Easy dyeable wholly aromatic meta-type fibre. RU patent 2508421.
 Thread of aromatic polyamide and method of its manufacturing / 2505629Thread consists entirely of aromatic polyamide. The thread is characterised by a narrow range of polydispersity index (PDI) and increased apparent size of the crystal (ASC). |
 Thread of aromatic polyamide and method of its manufacturing / 2505628Thread consists entirely of aromatic polyamide. The thread has a high crystallinity (C), large apparent crystal size (ACS) and a reduced amount of defects of the crystal itself. |
 Thread of aromatic polyamide and method of its manufacturing / 2505627Thread consists entirely of aromatic polyamide. The thread has a narrow range of polydispersity index (PDI) and lower paracrystalline parameter g11, which leads to decrease of defects of the crystal itself. |
 Method of producing ultra-high molecular weight polyamide fibres / 2493299Described is a method of producing ultra-high molecular weight polyamide fibres, particularly nylon, where the fibres have very high relative viscosity. The method involves a melt-phase polymerisation procedure which is optionally carried out in combination with a solid-phase polymerisation procedure. The procedures are carried out while observing selected controlled conditions, which enable to obtain polyamide fibres with denier from about 2 to about 100 (from about 2.2 dtex to about 111 dtex), having relative viscosity greater than about 200. |
 Method of producing high-strength high-modulus aramid threads (versions) / 2478143High-strength threads are obtained by a wet or dry-and-wet method of moulding an isotropic solution of an aromatic heterocyclic copolyamide in an organic solvent with leophilic salt additives, followed by washing, drying and heat treatment of the freshly moulded threads in a package under a vacuum and additional hot-stretching. Heat treatment is carried out in two steps: first under a vacuum of - 0.95 to -1.0 atm for 10-30 minutes, and the vacuum is reduced to - 0.75 to -0.9 atm and maintained until the end of the cycle; before hot-stretching, the threads are moistened to moisture content of 1.5-8.5%, said hot-stretching being carried out at temperature of 410-450°C. Heat treatment can also be carried out in a tubular heat chamber with gradient temperature distribution in the direction of movement of the thread from 30 to 500°C with a load of 0.05-0.5 cN/tex on the thread and oxygen content in the heat treatment zone of less than 1.5%. Air medium is fed by a stream which accompanies the movement of the thread at a speed which is at least twice as high as the speed of the thread. |
 Method of moulding and washing aramid fibre and regenerating sulphuric acid / 2473722Method employs a moulding apparatus and an apparatus for regenerating sulphuric acid. The method involves the following steps: a) moulding a (spinning) thread from aramid polymer from a spinning solution which contains sulphuric acid, and coagulating the thread in a coagulation bath having an inlet for water or diluted sulphuric acid and an outlet for water rich in sulphuric acid; b) washing the thread with water to obtain a washed thread and washing water containing 0.5-20.0 wt % sulphuric acid; c) reusing the water rich in sulphuric acid and, optionally, the washing water, which is fed into the apparatus for regenerating sulphuric acid; d) increasing content of sulphuric acid in the reused water which is rich in sulphuric acid and, optionally, in the washing water by evaporation to obtain sulphuric acid with concentration of 98% and water; e) mixing sulphuric acid with concentration of 98% with oleum to obtain sulphuric acid with concentration of 98-105%; f) reusing the sulphuric acid with concentration of 98-105% in the moulding apparatus as a spinning solution containing sulphuric acid. |
 Method and apparatus for manufacturing spinning solution for production of polymeric fiber / 2473721According to the method the polymer is mixed with a solvent, stirred, melted, homogenised and degassed, and then unloaded. Liquid sulfuric acid is used as a solvent, and at least stirring, homogenising and degassing is carried out in a single or twin screw kneading reactor, preferably of continuous operation. |
| Refined fibre / 2472879 Refined fibre has an average length of 2 mm to 4 mm, having the value of capacity for filler retention of at least 18% and the strength in the raw state of at least 1.8 mJ/mm2. The fibre is obtained by the method according to which the thread never exposed to drying or sliver having a length of at least 1 m are refined by performing at least the stage of feeding the thread or sliver and the liquid in the refiner which comprises refiner fillers comprising a housing that surrounds the central opening, and at least one inlet for the thread or sliver. The fibrillated fibre obtained in this way can be used for manufacture of friction materials, gaskets, brake pads or brake linings. |
 Particles consisting of para-aramid composite material and additional material / 2458191Invention relates to a method of producing particles from a polymer-additive composite material by: i) drawing a solution through a draw plate to obtain a fibre mass, fibril or a fibre product, wherein the solvent of the solution is selected from N-methyl-2-pyrrolidone, N,N'-dimethyl formamide, N,N'-dimethyl acetamide, tetramethyl urea, and 4-75 wt % composition consisting of 2-80 wt % para-aramid polymer and 20-98 wt % solid additional material to a total of 100 wt %, and where the aramid polymer is dissolved in the solvent, or ii) coagulation of the solution using a rotor-stator apparatus wherein the polymer solution is deposited through the stator onto the rotor such that the precipitated particle of the polymer-additive composite material is subject to shearing forces while in plastic deformation state. The aramid is preferably poly(para-phenylene terephthalamide) - PPTA. The additional material is selected from kaolin, talc, diatomite, zeolite, graphite, mineral fibre, calcium carbonate, barium sulphate, mica, dyes, pigments such as TiO2 and metal particles. The solution can be used to obtain particles such as fibre products, fibre mass and fibrils used in paper production. |
 Particle containing matrix and radical initiator / 2458081Invention pertains to a particle comprising a composition containing a matrix and a peroxide or azo radical initiator, as well as rubber-coated products, tyres, tyre treads and belts containing particle-elastomer systems. The particle is selected from aramid, polyester, polyamide, cellulose fibre and glass fibre. The matrix is selected from an extruded polymer, wax or mixture thereof. |
