiber used method of vertical transmission. Detection of the refracted x-ray radiation is measured using image plates (firm Fuji Photo Film) size 200 mm × 250 mm in terms of length of the chamber 250 mm, the Degree of orientation of the surface layer of the alumina is determined by the following formula of intensity distribution measured along the Debye ring of the reflection peak in the plane (001).

In this equation, w denotes the width of the intensity distribution measured along the Debye ring of the reflection peak.

(Matte spinning liquid)

Matte spinning fluid that fills the cell with optical path length of 1 cm, measured using a turbidity meter NDH2000, produced by Nippon Denshoku.

(The average thickness of the layer of alumina particles of the mineral with a layered structure)

The layer thickness of all particles of alumina mineral with a layered structure observed in cross section with the measured size of 25 μm2in electron micrographs napromustine (TEM - transmission electron microscope, the magnification of 100,000 times) longitudinal section of the fiber, determined using electron microscope H-800, produced by Hitachi, Ltd., with the subsequent calculation of the average thickness.

(The degree of dispersion (Y) alumina mineral with a layered structure)

The above wholly aromatic polyamide fiber cut in the fiber axis and the resulting longitudinal section examined at magnification of 100,000 times using a transmission electron microscope (Model H-800), produced by Hitachi, Ltd. When examining the total surface area S1, there are many areas in which state changes occur cross-section of the fiber, due to the action of the particles of the above alumina mineral with a layered structure observed in cross-sectional area equal to 25 μm2the degree of dispersion of Y-alumina particles of the mineral with a layered structure in the fibers, as defined by the above formula (1), calculated according to the following formula:

The average value of Y is determined by three dimensions.

(Shear viscosity solution)

Shear viscosity of the solution in the preparation of the spinning liquid is measured at a temperature of 70°using device Rheomat 115, produced by Rheometric Scintific.

(The content of the solvent in the fiber, N)

The fibers are centrifuged for 10 minutes (the rotation speed of 5000 rpm), to pull, and then boiled for 4 hours in methanol to extract the solvent and water from the fibers. Measure the mass of a methanolic solution of M2 after extraction and the mass of dry fiber M1 and the mass concentration of solvent (%) in the extract using gas chromatograph, with subsequent calculation of the content of the solvent N, according to the following formula:

(Breakage threads)

Many of the resulting extruded fibers are uniformly formed in the beam, with one end of the bundle of fibers is fixed, and then the beam is cut so that the length from the fixed end to the other end was 20 see the Total number of filaments in a bundle of fibers for a given moment is designated as N. Then the beam of fibers moves back and forth 10 times in the longitudinal direction in a bath filled with water (longitudinal width of 0.5 m), then the bundle of fibers is removed and then count the number of threads remaining in the bath. This procedure is repeated five times, and the total number of threads remaining in the bath, denoted as M, Then count the number of dangling threads on the length of 15,000 m (X), using the following formula: the calculation is repeated three times in order to determine the ü average.

X=M×15000/(N×T×0,2)

Example 1

Polymethylpentene (215 g), having a characteristic viscosity of 1.35 DL/g, is dissolved in 785 g of the NRM and mix, receiving a uniform, transparent spinning solution. Separately from this procedure aluminous mineral with a layered structure in the form smectite alumina mineral, processed chloride Polyoxypropylenediamine (brand: Lucentite SPN, the firm Co-op Chemical), are mixed and dispersed in the NRM at a concentration of 1 wt.%. The resulting dispersion of alumina mineral with a layered structure added to a solution of fully aromatic polyamide, in order to obtain the composition shown in table 1, and then stirred to prepare a spinning liquid (spinning solution). The resulting spinning solution has a score of Mat 2,41. After degassing the resulting spinning solution is extruded in the form of filamentary streams of the multi-channel mouthpiece, having a diameter of cap 0.07 mm and 100 holes; these filamentary streams is introduced into the coagulating bath consisting of a solution of 43% of calcium chloride in water (containing 1 wt.% The NRM), at 85°and then the solid coagulated at a speed of spinning of 7 m/min After washing the resulting devicenote fiber pull 2.4 times in boiling water, followed su is coy at 120° C and then subjected to stretching 1.75 times with thermal stabilization at 350°to obtain the wholly aromatic polyamide fibers containing alumina mineral with a layered structure. Measurement of the longitudinal section of threads using TEM show that the average thickness of a layer of particles of aluminous minerals with a layered structure is 90 nm. In addition, the degree of orientation And the alumina particles of the mineral with a layered structure, was found from the results of x-ray diffraction, is 91%. The data of tensile strength, ultimate elongation and impact strength (TF) of the resulting fibers are shown in table 1.

