JP4626172B2 - Melt spinning apparatus, method for producing the same, and melt spinning method using the same - Google Patents

Description

  The present invention relates to a thermoplastic polymer melt spinning apparatus, a method for producing the same, and a melt spinning method using the same. More specifically, at least a part of the surface of the melt spinning apparatus that comes into contact with the molten polymer is formed by a high-hardness vapor-deposited film that is excellent in releasability from the molten polymer and excellent in corrosion resistance and wear resistance. The present invention relates to a melt spinning apparatus, a manufacturing method thereof, and a melt spinning method using the same.

  Usually, an apparatus for melt spinning thermoplastic polymer (FIG. 1) consists of an extruder, a polymer tube, a metering pump and a spin pack. An extruder is a device for melting a pellet-shaped thermoplastic polymer, and the extruder is generally composed of a screw, a barrel, and a cylinder. In addition, the thermoplastic polymer melted by the extruder is extruded through a polymer tube heated and kept warm while continuously measuring the molten polymer with a metering pump, and formed into a yarn with a melt spinneret placed in a spin pack. To do.

  By the way, the thermoplastic polymer to be melt-spun contains various additives. For example, polyester has a polymerization catalyst antimony trioxide, a heat-resistant phosphorus compound and a matting agent titanium oxide, and nylon has a copper compound as a thermal antioxidant used in industrial fibers and a matting agent. There are titanium oxide and the like, and both polymers are added with pigments for the original fibers. Further, high hardness metals such as titanium oxide, carbon black, iron oxide, magnesium oxide, etc. need to be added in order to improve customer requirements and production efficiency.

  The above-mentioned additives for thermoplastic polymers, especially metal compounds such as antimony trioxide, copper compounds, titanium oxide, carbon black, etc., separate from the molten polymer and deposit and adhere to the inner wall of the spinning machine, blocking the polymer tube. In the past, there has been a problem that wear occurs on the wall surface where a high shear stress is applied due to the molten polymer.

  The phenomenon of sticking and depositing is caused by, for example, precipitation of copper sulfide in the melt spinning of industrial nylon 6 fiber, precipitation of metallic copper in the melt spinning of industrial nylon 66 fiber, and precipitation of metal antimony in the spinning of industrial polyester fiber. Occur. These deposits adhere to and accumulate on the inner wall of the pipe where the molten polymer comes into contact, such as the polymer pipe of the spinning device, the metering pump, the filter of the spin pack member, the distribution plate, the back surface of the melt spinneret and the melt spinneret hole. The path was occluded and became an obstacle to normal spinning. In particular, industrial fibers use a polymer with a high degree of polymerization in order to obtain high-strength yarns, and are melt-spun at a high temperature, so that the precipitation reaction of the additive is promoted, and the above-described fixed deposition is remarkable.

  The formation of copper sulfide precipitated by melt spinning of industrial nylon 6 fiber is because a decomposition reaction of the copper compound as an antioxidant and the sulfur-containing machine compound occurs in the spinning device. Further, the precipitation of copper metal and polyester metal antimony in industrial nylon 66 fiber is due to the reduction reaction occurring in the spinning device. The reduction reaction of nylon 66 is promoted by a metal halide and a molten polyamide polymer added together as an antioxidant. The reduction reaction for precipitation of metallic copper and metallic antimony in the melt spinning of nylon 66 and polyester occurs remarkably on the surface of the melt spinning member in contact with the molten polymer. From this, it is speculated that the metal deposition is caused by an electrochemical reaction due to an ionization tendency between the metal compound in the molten polymer and the surface of the melt-spun member. That is, it is considered that iron ions are eluted from the material of the melt-spun member, metal copper or metal antimony is deposited, and is fixedly deposited on the surface of the melt-spun member. In particular, it is known that a metal is remarkably deposited on a metal nonwoven fabric filter of a spin pack, which has a remarkably large contact area with a molten polymer, and causes an increase in filtration pressure. Note that the metal produced and deposited and fixed on the surface of the melt-spun member clogs the polymer tube and the like after a long period of time, and makes normal spinning impossible. For example, spinning failures such as an increase in the filtration pressure of the spin pack, a decrease in the metering accuracy of the metering pump, and a loss of the required amount of polymer due to blockage of the polymer tube occur. When such a failure occurs, the spinning device is disassembled and washed, reassembled, and returned.