 Composition for manufacturing polycaproamide thread / 2270280Invention relates to polymer composition based on granulated polycaproamide, which contains polycaproamide, oligomers, water, titanium dioxide, and, additionally, complex modifying additive constituted by 1,1,5-trihydroperfluoripentanol and N,N-bis(2,2,6,6-yrytamethyl-4-piperidiniyl) 1,3-benzenedicarbamide. |
 Method of manufacturing thread from aromatic heterocyclic polyamide / 2277139Invention relates to heat-resistant thread manufacture technology and can be utilized in manufacture of special materials for flak jackets, high-pressure containers, and in airplane construction. Thread is made from aromatic heterocyclic polyamide prepared via low-temperature polycondensation of a mixture composed of 25-70 mol % diamine of formula: , where X represents -NH, -S, -O, -N(CH3), and N(C2H5) and Z represents N or C, and 30-75 mol % of p-phenylenediamine with aromatic dicarboxylic acid chloride used in equimolar proportions in organic solvent and in presence of lithium or calcium chloride. Thus prepared solution is molded into water-dimethylacetamide precipitation bath. Thread is rinsed, dried, thermally treated for 10-30 min at 340-360°C, and then is drawn at 230-270°C at heating time 1-3 sec. |
| Thermoplastic monofilament for bristle / 2287030 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. |
 Fine fiber compositions, methods for preparation thereof, and a method of manufacturing fine-fiber material / 2300543Invention 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. |
| Articles possessing antibacterial and antifungal activity / 2321690 Invention relates to using zinc sulfide in articles possessing N antibacterial and antifungal activity. In particular, it can be used in preparing any product able to interact with microorganisms and/or fungi, such as dress, carpets, curtains, bed affiliations and textile materials used for medicinal aims. |
| Method of production of thermally-light-stabilised polycaproamide thread / 2330131 Invention is related to technology of production of polycaproamide fibers and may be used in production of cord and technical threads for their stabilisation. Method of production of thermally-light-stabilised polycaproamide thread includes melting of polycaproamide granulated material and thread spinning. Prior to spinning via polymer concentrate multi-component thermal light stabiliser is introduced, which is taken in the following ratio: granulated material "ПА"-6 - 90-92%, multi-component thermal light-stabiliser - 8-10%. The latter consists of the following: - univalent copper salt 0.6-0.7%, potassium halogenide 2.4-5.6%), auxiliary additive: organic component from triazols class, plasticisers on the basis of stearates, phenol anti-oxidant 3.7-5%, optical bleach from class of benzoxazole 0-0.05%. |
| Nonfibrous polymer solution para-aramide with high relative viscosity / 2342474 Invention concerns receiving technology of para-aramide fibers, films, paper. Particularly it concerns receiving of polymer solutions for its manufacturing. Nonfibrous polymer solutions contains from 1 till 8 % wt of para-aramide at least, 50 % mol. aromatic remains of which are unreplaced; polar amide solvent, chosen from N- methyl -2- pyrrolidone, N,N'- dimethyl formamide, N,N'- dimethyl acetamide, tetra methyl urea and its mixtures; from 0.5% wt of chloride of alkaline or alkali-earth metal and till 7.5 % wt chloride of alkaline or alkali-earth metal, and till 5% wt of water. At least 50 % wt of formed hydrochloric acid is neutralised with receiving of solution, allowing dynamic viscosity, which is at least three times less than dynamic viscosity of polymer solution without neutralisation. |
 Lightproof and heat-resistant composition / 2351621Invention refers to lightproof and/or heat-resistant composition, method of production, to threads, fibres and/or filaments, as well as to textile product. The composition contains the following components: polyamide matrix, at least, one lightproof and/or heat-resistance stabilising agent containing, at least, one hindered functional amino group, titanium dioxide and manganese salt. Method of producing the composition consists that, at least, one lightproof and/or heat-resistance agent, titanium dioxide and manganese salt are introduced to polyamide base monomers before or with polymerisation. Threads, fibres and/or filaments are made of cast composition. Textile product contains, at least, threads, fibres and/or filaments made of above-stated composition. |
 Aramid fibrils / 2363780Invention concerns obtainment of para-aramid fibrils, as well as paper based on the claimed fibrils. In humid phase poly(para-phenylethylene terephthalamide) fibrils show drainage rate by Canada Standard under 100 ml, specific surface area after drying under 7 m2/g and weight-average particle length under 1.2 mm, defined respective of weight for particles over >250 mcm long (WL0.25). Method of fibril obtainment involves polymerisation of aromatic diamine and aromatic dicarboxylic acid haloid up to para-aramide polymer stage in the mix of N-methylpyrrolidone or dimethylacetamide and calcium or lithium chloride to obtain spinning solution. Concentration of polymer dissolved in the mix is 2-6 wt %. Obtained spinning solution is transformed into fibrils by spinning nozzle in gas flow, and fibril coagulation is performed by coagulation jet. Paper is made of components where at least 2 wt % corresponds to the claimed para-aramide fibrils. |
 Para-aramide fibrid film / 2366670Film is featured with para-orentation of at least 95% polymer bonds. The method for film making includes polymerisation of para-oriented aromatic diamine and para-oriented aromatic dicarbon acid haloid in the mixture of solvents consisting of N-methylpyrrolidone or dimethylacetamyde and calcium chloride or lithium with obtaining of aramide polymer containing only para-oriented bounds. Then the spinning solution is obtained by solution of the polymer in solvent mixture up to concentration 2 - 6 wt %. The spinning solution is transformed to para-aramide fibrid film with usual known methods used for meta-aramide fibrids production. |
FIELD: textiles, paper.
SUBSTANCE: proposed easy dyeable wholly aromatic polyamide meta-type fibre is obtained by using an aqueous solution containing the amide solvent in a concentration of from 45 to 60 wt % at the coagulation stage. The coefficient of plastifying stretching of the fibre at the stage of plastifying stretching is in the range from 3.5 to 4.5. The temperature of dry heat treatment of the washed fibres at the stage of dry heat treatment is in the range from 260 to 330°C and the residual solvent content in the said fibre is 0.05-0.1 wt %. The degree of dye extraction is 90-92.4%, the index of dyed fibre strength retention after immersion for 150 hours in a 20 wt % aqueous solution of sulfuric acid at 50°C is 65-73%.