Example 2

Wholly aromatic polyamide fibers having the composition specified in table 1, receive the same manner as in example 1, except that alumina mineral with a layered structure using smectitic aluminous mineral with a layered structure (brand: Lucentite STN, the firm Co-op Chemical), processed chloride trioctylamine. At this stage, the indicator opacity of the spinning liquid is equal 1,92. In addition, the average thickness of the alumina particles of the mineral with a layered structure is 86 nm, and the degree of orientation And equal to 91%. The data of tensile strength, ultimate elongation and shock factor visco is ti (TF) of the resulting fibers are shown in table 1.

Comparative example 1

Wholly aromatic polyamide fibers produced in the same manner as in example 1, except alumina mineral with a layered structure. The data of tensile strength, ultimate elongation and impact strength (TF) of the resulting fibers are shown in table 1.

Table 1
ExampleAdditive alumina mineral with a layered structure (wt.%)The degree of pulping fiber (decitex)The degree of orientation of the particles of alumina mineral with a layered structure (%)The tensile strength, CN/decitexUltimate elongation (%)Factor toughness
12,01,74914,4240,732
21,01,21915,5628,934
Comparative 10of 2.26-3,8929,524

Example 3

Polymethylpentene (0.16 wt. parts), having a characteristic viscosity of 1.9 DL/g, is dissolved in NRM (1.46 wt. parts) and stirred, polycationic, transparent spinning solution. Aluminous mineral (of 0.18 wt. parts) with a layered structure in the form smectite alumina mineral, processed chloride Polyoxypropylenediamine (brand: Lucentite SPN, the firm Co-op Chemical), add this spinning solution, followed by stirring, to prepare a polymer solution A. Separately from this procedure dissolve 17,44 wt. parts polymethacrylamide in the NRM (63,68 wt. parts), obtaining a clear solution of polymer Century

After mixing the polymer solution and stirring this mixture add 17,08 wt. parts of the NRM in order to obtain a spinning liquid, comprising 17,60 wt. parts polymethacrylamide, of 0.18 wt. parts Lucentite SPN (trade mark) and 82,22 wt. parts of the NRM.

This spinning liquid is heated to 85°and is extruded in the form of filamentary streams of the multi-channel mouthpiece with 1500 holes with a diameter of 0.07 mm, and then the flow is introduced into the coagulating bath at 85°to get devicenote fiber. The composition of the coagulating bath solution (40 wt.%) of calcium chloride, 5 wt.% NRM and 55 wt.% water, and the length of immersion (effective length coagulating bath) is 100 cm After passing devicenote fibers through the coagulating bath with a speed of 7 m/min fibers temporarily removed from the BA and in the air. Coagulated devicenote threads sequentially washed in three water washing baths. The total residence time in the baths is 50 sec. In addition, these three wash tubs use water with a temperature of 30°C. Then washed and devicenote fiber pull 2.4 times in hot water at 95°and after washing by continuous immersion for 48 seconds in hot water at 95°filament is dried with heat treatment by winding on the roller having a surface temperature of 130°C. In the following thread pull 1.75 times when getting in touch with a heating tile having a surface temperature of 330°to get polymethylenepolyphenylene fiber. The degree of pulping of these fibers is 2.26 and decitex, tensile strength equal 5,16 CN/decitex and the ultimate elongation is 43.2 per cent.

The maximum degree of stretching in the above-mentioned operation is 4.7 (degree of stretching to the maximum extent stretching k=0,51).

In addition, the number of dangling threads in the above processes of spinning and drawing 6 on the length of 15,000 m and the degree of dispersion of Y-alumina mineral with a layered structure equal to 3%. The results are given in table 2.