  In addition, in melt spinning of nylon 66, it is known that the polymer itself is thermally decomposed during melt spinning and causes a gelation reaction, in addition to the obstacle caused by precipitation of metallic copper due to the decomposition reaction of the copper compound. Yes. This gelled polymer stays without flowing through the melt-spun member, and is further thermally decomposed, and is deposited and fixed on the surface of the melt-spun member, thereby closing the polymer tube. The thermal decomposition and gelation in the melt spinning of nylon 66 are affected by the quality of the polymer, spinning temperature, abnormal residence in the spinning machine, etc., and technical development for preventing gelation has been conducted for some time. It was.

  On the other hand, in the melt spinning of nylon 6 or polyester, gelation does not occur because the thermal decomposition reaction is mainly a molecular cutting reaction. However, in a polymer tube or the like of a spinning device, the polymer is abnormally accumulated, and the molten polymer decomposed due to a long thermal history is carbonized and does not flow, and the polymer tube or the like may be blocked similarly. Although the mechanism is different, there is a common problem of blockage of the polymer tube due to decomposition of the molten polymer.

  The above-mentioned copper sulfide, copper metal, metal antimony, and polymer pyrolysis gel and polymer carbide precipitated by thermal decomposition during melt spinning clog the polymer tube and cause an increase in the filtration pressure of the spin pack. Often, it passes through the filter and gets mixed into the spun yarn, causing yarn breakage or single yarn breakage in the drawing process. In particular, the metal foreign matter that has passed through the micropores of the filter is agglomerated again until it passes through the melt spinneret hole, that is, the polymer distribution plate, the backside of the melt spinneret, and the melt spinneret hole, and becomes foreign matter. It has been found that it is mixed in the yarn.

  Furthermore, when the molten polymer often contains inorganic hard metal particles, such as titanium oxide, magnesium oxide, carbon black, bengara, etc., the surface where the molten spinning member, which is a melt spinning apparatus, and the molten polymer contact is worn. There was also a problem.

  In particular, the metering pump has a problem in that wear occurs with time and the clearance increases, the meterability is lowered, and the metering pump cannot be used. In addition to the problem of the above-mentioned fixed deposits, there has been a demand for a solution to this problem of preventing wear.

  In order to prevent the formation of the metal, gelled polymer, and carbonized polymer deposited and fixed on the surface of the melt spinning member as the melt spinning apparatus as described above, a technique for cutting off the generation cause has been conventionally developed. For example, in Patent Document 1, in order to suppress the electrochemical reaction with the surface of the melt-spun member and prevent the formation of metal, the surface of the melt-spun member with which the polymer comes in contact is coated with silica, In particular, proposals have been made to use a metal filter having a large surface area by treating it with silicone.

  In addition, generation of metal, generation of gelled polymer, and generation of polymer carbide are all significant in the portion of the melt-spun member where the flow of the molten polymer stays, so the portion where the molten polymer stays abnormally is reduced as much as possible. A proposal for improving the spinning pack structure is described in Patent Document 2, for example.