EFFECT: fibre is easy dyeable completely.
1 tbl, 5 ex
The technical field to which the invention relates
The present invention relates to fully aromatic proof polyamide fiber meta-type. More particularly, the invention relates to easily fully aromatic fiber meta-type, possessing excellent ecological security, excellent acid resistance.
The level of technology
Fully aromatic polyamide fiber meta-type, such as fiber, has a molecular structure that mainly includes aromatic rings, and therefore exhibits excellent heat resistance and dimensional stability. With regard to the superiority of these characteristics, fully aromatic polyamide fiber meta-type preferably used not only in industry but also in the areas where the importance of temperature resistance, flame retardant properties and fire resistance, or in other applications. In recent years there has been a rapid expansion of applications in the fields of bedding, clothing, articles of interior, and the like. Then, particularly in the area of service, in addition to the fire-resistance and flame retardant properties, in addition, are also required colorability and acid as important characteristics.
However, fully aromatic polyamide fiber meta-type is unfavourable, as it is difficult painted by conventional methods, due to the rigidity of the molecular chain of the polymer.
In the circumstances, as a method to improve , we propose a way in which salt add the spinning solution, and thus, get the aromatic polyamide fiber meta-type, which are relatively easy to paint cationic dye (JP-A-08-081827). This way you can get aromatic polyamide fiber meta-type, having a suitable colorability in respect of cationic dyes.
However, fiber, containing additive salt has a high cost. In addition, in order to prevent falling salt of fiber during the production of yarn, during subsequent handling, etc. cannot detect hard conditions coagulation in fibre production. As a result, in the fiber remains a large amount of solvent, which leads to deterioration of ecological safety.
As another method to improve the proposed the following way. Get amorphous fiber, having pores, and fiber, in water, heated by steam to dye pores in the fiber. The result is a fiber impregnated with dye on the whole structure of fiber. Subsequently fiber heated by steam sufficient time to a temperature higher than the glass transition temperature to destroy the pores. As a result, the dye is irreversibly in the fiber to crystallize fiber (JP-A-62-184127).
Using this method, you can get fiber, having appropriate colorability, and having a small residual solvent content. However, when such a thermal treatment to the destruction of the pores with the use of steam heated to a temperature of 110 C up to 140 C, crystallization fiber is inadequate, making it difficult to obtain suitable acid.
Therefore, so far not received fully aromatic polyamide fiber meta-type, which has a light , which remains a small amount of solvent, and fiber is acid resistance.
Brief disclosure of the invention
Problem to be solved in the present invention
The present invention is performed taking into account the level of technology. The aim of the invention is development of easily painted completely aromatic polyamide fiber meta-type, having excellent and acid resistance, which has a very small residual solvent content.
The means for achieving the objectives of the invention
The authors of the present invention completed the intensive study of this problem. The result revealed the following: the problem can be solved by the corresponding regulation of components or conditions in a precipitation tub to get besieged form, not having a shell on the core, the implementation of the plasticizer, pulling at a certain ratio, and the completion stage of leaching, with the subsequent implementation of dry heat treatment at a certain temperature. This led to the finalization of the present invention.
In other words, the invention is easily fully aromatic polyamide fiber meta-type, which has a residual solvent content of 0.05 wt.% or more and OD wt.% or less in the form of fiber, and having indicator maintain strength 65% or more and 73% or less in the form of painted fibre, after dipping to 150 hours at 50 C in aqueous solution of sulfuric acid (20%of mass), and having the degree of extraction of dye 90% or more and 92.4 per cent or less in the form of a colored fibers.
Advantages of the invention
In the present invention easily fully aromatic polyamide fiber meta-type is appropriate for in relation to the dye, and has excellent acid resistance, as well as ecological safety. For this reason, fiber has great industrial importance in areas that require such characteristics. Preferably fiber can be used in areas where they learn the value of aesthetic properties and visual characteristics, such as bedding, clothing and articles of interior.
Realization of the invention
Easily fully aromatic polyamide fiber meta-type
In the present invention easily fully aromatic polyamide fiber meta-type has the following specific physical characteristics. Below is the description of the physical characteristics, configuration, production methods, and so forth easily painted completely aromatic polyamide fiber meta-type of the present invention.
Physical characteristics easily painted completely aromatic polyamide fiber meta-type
Residual solvent content
Usually completely aromatic polyamide fiber meta-type is produced from the source spinning solution containing polymer is dissolved in solvent. Therefore, it is natural that the solvent remains in the fiber. However, according to the invention for a fully aromatic polyamide fiber meta-type, the quantity of solvent remaining in the fiber is 0.1 wt.% or less per mass of the fiber. The specified number, essentially, is 0.1 wt.% or less, and is more preferable to 0,08% of mass or less.
When the number of solvent remaining in the fiber is more than 0.1 wt.%) in calculating the masses fiber, during processing or use in the atmosphere with high temperatures reach more than 200 OC, residual solvent evaporates, which leads to deterioration of ecological safety. In addition, breaks down the molecular structure, which is undesirable, since it leads to a significant reduction in strength.
In the present invention is to install the residual solvent content in the fiber at the level of 0.1 wt.% or less, at the stage of production of fiber components or conditions in a precipitation tub regulated so as to obtain the besieged form, not having a shell on the core, and the plasticizing pulling held at a certain ratio.
In this context, the expression "residual solvent content in the fiber" in the invention means the amount obtained as follows.
Method measurement of the residual content of solvent
Gather about 8.0 g of fiber and dried at 105 OC for 120 minutes. Then the fibre is allowed to cool in a drying Cabinet for defining the weight of the fiber (M1). After the extraction is carried out fiber in boiling methanol within 1.5 hours by using the extractor ml Soxhlet extractor. So extraction amide solvent contained in the fiber. Take out the fiber, which undergone a complete extraction, and dried in a vacuum at 150 C for 60 minutes. Then the fibre is allowed to cool in a drying Cabinet for defining the weight of the fiber (M2). The number N(%) solvent (mass amide solvents), remaining in the fiber, calculated using the obtained values of M1 and M2 by the following equation:
N(%)=[(M1-M2)/M1]x 100.