Example 4

Powder polymethacrylamide (0.32 wt. parts), a similar line is used in example 3, dissolve in NRM (6,46 wt. parts)cooled to -10°to prepare a clear solution of the polymer. To this solution add aluminous mineral with a layered structure (to 0.72 wt. parts) in the form smectite alumina mineral (brand: Lucentite SPN, the firm Co-op Chemical) and then stirred for receiving the polymer solution A. Separately from this procedure dissolve 13,28 wt. parts polymethacrylamide in the NRM (48,49 wt. parts)cooled to minus 10°to prepare a clear solution of polymer Century

After mixing the polymer solution and stirring this mixture add 30,73 wt. parts of the NRM in order to obtain a spinning liquid, comprising 17,60 wt. parts polymethacrylamide, 6,80 wt. parts Lucentite SPN (trade mark), and 76.6 wt. parts of the NRM.

This spinning liquid form and pull on the same method and under the same conditions as in example 3 to obtain polymethylenepolyphenylene fibers having a degree of pulping 2,18 decitex, the tensile strength 6,03 CN/decitex and ultimate elongation of 45.3%.

The number of dangling threads in the above processes of spinning and drawing is 10 in a length of 15,000 m, and the degree of dispersion of Y-alumina mineral with a layered structure is 25%. The results are given in table 2.

Table 2
Example 3Example 4
Aluminous mineral with a layered structure, wt.%*1,04,0
The viscosity of the solution:
Shear viscosity at 0.1 sec-1(PZ)27303420
Shear viscosity at 10 s-1(PZ)9095
The viscosity of the solution:
Shear viscosity at 0.1 sec-1(PZ)420410
The degree of pulping (decitex)of 2.262,18
The tensile strength (CN/decitex)5,175,32
Ultimate elongation (%)43,245,3
Factor impact strength (TF)a 38.540,6
Breakage of threads (the number of breakages on 15,000 m)610
The degree of dispersion Y (%)325
*Based on the weight of the wholly aromatic polyamide.

Example 5

Spinning and stretching spend on it the same method and under the same conditions, as in example 3. However, although it uses the same spinning solution as in example 3, the degree of stretching in hot water is 2.8 times and the degree of stretching on a hot tile at 330°is 1.50 times. Get polymeta-phenyleneterephthalamide fibers, which have a degree of pulping threads 2.22 decitex, the tensile strength 5,49 CN/decitex and ultimate elongation of 40.7%.

The maximum degree of stretching in the process of drawing in hot water equal to 4.7 (degree of stretching to the maximum extent stretching = 0,60), and the solvent content in the fiber before stretching is 5.0 wt. parts per 100 wt. parts of the wholly aromatic polyamide.

In addition, the number of dangling threads in these fibers is equal to 8 for the length of 15,000 m the Results are given in table 3.

Example 6

Spinning and stretching is conducted according to the same method and under the same conditions as in example 3. However, although it uses the same spinning solution as in example 3, the washing time to pull in hot water is 34 seconds. The resulting fibers have a degree of pulping threads 2.21 decitex, the tensile strength 6,12 CN/decitex and the ultimate elongation was 48.3%.

The maximum degree of stretching in the process of drawing in hot water equal to 4.9 (degree of stretching to maximum the Noah degree of stretching = 0,49), and the content of the solvent in the fiber before stretching is of 14.0 wt. parts per 100 wt. parts of the wholly aromatic polyamide.

In addition, the number of dangling threads in these fibers is 2 to the length of 15,000 m the Results are given in table 3.

Table 3
Example 3Example 5Example 6
Aluminous mineral with a layered structure, wt.%*1,01,01,0
The content of the NRM in devicenote fibers, wt. h**5,05,014,0
The maximum degree of stretchingthe 4.7the 4.7a 4.9
The degree of stretching2,42,82,4
The ratio of the degree of stretching/Max. degree of stretching0,510,600,49
The degree of pulping thread (decitex)of 2.262,22of 2.21
The tensile strength (CN/decitex)5,165,496,12
Elongation (%)43,240,748,3
Obryan the threads here (the number of breakages on 15,000 m) 682
*Based on the weight of the wholly aromatic polyamide.