The above-described conventional techniques, that is, the inactivation technique of the surface in contact with the molten polymer of Patent Document 1 and the technique of reducing the abnormal residence portion in the spinning apparatus of the molten polymer of Patent Document 2 are as effective as they are. I was there, but I was not yet satisfied. In other words, it is an effective means for preventing foreign matter generation, but it is a technique that is practically difficult to apply effectively. For example, a metering pump whose polymer meterability deteriorates in a short period due to remarkable generation of foreign matter is not only difficult to inactivate the surface of the molten polymer, but is inferior in durability and heat resistance even when it is bent. Although it can be confirmed that the process is effective at the beginning of the process because the yarn-making property and the texture are lower than the normal level, the state is not maintained for a long time. This is because the durability and heat resistance are inferior as described above. In view of the above, the prior art cannot sufficiently exhibit the effect, and it has been substantially difficult to reduce the abnormal retention portion of the metering pump.
Japanese Patent Laid-Open No. 10-273810 Japanese Patent Laid-Open No. 08-269816

  An object of the present invention is to solve the above-described problems in the prior art.

  That is, the problem to be solved by the present invention is that when a thermoplastic polymer is melt-spun, the melt-spinning member of the melt-spinning apparatus, that is, the polymer tube, the metering pump, and the spinneret except for the spinneret, is released from the molten polymer. A melt spinning apparatus capable of reducing the occurrence of yarn breakage and fluff by providing an excellent, corrosion-resistant, and wear-resistant high-hardness vapor-deposited film, and extending the life of each member, and a method for producing the same Another object of the present invention is to provide a melt spinning method using the same.

The present invention that solves the above-mentioned problems is an apparatus for melt spinning thermoplastic polymers, wherein at least one of the surfaces of the melt spinning member constituting the apparatus, the metering pump, and the spin pack member in contact with the molten polymer. The contact angle between the surface of the deposited film and water is 65 to 115 °, the deposited film hardness (room temperature HV) is 1500 to 6000 , and the volume resistivity of the deposited film surface is 10 ⁺⁵ to 10 ⁺¹⁴ Ω · cm der is, the deposition film FHC (flow Rick hardcoat), CFC (fluoride carbon coating), TiBN (titanium boron nitride), CRBN (chromium nitride, boron), SiBN (silicon nitride boron) characterized Rukoto such at least one member selected from.

In the polymer tube, metering pump, and spinning pack, which are the melt spinning members constituting the melt spinning apparatus of the present invention, the following (1) can be cited as preferred embodiments.
(1) thickness of the deposited film 0.5~15μm Dearuko with.

In addition, the method for manufacturing a melt spinning apparatus according to the present invention includes performing ion cleaning on at least a part of the surface of the melt spinning member constituting the melt spinning apparatus that contacts the polymer tube, the metering pump, and the spinning pack member, and applying vacuum. Under the control, the acceleration voltage of the substrate is controlled in the range of −100 to −3 kV, and the organic gas component of the CF-based gas or the CH-based gas is ionized to form a deposited film.
Preferably the is found, the following (3), mentioned as each preferred embodiment (4).
( 3 ) The deposited film is any one selected from FHC (floric hard coat), CFC (fluorinated carbon coat), and DLC (diamond-like carbon).
( 4 ) The fluorine addition amount of the FHC (floric hard coat) or CFC (fluorinated carbon coat) is 2% or more.

In another melt spinning apparatus manufacturing method, ion cleaning is performed on at least a part of the surface of the melt spinning member constituting the melt spinning apparatus that contacts the polymer tube, the metering pump, and the spinning pack member. The substrate acceleration voltage is controlled in the range of −50 to −2 kV and at least one metal component selected from B (boron), Ti (titanium), Cr (chromium), and Si (silicon) is ionized. Further, the film is further substituted with nitrogen to form a deposited film.

The following ( 5 ) and ( 6 ) can be cited as preferred embodiments. ( 5 ) Impurity content of B (boron), Ti (titanium), Cr (chromium), Si (silicon) is 0.01%. Less than.
( 6 ) The deposited film is made of at least one selected from TiBN (titanium boron nitride), CrBN (chromium boron nitride), SiBN (silicon boron nitride), and CrN (chromium nitride).

  The melt spinning method of the present invention is a melt spinning method of a thermoplastic polymer, and is characterized by using a spin pack member excluding the polymer tube, metering pump and spinneret which are the melt spinning members.