Indicator maintain strength painted fibre
According to the invention for easy painted completely aromatic polyamide fiber meta-type indicator maintain strength painted fibre, after dipping to 150 hours at 50 C in aqueous solution of sulfuric acid (20%of mass) is 65% or more. Indicator maintain strength, essentially, is 65% or more, preferably 70% or more, and more preferably 75% or more.
Indicator maintain strength painted fibre serves as an indicator of acid. When the indicator maintain strength is less than 65%, the acid fiber for use as a working service is insufficient, which leads to undesirable reduce security.
According to the invention to install indicator maintain strength colored fiber at 65% or more in the stage production of fiber components or conditions in a precipitation tub regulated so as to obtain the besieged form, not having a shell on the core, and completes phase washing, and then is dry heat treatment at a certain temperature.
In this regard, measure maintain strength" in the invention means the amount that can be obtained as follows.
A method of determining the term durability (acid test)
In this regard, the term "tensile strength" according to the invention determines the amount obtained when measuring in the following conditions using the model of the device 5565, produced by the firm INSTRON Co., according to the Japan standard JIS L 1015.
Measurement conditions
Length capture: 20 mm
Initial load: 0,044 SN (1/20 g)/
Stretch speed: 20 mm/min
At the same time, the term "staining" according to the invention means staining using the following method dyeing, unless otherwise noted.
Method of staining
Prepare a coloring solution containing 6% cationic dye (brand name: Kayacryl Blue GSL-ED (54), produced at the company NIPPON KAYAKU Co., Ltd.), 0.3 ml/l acetic acid 20 g/l of sodium nitrate, 70 g/l of benzyl alcohol as transporting agent and 0.5 g/l subsidiary colouring agent (brand name: DISPER TL, produced at the company MEISE1 CHEMICAL WORKS, Ltd.) as dispersal agent. Subsequently spend 60-minute dye processing at 120°C, and the ratio of fiber to solution in the tub is equal to 1:40. After colouring processing using processing solution containing 2,0 g/l bisulfite, 2.0 g/l AM1RADINE D (brand name AMlRADINE D, produced at the company DAI-ICHI KOGYO SEIYAKU CO., Ltd.), and of 1.0 g/l sodium hydroxide, in the specified proportions, hold 20-minute replacement leaching at 80 C with a ratio in the bath, is equal to 1:20. After washing with water, drying is conducted, which leads to painted fiber.
Tensile strength and elongation at break fiber
Preferably tensile strength (fiber prior to dyeing) easily painted completely aromatic polyamide fiber meta-type according to the invention is 2.5 mV/ or more. Preferably it is 2.7 CN/ or more, and especially preferably 3,0 CN/ or more. When the tensile strength is less than 2.5 mV/, fiber destroyed during the subsequent stages of processing, such as spinning, and undesired deterioration of the road.
At the same time elongation (fiber prior to dyeing) easily painted completely aromatic polyamide fiber meta-type according to the invention is preferably 30% or more. Preferably it is 35% or more, and especially preferably 40% or more. When elongation is less than 30%, it is undesirable worsens patency during subsequent stages of processing, such as spinning.
In this context, the terms "tensile strength and elongation at break", used in the invention of the mean values obtained when measuring conditions "tensile strength" according to the standard JIS L 1015.
In the present invention "tensile strength" easily painted completely aromatic polyamide fiber meta-type can be controlled via operations with the appropriate coefficient of extraction stage plasticizing pulling the bath and the temperature of thermal processing on the stage of dry heat treatment in a production method, described later. To obtain a tensile strength at 2.5 mV/ or more of importance only that drawing ratio set in the range from 3.5 to 5.0 times, and in addition, temperature dry heat set in the range from 260 to 330 OC C.
According to the invention "elongation" easily painted completely aromatic polyamide fiber meta-type can adjust creating suitable conditions in precipitation tub on the stage of coagulation in production method, described later. To achieve lengthening in 30% or more, the great value has only what coagulation solution is a water solution with concentration of N-methyl-2- (N) from 45 to 60 wt.%, moreover, the temperature of the solution in the tub set in a range from 10 to 35 C.
The degree of extraction of dye colored fiber
With regard to easily painted completely aromatic polyamide fiber meta-type according to the invention, the degree of extraction of dye colored fiber by the above method of coloring dye preferably 90% or more. The degree of extraction. dye colored fiber preferably 90% or more, and more preferably 92% or more. When coloured fibre has a degree of extraction of dye less than 90%, then this is undesirable for reasons of aesthetic properties required in the area of service. Thus, painted fiber can not be painted in desired color tone.
In this regard, the term "degree of extraction of dye" in the invention means the amount that can be obtained as follows.
The degree of extraction of dye
The solution with the rest of the dye, which was colored fiber, add dichloromethane in a volume equal to the volume of solution with the remaining dye to extract the remaining dye. After that they measure the value of optical density extraction solution at a wavelength of 670 nm, 540 nm and 530 nm, respectively. According to the data of the calibration curve for the given values of wavelength, pre-built for solutions with known concentration of dye, respectively determine the concentration of the dye in the extraction solution. Average concentrations at three wavelengths is taken for the concentration of the dye (C) extraction solution. The value obtained using the concentration of the dye to colour (Co) from the following equation, called the degree of extraction of dye (U).
The degree of extraction of dye (U)=[(-)/From]x 100
According to the invention, the degree of extraction of dye colored fiber easily painted completely aromatic polyamide fiber meta-type can be adjusted by optimizing the degree of crystallization fiber as follows. At the stage of coagulation mode of production, described below, the conditions in precipitation tub regulated so as to obtain the besieged form, not having the shell to the kernel. Besides, at the stage of dry heat treatment, specified thermal treatment is carried out at a certain temperature. To install the recovery of dye colored fiber at the level of 90% or more, great importance is the only fulfillment of the following conditions: coagulation solution is a water solution with concentration NMP from 45 to 60 wt.%; temperature of the solution in the bath is 10 to 35 C; and temperature dry heat treatment is in the range from 260 to 330 C, which is equal to or above the glass transition temperature (Tg) of the fiber.