**Content, per 100 wt. parts of the wholly aromatic polyamide.

Industrial applicability

Since the wholly aromatic polyamide fibers of the present invention to improve the mechanical strength, the degree of elongation factor toughness compared with the fibers of the prior art, which do not contain aluminous mineral with a layered structure, they can be used in a variety of applications that will take advantage of these properties. In addition, according to the method of obtaining of the present invention, it is possible to reduce the number of yarn breaks during spinning and drawing, and fiber standard quality can be produced in the industry.

1. Elongated wholly aromatic polyamide fiber comprising a resin composition, which contains a matrix consisting of a wholly aromatic polyamide resin and particles of alumina mineral with a layered structure, dispersed and distributed in the matrix in an amount of from 0.05 to 20 wt. o'clock, per 100 wt. h matrix, which has many areas in which the alumina particles of the mineral with a layered structure spread is relatively high distribution density preferably statistically distributed in the fully aromatic polyamide matrix, and particles of alumina mineral with a layered structure are particles treated intercalating agent containing organic onevia ions.

2. Elongated, wholly aromatic polyamide fiber according to claim 1, in which, provided that the wholly aromatic polyamide fibers have a cross-section along the axis of the fibers, the resulting profiles of the cross section is observed with an electron microscope with magnification of 100,000, and each profile is the total area S1 of the many areas in which the changing profile of the fiber, due to the influence of alumina particles of the mineral with a layered structure, distributed in the measured field observations of S2 is equal to 25 μm2the degree of dispersion of Y-alumina particles of the mineral with a layered structure in each fiber, defined by equation (1):

Y(%)=(S1/S2)·100, (1)

is in the range from 0.1 to 40.

3. Wholly aromatic polyamide fiber according to any one of claims 1 and 2, in which the aluminous mineral with a layered structure includes at least one selected from hectorite, saponite, stevensite, beidellite, swelling montmorillonite and mica.

4. Elongated wholly aromatic floor the amide fiber according to any one of claims 1 and 2, in which layer of the alumina particles of the mineral with a layered structure has an average thickness of from 10 to 500 nm.

5. Elongated wholly aromatic polyamide fiber according to any one of claims 1 and 2, in which the alumina particles of the mineral with a layered structure, have a degree of orientation And 50% or more, And is determined according to the equation (2):

A(%)=[(180-w)/180]·100 (2)

in equation (2) w denotes the width of the intensity distribution found by x-ray analysis of the alumina particles of the mineral with a layered structure along the Debye ring of the reflection peak in the plane (001) of the alumina particles of the mineral with a layered structure.

6. Elongated wholly aromatic polyamide fiber according to any one of claims 1 and 2, in which the ratio (T/M) tensile strength (t) of the wholly aromatic polyamide fibers to the tensile strength (That) comparative wholly aromatic polyamide fibers, identical wholly aromatic polyamide fibers, with the exception of the alumina particles of the mineral with a layered structure that is missing, is preferably 1.1 or more.

7. Elongated wholly aromatic polyamide fiber according to any one of claims 1 and 2, in which the ratio (E/EO) ultimate elongation (E) wholly aromatic polyamide fibers to prodelin the mu elongation (SW) comparative wholly aromatic polyamide fibers, identical wholly aromatic polyamide fibers, with the exception of the alumina particles of the mineral with a layered structure that is missing, is preferably 1.1 or more.

8. Elongated wholly aromatic polyamide fiber according to any one of claims 1 and 2, in which the factor of impact strength (TF) wholly aromatic polyamide fibers is determined according to the equation (C):

TF=T′·E′1/2(3)

in this equation (3), T′ represents the numerical value of the tensile strength, in units of g/1.1 decitex", wholly aromatic polyamide fibers and E′ represents the numerical value of the maximum elongation, in units of %, wholly aromatic polyamide fibers is preferably 30 or more.