  In the present invention, when melt spinning a thermoplastic polymer, the polymer tube, which is a melt spinning member of a melt spinning apparatus, a metering pump and a spin pack member excluding a spinneret are excellent in releasability from the molten polymer, and are resistant to corrosion and resistance. By applying a high-hardness vapor-deposited film with excellent wear, the occurrence of yarn breakage and fluff can be reduced, and the life of each member can be extended.

  The thermoplastic polymer in the present invention is not particularly limited as long as it is a melt-spinnable thermoplastic polymer. For example, polyamides such as nylon 6, nylon 66, nylon 46, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, poly Polyesters such as lactic acid, polyolefins such as polyethylene and polypropylene, polysulfides, polyimides, polyether ketones, polyether nitriles, and the like, are thermoplastic polymers that can be melt-spun, and are copolymer copolymers mainly composed of the above polymers, and the above A polymer used by blending or combining two or more polymers.

  A polymer tube, a metering pump, and a spin pack (excluding a spinneret), which are melt spinning members in the present invention, are apparatuses for melt spinning thermoplastic polymers, and are provided on the surface of the melt spinning member in contact with the molten polymer. At least a part is formed of a vapor deposition film, the contact angle between the vapor deposition film surface and water is 65 to 115 °, and the vapor deposition film hardness (room temperature HV) is 1500 to 6000. In the present invention, the spin pack does not include a spinneret.

  The surface of the melt-spun member that contacts the molten polymer is at least a part of the sliding surface of each member of the metering pump, a member such as a polymer distribution plate disposed in the spinning pack, or the surface of the mixer for kneading disposed in the polymer tube. Of these, the molten polymer is in contact with the part, and a part of the part may be formed of a deposited film. One of the characteristics of the deposited film surface is releasability from the molten polymer. This is because the material of the conventional melt spinning apparatus is inferior in the releasability of the molten polymer, tends to abnormally stay on the inner wall of the polymer tube, and is a main cause of depositing insoluble matter in the molten polymer on the inner wall of the polymer tube. The releasability of the vapor deposition film of the present invention is specified when the contact angle between the vapor deposition film surface and water is 65 to 115 °. Originally, it should be specified by the releasability between the molten polymer and the deposited film, but it can be expressed by a contact angle with water at room temperature as an alternative characteristic.

  The preferable range of the contact angle of the deposited film with water at room temperature is 65 to 115 ° in the present invention. If it is less than 65 °, the releasability from the melted polymer intended by the present invention cannot be obtained. On the other hand, a contact angle of 115 ° or more means more preferable releasability, but it is difficult to achieve with current practical technology. The contact angle is largely determined by the material of the deposited film. Preferably, a deposited film made of fluoride such as FHC or CFC is very excellent in water repellency and releasability. Further, as a matter of course, the surface form obtained also varies depending on the vapor deposition method and the vapor deposition apparatus. For example, the raw material of the deposited film can be roughly classified into a gas system such as an organic gas, and a metal system made of a single metal or an alloy. In general, ionizing a gas system and depositing it reflects the finish of the substrate surface without the roughness of the substrate surface becoming rough. In order to further improve the finish of the deposited film surface after vapor deposition, it is further preferable to control the acceleration voltage of the base material in the range of −100 to −3 kV and to keep the addition amount of fluorine at 2% or more. is there.

  In the present invention, the amount of fluorine added to the deposited film is determined by performing quantitative analysis using, for example, an EPMA-8705 type electron microanalyzer manufactured by Shimadzu Corporation under the analysis conditions of an acceleration voltage of 8 kV, a sample current of 50 nA, and a beam diameter of φ100 μm. Can be measured.

  On the other hand, when vapor-depositing a metal system, the ionized metal is physically collided with the substrate surface using a strong potential energy difference from the substrate. Therefore, the stronger the impact energy, the higher the adhesion between the deposited film and the substrate. Thus, the surface of the obtained substrate is finished to a surface that is relatively rougher than the gas system. Therefore, in order to finish the surface roughness like a gas system, the irradiation amount and irradiation speed of ionized metal are controlled and improved. In order to further improve the finish of the deposited film surface after deposition, it is more preferable to control the acceleration voltage of the base material in the range of −50 to −2 kV. Furthermore, it is also devised to wrap the obtained deposited film and finish the surface.