Configuration of completely aromatic polyamide meta-type
Fully aromatic polyamide meta-type, forming easily fully aromatic polyamide fiber meta-type according to the invention, includes a component of aromatic diamine meta-type and the component aromatic dicarboxylic acid meta-type. Other. components, such as para-isomers components can together with meta-isomers in the specified range, while they do not degrade the product inventions.
From the point of view of the dynamic characteristics and heat resistance, especially preferred components used in the present invention, are fully aromatic polyamides meta-type, containing as main component link meta-. Preferably fully aromatic polyamide meta-type including links meta- contains links meta- of 90 mol.% or more, preferably 95 mol.% or more, and especially preferably 100 mol.%, in calculating the total number of repeating units.
Source material for completely aromatic polyamide meta-type
Component aromatic diamine meta-type
As components of aromatic diamines meta-type, used as a source material for completely aromatic polyamide meta-type, can be mentioned meta-phenylenediamine, 3,4'- ether, 3,4'-diaminodifenilsulfon resulting, and the like, and their derivatives, have the aromatic rings these deputies, as halogen and alkyl groups have from 1 to 3 carbon atoms, for example 2.4-, 2,6-, 2,4- and 2,6-. Of them it is preferable to clean meta-phenylenediamine, or mixed diamine containing meta-phenylenediamine in the amount of 85 mol.% or more, preferably 90 mol.% or more, and especially preferably 95% or more.
Component aromatic dicarboxylic acid meta-type
As components of aromatic dicarboxylic acid meta-type, used as a source material for completely aromatic polyamide meta-type, can be mentioned, for example, halides aromatic dicarboxylic acids meta-type. As halides aromatic dicarboxylic acids meta-types can be mentioned isophthalic acid halides, such as isophthalic acid chloride and bromide isophthalic acid, and their derivatives, have the aromatic rings these deputies, as halogen and groups with 1 to 3 carbon atoms, e.g. chloride 3- acid. Of them it is preferable to actually isophthalic acid chloride or mixed halide carboxylic acid, containing chloride isophthalic acid in the amount of 85 mol.% or more, preferably 90 mol.% or more, and especially preferably 95% or more.
A way of reception of completely aromatic polyamide meta-type
According to the invention easily fully aromatic polyamide fiber meta-type is produced with the use of completely aromatic polyamide meta-type, obtained as aforesaid production, for example, with the consecutive stages of preparation spinning solution, spinning/coagulation, plasticizer, pulling out of the bath, washing, relaxation processing and stage thermal treatment described below.
Stages of preparation for spinning solution
At the stage of preparation spinning solution fully aromatic polyamide meta-type is dissolved in solvent to make the spinning solution (solution of completely aromatic polyamide polymer meta-type). Usually for the preparation of spinning solution is used solvent. As amide solvents to be used, can be mentioned the N-methyl-2-pyrrolidone (NMP), dimethyl formamide (DMF), dimethylacetamide (DMAc), and similar. Of them are preferably used NMP or DMAc from the point of view of the solubility and security manipulation.
With regard to the concentration of the solution, then the corresponding concentration can be selected properly in terms of the rate of coagulation stage spinning/coagulation, which is the next stage, and the solubility of polymer. For example, when the polymer is a , and the solvent is the NMP, usually preferred concentration range is from 10 to 30 wt.%.
Stage spinning/ coagulation
At the stage of spinning/ coagulation obtained above the spinning solution (the solution is fully aromatic polyamide polymer meta-type) is spun in solution and coagulates (precipitated).
Device spinning specifically not limited. Can be used traditionally known devices wet spun. In addition, the device is not required specifically limit the number of holes for spinning, order placement and shape of the holes in etc. provided that wet spinning can be done consistently. For example, can be used dies for spinning synthetic fiber, having from 500 to 30,000 spinning holes with a diameter of 0.05-0.2 mm
At the same time suitable temperature spinning solution (solution of completely aromatic polyamide polymer meta-type)when the spinning solution is subjected spun from the die is in the range from 10 up to 90 degrees C.
As of setting bath, which can be used for fiber according to the invention, aqueous solution, containing inorganic salts and having a concentration of NMP from 45 to 60 wt.%, when the temperature of the solution in the tub in the range from 10 to 35 degrees C. At a concentration of NMP less than 45% of mass a structure is formed with thick skin, which reduces the leaching efficiency on the stage of leaching. This leads to difficulties in obtaining fiber with the specified residual solvent content at the level of 0.1 wt.% or less. At the same time, when the concentration of NMP exceeds 60 wt.%, impossible to implement uniform coagulation inside the fiber. This leads to difficulties in obtaining fiber with the specified residual solvent content at the level of 0.1 wt.% or less, and in addition, leads to poor acid. In this connection, the appropriate time to dive fiber into the precipitation tub is in the range from 0.1 to 30 seconds.
In the present invention by regulation of the components or conditions in a precipitation tub, as described above, may decrease the thickness of the shell, formed on the surface of the fiber, and get a uniform structure inside the fiber. This can result in an additional improvement and acid, and besides, improvement elongation at fracture of the obtained fiber.
Stage plasticizing pulling in the bath
At the stage of plasticizing pulling in the tub until the fibre, obtained by coagulation in a precipitation tub, is condition, fiber exposed to pull treatment in a bath plasticizing stretching.
Solution in the tub plasticizing pulling specifically not limited. Can be used traditionally known solutions in the tub.
To obtain fiber according to the invention required to drawing ratio in the tub plasticizing pulling ranged from 3.5 to 5.0 times, and more preferably in the range between 3.7 and 4.5 times. In the present invention due to plasticizing pulling in the range defined ratios in the tub plasticizer, stretching, you can stimulate the removal of solvent from the coagulated yarn. As a result of residual solvent content in the fiber can be set at the level of 0.1 wt.% or less.