9. Elongated wholly aromatic polyamide fiber according to any one of claims 1 and 2, in which the ratio (TF/TFo) factor impact strength (TF) wholly aromatic polyamide fibers to the factor of adhesion (TFo) comparative wholly aromatic polyamide fibers, identical wholly aromatic polyamide fibers, with the exception of the alumina particles of the mineral with a layered structure that is missing, is preferably 1.1 or more.

10. Elongated wholly aromatic polyamide fiber according to any of the claim 1 and 2, in which organic onevia ions contained in the intercalating agent, are located between the layers of the alumina particles of the mineral with a layered structure.

11. Elongated wholly aromatic polyamide fiber according to any one of claims 1 and 2, in which a fully aromatic polyamide resin selected from fully meta-aromatic polyamide resin.

12. The method of obtaining elongated wholly aromatic polyamide fibers, as claimed in claims 1 to 11, which includes the selection of the spinning liquid, solvent, and wholly aromatic polyamide resin, and particles of alumina mineral with a layered structure in an amount of from 0.05 to 20 wt. hours at 100 wt. including a fully aromatic polyamide resin through a multichannel mouthpiece with the formation of filamentary streams of the spinning liquid;

introduction filamentary streams of the spinning liquid in an aqueous coagulating bath to coagulate filamentary streams of the spinning liquid;

pulling obtained devicenote threads in a humidified atmosphere; and drying heat treatment of the obtained extruded threads.

13. Way to obtain the wholly aromatic polyamide fibers in item 12, in which the spinning liquid is prepared by mixing solution a, which includes part of the solvent portion completely aromatizes the Oh polyamide resin and particles of alumina mineral with a layered structure in an amount of from 30 to 300 wt. hours at 100 wt. including a fully aromatic polyamide resin with a solution containing the remainder of the solvent, the rest of the wholly aromatic polyamide resin, and satisfies the requirements (1) and (2):

(1) the viscosity of the solution (A) at the shear rate of 0.1 s-1in 15-80 times greater than the viscosity of the solution And at a shear rate of 10-1and

(2) the viscosity of the solution (A) at the shear rate of 0.1 s-1in 40-20 times greater than the viscosity of the solution (C) at the shear rate of 0.1 s-1.

14. Way to obtain the wholly aromatic polyamide fiber according to item 12 or 13, in which the concentration of the wholly aromatic polyamide resin in the spinning solution is from 0.1 to 30 wt.%.

15. Way to obtain the wholly aromatic polyamide fiber according to item 12 or 13, in which the degree of stretching devicenote threads in a humidified atmosphere preferably is in the range from 30 to 60% of the maximum stretching devicenote threads.

16. Way to obtain the wholly aromatic polyamide fiber according to item 12 or 13, in which the solvent is selected from polar amide solvents.

17. Way to obtain the wholly aromatic polyamide fiber according to item 12 or 13, in which a fully aromatic polyamide resin selected from fully meta-aromatic polyamide resin.



 

Same patents:

FIELD: processes for producing of fibers, fibrids and articles from said fibers and fibrids, in particular, non-woven products, paper, and may be used for manufacture of electric insulation.

SUBSTANCE: articles are reinforced with fibers and/or fibrids produced from mixture of thermally stable polymers - aromatic polyamides, aromatic polyamide-imide resins or polyimide resins and thermoplastic polymers - polysulfides, polysulfones. Method involves reinforcing articles by thermal pressing at temperature exceeding glass transition temperature of thermoplastic polymer.

EFFECT: improved mechanical properties and air permeability and high processability.

23 cl, 2 dwg, 7 tbl, 20 ex

FIELD: production of thermally- and fire-resistant textile materials, in particular, materials produced from mixture of thermally stable synthetic fiber and oxidized polyacrylonitrile fiber, which may be used for manufacture of protective clothing for rescuers, servicemen, firemen, oil industry workers, and gas industry workers, filtering fabrics for cleaning of hot gases from toxic dust in metallurgical, cement and other branches of industry, decorative materials, thermally-resistant isolation, and toxic asbestos substitutes.

SUBSTANCE: method involves mixing non-oxidized polyacrylonitrile fiber with thermally stable synthetic fiber in the ratio of from 30/70 to 80/20, respectively; subjecting resulting mixture in the form of yarn, tape, fabric to thermally oxidizing processing at temperature of 240-310 C during 10-180 min.