  In any method, the deposition surface is preferably smoothed so that the surface roughness Ra is 0.5 μm or less.

  Next, as for the hardness of the vapor deposition film concerning this invention, vapor deposition film hardness (normal temperature HV) is 1500-6000. Preferably it is 2000-6000. If it is less than 1500, for example, the polymer tube of the melt-spun member and the spin pack member excluding the spinneret are significantly worn by the additive made of the metal of the molten polymer, and particularly inorganic materials such as titanium oxide, magnesium oxide, carbon black, and bengara. When the additive is contained, wear occurs remarkably. The phenomenon is the same for the metering pump. Parts that are constantly driven and used like a metering pump are subject to wear. This is because the molten polymer passing through the metering pump is extruded at a high pressure of several tens of kg / cmG or more, so that the flow of the molten polymer containing the inorganic additive is so-called fluid polishing. As a result, the members inside the metering pump are worn, and the meterability deteriorates with time. The vapor deposition film hardness is determined mainly by the type of vapor deposition component. Therefore, in order to make the vapor deposition film hardness of the vapor deposition film forming portion of the melt spinning apparatus in the range of 1500 to 6000, it is important to select the type of film forming component suitable for this.

  Note that it is preferable to increase the adhesion by performing ion cleaning in an environment of 10 −3 Torr or higher by setting the vapor deposition tank to a high vacuum, and it is more preferable to implant ions into the substrate. For that purpose, it is most important to set the acceleration voltage of the base material according to the material of the base material, generate a clean plasma, and perform the deposition. Further, it is more preferable to use a high-purity metal source for vapor deposition with an impurity content of 0.01% or less.

  In the present invention, the impurity content of the metal raw material is measured by, for example, quantitative analysis using an EPMA-8705 type electron beam microanalyzer manufactured by Shimadzu Corporation, and the analysis conditions are an acceleration voltage of 8 kV, a sample current of 50 nA, and a beam diameter of φ100 μm. it can. Specific examples of impurities contained in a trace amount in the deposited metal include Fe (iron), K (potassium), Ca (calcium), and Na (sodium).

The electrical characteristics of the deposited film according to the present invention are such that the volume resistivity of the deposited film surface is 10 ⁺⁵ to 10 ⁺¹⁴ Ω · cm . Good Mashiku is a 10 ⁺⁸ ~10 ⁺¹⁴ Ω · cm. This volume resistivity specification prevents the metal compound added to the melt-spun polymer from depositing metal due to the electrochemical reaction caused by the ionization tendency with the material of the melt-spinning apparatus with which the melt polymer contacts. It is effective. In particular, the metering part of the metering pump that comes into contact with the molten polymer is subject to reduction / precipitation reaction of the metal compound due to the high temperature and high pressure of the molten polymer and the high shear rate. Deposition is significant. Conventional improvement techniques have recommended an inert silica coating or silicone film forming treatment, but the formation of the deposited film of the present invention is the most effective for the surface treatment in the metering member of this metering pump. Although the volume resistivity is substantially determined by the material of the deposited film, the volume resistivity increases as the amount of the components constituting the deposited film, for example, the amount of carbon increases, and is also affected by the purity of the deposited film. It is important that the volume resistivity falls within the range specified in the present invention in view of the fact that the volume resistivity is lowered when there are many impurities in the deposited film. When the volume resistivity on the surface of the deposited film is in the range of 10 ⁺⁵ to 10 ⁺¹⁴ Ω · cm, the electrochemical reaction between the metal compound in the molten polymer and the tube inner wall base material in contact with the molten polymer of the melt spinning apparatus Reaction can be appropriately suppressed, and the effects of the present invention can be promoted.