The bath temperature plasticizing pulling preferably in the range from 10 up to 90 degrees C. When the temperature is in the preferred range from 10 to 90 degrees Celsius, conditions stage are satisfactory.
Stage of leaching
On the stage of leaching fiber, stretched out with the bath plasticizer, stretching, effectively washed. Rinsing impact on the indicators of the quality of the fiber, and therefore preferably be held in several stages. Specifically, the temperature in tub on the stage of leaching and concentration of the amide solvent in solution affect the state of the extraction of the amide solvents fiber and state water intrusion from baths inside the fiber. For this reason, the purpose of these indicators in optimal condition, preferably stage of leaching is conducted in several stages and are regulated by temperature and concentration of the amide solvents.
Conditions of temperature and concentration of the amide solvent specifically not be limited provided that they can provide fiber satisfactory quality. However, when the temperature in tub reach the level of 60 C or more, the penetration of water into the fiber is fast. Accordingly, in the fiber produced huge void that cause deterioration of the quality. For this reason, the temperature in the first tub preferably set at 30 C or less.
When the solvent remains in the fiber, environmentally safe processing of products with use of such fibres, and the use of products derived from this fiber, becomes undesirable. For this reason, the quantity of solvent contained in the fiber according to the invention, is 0.1 wt.% or less, and is more preferable to 0,08% of mass or less.
Stage dry heat treatment
At the stage of dry heat treatment fiber, which was processed at the stage of leaching, subjected to drying/thermal treatment. Method of dry heat treatment is not specifically limited. However, as an example can be mentioned method with the use of hot drum, heating plate, etc. Upon completion of dry heat treatment could be obtained easily , fully aromatic polyamide fiber meta-type, according to the invention.
To obtain fiber according to the invention requires that the temperature at the stage of dry heat treatment ranged from 260 to 330 C and preferably in the range from 270 to 310°C. When the temperature in thermal processing of fibre is less than 260 C, crystallization fiber becomes unsatisfactory. Accordingly, becomes unsatisfactory target acid. On the other hand, when the temperature is higher than 330 OC C, the degree of crystallization fiber becomes too large. Consequently, significantly reduces the colorability fiber. In addition, regulation of temperature of dry thermal treatment in the range from 260 to 330 OC C contributes to the improvement of the tensile strength of the received fiber.
ExamplesBelow, the present invention will be more specifically described with examples, etc. that should not be considered in terms of limiting the volume of the invention.
Method of measurement
The corresponding values of the physical characteristics of the examples and Comparative examples measured as follows.
Fineness of yarn
The measurements are carried out in accordance with the method And standard JIS L 1015 determine the fineness of yarn per adjusted lot, and this value is expressed in units of apparent fineness of yarn.
Tensile strength, elongation at break
The measurements are carried out using the model 5565 device produced at the company INSTRON Co., JIS L 1015, in the following terms:
Measurement conditions
Length capture: 20 mm
Initial load: 0,044 SN (1/20 g)/
Stretch speed: 20 mm/min
The degree of extraction of dye
The solution with the rest of the dye, which was colored fiber, add dichloromethane in a volume equal to the volume of solution with the remaining dye to extract the remaining dye. After that they measure the value of optical density extraction solution at a wavelength of 670 nm, 540 nm and 530 nm, respectively. According to the data of the calibration curve for the given values of wavelength, pre-built for solutions with known concentration of dye, respectively determine the concentration of the dye in the extraction solution. Average concentrations at three wavelengths is taken for the concentration of the dye (C) extraction solution. The value obtained using the concentration of the dye to colour (Co) from the following equation, called the degree of extraction of dye (U).
The degree of extraction of dye (U)=[(- C)/With]x 100
Index-term durability (acid test)
Collect fiber in the amount of about 8.0 g and dried at 105 C for 120 minutes. Then the fibre is allowed to cool in a drying Cabinet for defining the weight of the fiber (M1). After the extraction is carried out fiber in boiling methanol within 1.5 hours by using the extractor ml Soxhlet extractor. So extraction amide solvent contained in the fiber. Take out the fiber, which undergone a complete extraction, and dried in a vacuum at 150 C for 60 minutes. Then the fibre is allowed to cool in a drying Cabinet for defining the weight of the fiber (M2). The number N(%) solvent (mass amide solvents), remaining in the fiber, calculated using the obtained values of M1 and M2 by the following equation:
N(%)=[(M1-M2)/M1]X 100
Example 1. Stages of preparation for spinning solution
Powder in the amount of 20 parts by mass, and with the characteristic viscosity (XB), equal to 1.9, produced using the method of inter-phase polymerization according to the method described in the document JP-B-47-10863, suspended in N-methyl-2- (NMP, 80,0 parts by weight), cooled to - 10 degrees Fahrenheit, so get a suspension. After this suspension is heated up to 60 C in order to dissolve, which leads to a transparent polymer solution A.
Stage spinning/coagulation
Polymer solution And unloaded as the source spinning solution through the die with a diameter of holes 0.07 mm and 500 holes inside of setting bath at a temperature of 30 C in the tub for spinning. Coagulation solution has the composition of water/NMP=45/55 (in parts by weight)and is entered into the precipitation tank for spinning with a speed of 7 m/min
Stage plasticizing pulling in the bath
Then spend pulling factor of extraction in the tub plasticizing pulling equal to 3.7 times at a temperature of 40 C and the composition of the solution water/NMP=45/55.
Stage of leaching
After pulling conduct leaching fiber in the bath (immersion length 1.8 m) 20 C, the ratio of water/NMP=70:30, and then in the tub with water at 20 C (immersion length 3,6 m). In addition, do final rinse the tub with warm water at 60 C (immersion length 5.4 mm).
Stage dry heat treatment Fiber after washing subjected to dry heat treatment with the use of hot drum surface temperature of 280 C, which leads to a fully aromatic aramid fibre meta-type.
The physical characteristics of the fiber
The resulting fiber has the following physical characteristics: fineness of yarn 1,7 , tensile strength 2,8 CN/, elongation 51,0%, and residual solvent content of 0.08%mass, and demonstrates the appropriate dynamic characteristics. The physical characteristics of fibres obtained are shown in table 1.