EFFECT: elimination of problems connected with textile processing of frangible oxidized polyacrylonitrile fibers owing to employment of elastic polyacrylonitrile fibers rather than such oxidized fibers.

2 cl, 7 tbl, 6 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to technology of manufacturing thermoplastic monofilaments and can be used in fabrication of bristle used under high humidity conditions. Monofilament is composed of polymer blend constituted by at least one polyamide and at least one thermoplastic polyester. Ratio of constituents in the blend is selected according to technical and functional properties determined, on one hand, by destination of bristle and, on the other hand, by environmental conditions in the bristle application location. Polyamide fraction ranges from 10 to 30% and that of polyester from 70 to 90%. Bristle completely meets functional and technical requirements as well as environmental conditions.

EFFECT: reduced manufacturing cost.

16 cl

FIELD: production of electric conducting pulp for manufacture of paper, reinforcing polymer materials and packaging films.

SUBSTANCE: pulp contains fibrous particles including 65-95 mass-% of para-amide and 5-35 mass-% of sulfonated polyaniline containing sulfur in the amount of 8.5-15 mass-% which is dispersed over entire para-amide partially covering the particles externally. Specific area of surface of fibrous particles exceeds 7.5 m2/g. Pulp may be mixed with 95 mass-% of pulp of other material including poly-n-phenylene terephthlamide. Paper made from this pulp reduces rate of electric charge lesser than 150 ml.

EFFECT: enhanced efficiency.

6 cl, 4 tbl, 1 ex

FIELD: processes for manufacture of synthetic threads, fibers and filaments from polyamide.

SUBSTANCE: method involves mixing melts of two compounds, namely, linear polyamide and polyamide including macromolecular star-like or H-like chains comprising one or more nuclei, and at least three polyamide side chains or segments, which are bound with nucleus and produced from amino acid and/or lactam monomers, or multifunctional compounds with three similar acidic or amine functional groups; forming resultant melt mixture into threads, fibers or filaments and drawing if necessary.

EFFECT: increased effectiveness of process for producing of threads, fibers and filaments and improved elongation properties.

22 cl, 4 tbl, 6 ex

The invention relates to a technology for obtaining molded products - fibers or films based on aromatic copolyamid with heterocycles in the chain and can be used in the chemical industry for the reinforcement of plastics, rubber products, as tire cord, for obtaining fabrics and other materials for technical purposes and for the manufacture of films and pulp

The invention relates to the production of high-quality fiber pulp

The invention relates to the field of synthetic fibers, particularly synthetic fibers, spun from anisotropic solutions in sulfuric acid of rigid-rod aromatic polyamides, mixed with aliphatic polyamides

The invention relates to the field of production of high strength fibers based on aromatic depolimerization (ABI) used, usually in organoplastic aerospace, defense, etc

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to novel chemical compounds that can be used for protection of textile materials from biodamages, and to a method for their synthesis. Invention proposes antibacterial oligoethoxy-(4-organocarboxyphenyloxy)-tetrasiloxanes. These compounds are able to protect textile materials from biodamages and not to be washed off from surface of their fibers in multiple launderings and chemical cleansings. Invention proposes a method for synthesis of claimed oligoethoxy-(4-organocarboxyphenyloxy)-tetrasiloxanes by the condensation reaction of 1 g-mole of decaethoxytetrasiloxane with a desired amount of g-moles of the corresponding 4-organocarboxyphenol representing 4-hydroxybenzoic acid ester in the presence of catalytic amount of tetrachlorosilane at heating and stirring and with simultaneous distillation of formed ethyl alcohol.

EFFECT: improved method of synthesis.

3 cl, 1 dwg, 3 tbl, 7 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to manufacture of polymer materials and, in particular, micro- and nanofibers showing elevated strength and durability, which can be employed in a variety of technical fields, including their use in various filters. Composition of fine fiber having diameters between 0,001 and 2 μm contains addition or condensation polymer and aromatic-nature resinous additive with molecular weight 500 to 3000, which additive may be disposed on the surface of fiber. Preparation method comprises exposure of polymer solution to electric field to form accelerated solution strands. Subsequent vaporization of solvent provides formation of fine fiber. Fibers are collected on a substrate and subjected to heat treatment at temperature not superior to melting point of polymer. From thus obtained fiber, fine-fiber material is manufactured.