  The thickness of the vapor deposition film concerning this invention melt spinning apparatus is 0.5-15 micrometers, Preferably it is 1-10 micrometers. Vapor deposition with a thickness of less than 0.5 μm is difficult to put into practical use at present. Further, it is mechanically damaged such as bruise, and is not sufficiently durable against corrosion. On the other hand, a thickness exceeding 15 μm is unnecessary because the effect is already saturated and the vapor deposition cost increases. The characteristics of the vapor deposition film surface formed on the surface of the melt spinning apparatus of the present invention are as described above, and specific vapor deposition film components and vapor deposition methods are as follows.

  The base material of the spin pack member excluding the polymer tube, metering pump, and spinneret, which are melt spinning members that come into contact with the molten polymer of the melt spinning apparatus of the present invention, is not particularly limited as long as it is a metal. Conventionally used metals such as stainless steel, iron and chrome molybdenum steel are used, but stainless steel is usually preferred.

  The components of the vapor deposition film to be vapor-deposited on the surface of the melt spinning apparatus of the present invention are fluorocarbon-based, fluorine-based compound FHC (floric hard coat), CFC (fluorinated carbon coat), carbon-based DLC (diamond-like carbon), Boron-based TiBN (titanium boron nitride), CrBN (chromium boron nitride), SiBN (silicon boron nitride), Cr-based CrN (chromium nitride), titanium alloy-based TiCN (titanium carbonitride), TiN (titanium nitride), These are metal workpieces and ceramic compounds selected from TiALN (titanium nitride aluminum) and other SiC (silicon carbide).

  These vapor-deposited films are excellent in releasability from the thermoplastic polymer and excellent in corrosion resistance such as acid or alkaline aqueous solution. In particular, chlorofluorocarbon, fluorine compound FHC (floric hard coat), CFC (fluorinated carbon coat), carbon-based DLC (diamond-like carbon), boron-based TiBN (titanium boron nitride), CrBN (chromium boron nitride) SiBN (silicon boron nitride) and Cr-based CrN (chromium nitride) exhibit better corrosion resistance.

  In the present invention, vapor deposition on the melt spinning apparatus is performed by either PVD method (Physical Vapor Deposition Process) or CVD method (Chemical Vapor Deposition Process). be able to. However, since the PVD method (physical vapor deposition) has a lower processing temperature during vapor deposition than the CVD method, it is preferable as a method for vapor deposition on the melt spinning apparatus of the present invention. However, among the CVD methods, the P-CVD method (plasma CVD) can be deposited in a low temperature environment equivalent to the PVD method, and is therefore used as a preferable processing method as in the PVD method.

  A specific method for forming a deposited film on the melt spinning apparatus of the present invention is, for example, as follows. First, as a pretreatment of the metal substrate prior to vapor deposition, the substrate is washed in order to facilitate the formation of a vapor deposition film on the surface of the metal substrate. For cleaning the substrate, a solvent such as ethanol or thinner is used, and then ultrasonic cleaning is performed in water to remove foreign matters entering the pores. Furthermore, pure water or conditioned water is used as the finish cleaning water.

If properly implemented the pretreatment, although not as damaging the adhesion of the deposited film, intends row ion cleaning as a substrate cleaning method further. Using a vacuum furnace, the degree of vacuum in the furnace is evacuated to 10 ⁻² to 10 ⁻⁷ Torr, applied to the substrate or electrode with an ion gun or radio frequency (RF) or DC voltage as an ion source, and then argon gas ( Ar) is introduced to generate plasma. Argon ions (Ar) are caused to collide with the base material with a potential difference, and the oxide film and deposits on the surface of the base material are removed by the collision energy.

  Next, the inside of the vacuum furnace used at the time of vapor deposition processing is also thoroughly cleaned. This is because if metal or metal oxide previously deposited is deposited in a vacuum furnace, it vaporizes during deposition and is deposited on the substrate as an impure component. In order to prevent this, it is preferable to perform cleaning by sticking a thin metal plate on the inner surface of the vacuum furnace and replacing it after vapor deposition, or by coating the inner surface of the vacuum furnace with a release agent to prevent adhesion of oxides. There is also a method of removing the previous film by a physical impact and shot by sandblasting at a place where masking or the like is not possible due to a complicated shape.