Stage coloring
Prepare a coloring solution containing 6% cationic dye (brand name: Kayacryl Blue GSL-ED (54), produced at the company NIPPON KAYAKU Co., Ltd.), 0.3 ml/l acetic acid 20 g/l of sodium nitrate, 70 g/l of benzyl alcohol as transporting agent and 0.5 g/l subsidiary colouring agent (brand name: DISPER TL, produced at the company MEISEl CHEMICAL WORKS, Ltd.) as dispersal agent. Sample fiber in a towed able to expose colouring treatment at 120°C for 60 minutes, and the ratio of fiber to solution in the tub is equal to 1:40. After colouring processing using processing solution containing 2,0 g/l bisulfite, 2.0 g/l AMlRADINE D (brand name AMlRADINE D, produced at the company DAI - ICHI KOGYO SEIYAKU CO., Ltd.) and of 1.0 g/l sodium hydroxide, in the specified proportions, hold 20-minute replacement leaching at 80 C with a ratio in the bath, is equal to 1:20. After washing with water drying is conducted, which leads to painted fiber.
Physical characteristics painted fibre and the like
The degree of extraction of dye colored fiber is to 92.4%, and demonstrated a suitable colorability. In addition, the tensile painted fibre is 2.9 CN/, and tensile strength painted fibre after the test acid is 1,9 CN/, and maintain strength indicator is 66%. Thus, demonstrated a suitable acid. The physical characteristics of fibres obtained are shown in table 1.
Example 2. Stages of preparation for spinning solution
In the reaction vessel, equipped with a device of mixing and a hole to download the source materials, enter 854,8 part methyl-2- (later abbreviated NMP). Dissolve 83,4 part of the meta-phenylenediamine (later abbreviated to ) in NMP. Additionally, this solution with stirring gradually add 156,9 part chloride isophthalic acid (later abbreviated to ) to carry out the reaction. Stirring is continued for 40 minutes from the start of the reaction, then add 57,1 parts of powder calcium hydroxide. Stirring is continued for another 40 minutes, and then the reaction is interrupted. solution pour out of the reaction vessel. The result is a transparent solution with the concentration of polymer equal to 16%.
Stage spinning/coagulation, plasticizer, pulling out of the bath, washing, stage of relaxation thermal processing of steam and dry heat treatment
Fiber from receive the same way as in example 1, except that the resulting solution is used as a source spinning solution, drawing ratio in the tub plasticizing pulling set at 3.5 times, and the surface temperature on the stage of dry heat treatment equal to 310°C.
The physical characteristics of the fiber
The resulting fiber has the following physical characteristics: fineness of yarn 1,7 , the tensile strength of 3.2 CN/, elongation of 45.3%, and residual solvent content 0,10%of mass). The physical characteristics of fibres obtained are shown in table 1.
Stage coloring
The resulting fiber handle on the stage of painting in the same way as in example 1.
Physical characteristics painted fibre and the like
The degree of extraction of the dye is 91,0%, and demonstrated a suitable colorability. In addition, the tensile painted fibre is 3.2 CN/, and tensile strength painted fibre after the test acid is equal to 2.4 mV/, and maintain strength indicator is 75%. Thus, demonstrated a suitable acid. The physical characteristics of fibres obtained are shown in table 1.
Example 3. Production of fibers
Fiber from receive the same way, as in example 2, except that the drawing ratio in the tub plasticizing pulling set at 4.5 times, and the surface temperature on the stage of dry heat treatment equal to 280 degrees C.
The physical characteristics of the fiber
The resulting fiber has the following physical characteristics: fineness of yarn 1,7 , the tensile strength of 3.6 CN/, elongation of 36.1%, and residual solvent content of 0.06%of mass. The physical characteristics of fibres obtained are shown in table 1.
Stage coloring
The resulting fiber handle on the stage of painting in the same way as in example 1.
Physical characteristics painted fibre and the like
The degree of extraction of the dye is 91,5%, and demonstrated a suitable colorability. In addition, the tensile painted fibre is 3.5 mV/, and tensile strength painted fibre after the test acid equal to 2.5 mV/, and maintain strength indicator is 71%. Thus, demonstrated a suitable acid. The physical characteristics of fibres obtained are shown in table 1.
Example 4. Production of fibers
Fiber from receive the same way, as in example 3, except that prescribe the solution of the coagulation with the ratio of water/NMP=55/45 at the stage of spinning/coagulation.
The physical characteristics of the fiber
The resulting fiber has the following physical characteristics: fineness of yarn 1,7 , the tensile strength of 3.7 CN/, elongation of 32.0%, and residual solvent content of 0.05 wt.%. The physical characteristics of fibres obtained are shown in table 1.
Stage coloring
The resulting fiber handle on the stage of painting in the same way as in example 1.
Physical characteristics painted fibre and the like
The degree of extraction of the dye is by 90.4%and to demonstrate a suitable colorability. In addition, the tensile painted fibre is 3.7 CN/, and tensile strength painted fibre after the test acid equal to 2.7 CN/, and maintain strength indicator is 73%. Thus, demonstrated a suitable acid. The physical characteristics of fibres obtained are shown in table 1.
A comparative example 1. Production of fibers
Fiber from receive the same way, as in example 2, except that prescribe the solution of the coagulation with the ratio of water/ NMP=70/30. at the stage of spinning/ coagulation, drawing ratio in the tub plasticizing stretching is 3.7 times, and the surface temperature on the stage of dry heat treatment equal to 280 degrees C.
The physical characteristics of the fiber
The resulting fiber has the following physical characteristics: fineness of yarn 1,7 , the tensile strength of 2.5 mV/, elongation of 25.0%, and residual solvent content of 0.30%of mass. The physical characteristics of fibres obtained are shown in table 1.
Stage coloring
The resulting fiber handle on the stage of painting in the same way as in example 1.