EFFECT: manufacture of high-durability and high-strength fibers.

31 cl, 21 dwg, 5 tbl, 18 ex

FIELD: polymer materials and composites.

SUBSTANCE: composite granulate, consisting of cylindrical granules 1-2 mm in diameter and 3-4 mm in height possessing residual magnetization 0.4-0.5 mTl, contains: (i) high-pressure polyethylene or polypropylene; (ii) filler dispersed in granulate functioning as modifying additive and being represented by powdered magnetically hard strontium ferrite in concentration 5-25%; and dioctyl phthalate as plasticizing agent with residual magnetization 0.4-0.52 mTl (2%).

EFFECT: improved adsorption properties of filter materials based on fibers made from composite granulate of invention.

2 tbl, 2 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to technology of fabricating polyolefin fibers used for woven and nonwoven materials, in particular to imparting wettability to the latter, and can be used in manufacture of hygienic appliances, filters, accumulator battery separators, and the like. Elementary threads and two-component fibers are made from molten mixture of polyolefin and at least one compound of formula: R1-hydrophilic oligomer, wherein R1 denotes straight-chain or branched C22-C40-alkyl and hydrophilic oligomer is homo- or cooligomer comprising 2-10 monomer units derived from monomers selected from group including ethylene oxide, propylene oxide, ethylene glycol, propylene glycol, epichlorohydrin, acrylic acid, methacrylic acid, ethyleneimine, caprolactone, vinyl alcohol, and vinyl acetate.

EFFECT: achieved excellent prolonged wettability of fibers and textiles.

15 cl, 4 ex

FIELD: methods of production of electret items, electret filters and respirators.

SUBSTANCE: the invention presents a method of production of electret items, electret filters and respirators with heightened resistivity to the oil mist. The invention falls into production processes of electret items, electret packed beds and respirators, and may be used for removal of corpuscles from gases, especially for removal of aerosols from air. The method provides for: formation of a melted material consisting of a mixture of a polymer composed of a mixture of a polymer representing a non-current-conducting thermoplastic resin with a specific resistivity exceeding 1014 Ohms·cm with a fluorine compound as an additive compound; shaping it to the required form and quenching it up to the temperature lower than the melting point of the polymer. The material is calcined and treated with an electric charge to give it electret properties. The invention improves the capability of filtering oily aerosols.

EFFECT: the invention improves the capability of filtering oily aerosols.

19 cl, 16 tbl, 19 dwg, 23 ex

The invention relates to the technology for screening materials, including film threads; these threads are made of a thermoplastic polymer, filled with Ferri - or ferromagnetic, and have a degree magnetic texture is not less than 20%, a thickness greater than at least 2 times the size of the filler particles, and the porosity is less than 30%

The invention relates to a method of manufacturing a fiber containing powdered functional minerals

The invention relates to the technology of production of nonwoven materials containing inorganic particles of polyolefin fibers or threads

FIELD: methods of production of electret items, electret filters and respirators.

SUBSTANCE: the invention presents a method of production of electret items, electret filters and respirators with heightened resistivity to the oil mist. The invention falls into production processes of electret items, electret packed beds and respirators, and may be used for removal of corpuscles from gases, especially for removal of aerosols from air. The method provides for: formation of a melted material consisting of a mixture of a polymer composed of a mixture of a polymer representing a non-current-conducting thermoplastic resin with a specific resistivity exceeding 1014 Ohms·cm with a fluorine compound as an additive compound; shaping it to the required form and quenching it up to the temperature lower than the melting point of the polymer. The material is calcined and treated with an electric charge to give it electret properties. The invention improves the capability of filtering oily aerosols.

EFFECT: the invention improves the capability of filtering oily aerosols.

19 cl, 16 tbl, 19 dwg, 23 ex

Up!