Physical characteristics painted fibre and the like
Tensile strength painted fibre is 2.6 CN/, and tensile strength painted fibre after the test acid is equal to 1.8 mV/, and maintain strength indicator is 69%. Thus, demonstrated the best results. However, the degree of extraction of dye accounted for 85.3%, which is unsatisfactory result. The physical characteristics of fibres obtained are shown in table 1.
A comparative example 2
Fiber from receive the same way, as in example 2, except that prescribe the solution of the coagulation with the ratio of water/ NMP=30/70 at the stage of spinning/ coagulation, drawing ratio in the tub plasticizing stretching is 3.7 times, and the surface temperature on the stage of dry heat treatment equal to 280 degrees C.
The physical characteristics of the fiber
The resulting fiber has the following physical characteristics: fineness of yarn 1,7 , the tensile strength of 2.4 mV/, elongation of 28.0%, and residual solvent content of 0.60%of mass. The physical characteristics of fibres obtained are shown in table 1.
Stage coloring
The resulting fiber handle on the stage of painting in the same way as in example 1.
Physical characteristics painted fibre and the like
The degree of extraction of the dye is 94.0%, which demonstrates the appropriate colorability. However, the tensile strength of the painted fibre 2,4 CN/, and tensile strength painted fibre after the test acid is 1.2 CN/, and maintain strength indicator is 50%, which is unsatisfactory result for indicator acid.
A comparative example 3. Production of fibers
Fiber from get through education source spinning solution in the same way as in example 2, except that establish drawing ratio in the tub plasticizer, pulling at the level of 3.0 times, and the surface temperature on the stage of dry heat treatment is 280 degrees C.
The physical characteristics of the fiber
The resulting fiber has the following physical characteristics: fineness of yarn 1,7 , tensile strength 2,2 CN/, elongation of 55.3%, and residual solvent content of 0.60%of mass. The physical characteristics of fibres obtained are shown in table 1.
Stage coloring
The resulting fiber handle on the stage of painting in the same way as in example 1.
Physical characteristics painted fibre and the like
The degree of extraction of the dye is 93,8%, which demonstrates the appropriate colorability. However, the tensile strength of the painted fibre 2,2 CN/, and tensile strength painted fibre after the test acid is 1.2 CN/, and maintain strength indicator is 55%, which is unsatisfactory result for indicator acid.
A comparative example 4. Production of fibers
The attempt of the production of fibre from in the same way as in example 2, except that establish drawing ratio in the tub plasticizer, pulling at the level of 5.5 times, and the surface temperature on the stage of dry heat treatment is 280 degrees C. However, these conditions stage were unsuccessful, leading to difficulties stable collection fiber over a long period.
A comparative example 5. Production of fibers
Fiber from receive the same way, as in example 2, except that establish drawing ratio in the tub plasticizer, pulling at 3.7 times, and the surface temperature on the stage of dry heat treatment is 220°C.
The physical characteristics of the fiber
The resulting fiber has the following physical characteristics: fineness of yarn 1,7 , the tensile strength of 2.6 CN/, elongation 53,0%, and residual solvent content of 0.08%of mass. The physical characteristics of fibres obtained are shown in table 1.
Stage coloring
The resulting fiber handle on the stage of painting in the same way as in example 1.
Physical characteristics painted fibre and the like
The degree of extraction of dye 94.8%, which demonstrates the appropriate colorability. However, the tensile strength of the painted fibre equal to 2.7 CN/, and tensile strength painted fibre after the test acid is 1.2 CN/, and maintain strength indicator is 44%, which is unsatisfactory result for indicator acid.
Example #
1 2 3 4Compare - final 1
Compare - final 2
Compare - final 3
Compare - final 4
Cf - 5'nii
Composition of setting bath NMP (water/NMP)
45/55 45/55 45/55 55/45 70/30 30170 45/55 45/55 45/55Coefficient of plasticizing pulling in the bath (some times)
3,7 3,5 4,5 4,5 3,7 3,7 3,0 5,5 3,7Temperature dry heat treatment (C)
280 310 280 280 280 280 280 280 220The physical characteristics of the fiber
Fineness of yarn ()
1,7 1,7 1,7 1,7 1,7 1,7 1,7 - 1,7Tensile strength (mV/)
2,8 3,2 3,6 3,7 2,5 2,4 2,2 - 2,6Elongation (%)
51,0 45,3 36,1 32,0 25,0 28,0 55,3 - 53,0Residual solvent content (%)
0,08 0,10 0,06 0,05 0,30 0,60 0,60 - 0,08Physical characteristics painted fibre
The degree of extraction of dye (%)
92,4 91,0 91,5 90,4 85,3 94,0 93,8 - 94,8Tensile strength (mV/)
2,9 3,2 3,5 3,7 2,6 2,4 2,2 - 2,7After the test acid
Tensile strength (mV/)
1,9 2,4 2,5 2,7 1,8 1,2 1,2 - 1,2Indicator maintain strength
Indicator conservation strength (%)
66 75 71 73 69 50 55 - 44Industrial applicability
Easily fully aromatic polyamide fiber meta-type of the present invention is a fiber with excellent and acid resistance, has a very small residual solvent content in the fiber, and has excellent environmental safety. For this reason, the industrial value of the specified fiber is significant in areas that require such characteristics. In areas where the importance of aesthetic properties and visual characteristics, such as bedding, clothing and articles of interior, can be obtained absolutely safe products, and therefore they have a very large utility.
Easily fully aromatic polyamide fiber meta-type, which has a residual solvent content of 0.05-0.1 wt.% in the form of fiber, and having indicator maintain strength 65-73% in the form of a colored fibers after dipping to 150 h 20 wt.% aqueous solution of sulfuric acid at 50 C, and has a degree of extraction of dye 90-92,4% in the form of painted fibre, coagulation solution is used at the stage of coagulation, is an aqueous solution containing solvent concentration from 45 to 60 wt.%, coefficient of plasticizer, pulling the fiber at the stage of plasticizing pulling is in the range of 3.5 to 4.5, temperature dry heat treatment washed fiber at the stage of dry heat treatment is in the range from 260 to 330 OC C.