In addition, a vacuum pump type must be selected according to the conditions for evacuating the vacuum furnace, that is, the degree of vacuum. When used in an environment where the degree of vacuum is high (10 ^-1 Torr or higher), a turbo molecular pump or cryopump may be used so that lubricating oil such as an oil rotary pump does not flow back into the furnace due to vacuum. The maintenance state of the pump has a very large weight with respect to the quality of the coating, so it needs to be sufficiently maintained.

The PVD method and the CVD method which are vapor deposition methods formed in the melt spinning apparatus of the present invention will be described in detail below.
(1) PVD method: An ionized vapor deposition apparatus, an ion plating vapor deposition apparatus, a sputtering apparatus, an arc ion plating apparatus, or the like is used as a main apparatus. The metal substrate to be deposited is ionized with a positively charged atom in a vacuum environment, and this is used to apply a negative voltage to the metal substrate using high potential energy. Is drawn and deposited.

An apparatus used in the PVD method performs processing in a vacuum environment using a vacuum furnace. The degree of vacuum once reaches 10 ⁻⁵ to 10 ⁻⁷ Torr, and Ti, nitrogen gas, hydrocarbon gas (acetylene) A gas such as argon gas is introduced as a reaction gas such as gas) or a carrier gas, and the final treatment is performed at 10 ⁻² to 10 ⁻⁴ Torr. Processing temperature is 100-400 degreeC, Preferably it is 100-280 degreeC. By treating in this temperature range, it is possible to prevent deterioration of mechanical properties of the deposited film, thermal deformation, cracks due to stress concentration on the complicated shape portion of the metal substrate, breakage, and the like. The vapor deposition time varies depending on the thickness of the vapor deposition, but is usually 1 to 5 hours.
(2) CVD method: A vacuum furnace is used as in the PVD method, and for example, a thermal CVD apparatus, a direct-current plasma CVD apparatus, a high-frequency plasma CVD apparatus, or the like is used. In this method, the metal base material to be vapor-deposited is heated at normal pressure and a high temperature in a decompression vessel, and a raw material gas is brought into contact with the metal base material, and the surface of the metal base material is vapor-deposited by a chemical reaction. The degree of vacuum at this time first reaches 1 to 10 ⁻⁵ Torr, and then a reaction gas is introduced and finally the processing is performed at normal pressure to 10 ⁻³ Torr. The processing temperature in a thermal plasma apparatus is 500-1200 degreeC, Preferably it is 500-600 degreeC. In addition, the processing temperature in the DC plasma CVD apparatus and the high-frequency plasma CVD apparatus is 100 to 400 ° C., and low-temperature film formation equivalent to the PVD apparatus is possible. The vapor deposition treatment time varies depending on the thickness of the vapor deposition film, but is usually 1 to 5 hours.

  Since the thermal CVD apparatus performs film formation in a high temperature environment, mechanical characteristics are deteriorated, deformation due to thermal strain, and cracks and breakage due to stress concentration are likely to occur in the case of a complicated shape. Therefore, this method is used for applications that require a relatively simple shape and little precision. Regardless of which method is used, the yarn introduction nozzle portion and the heating fluid injection are provided inside the yarn introduction nozzle portion and the heating fluid injection nozzle portion of the melt spinning apparatus of the present invention. In some cases, a deposited film may be formed up to the inside of the nozzle portion, and a method of forming a film from a reactive gas, such as a CVD method, is preferable. Like PVD sputtering, metal is melted in a vacuum furnace, and ions can only travel linearly as in sputtering, so that they reach the inside of the yarn introduction nozzle and the heating fluid injection nozzle. Is difficult. Therefore, when the vapor deposition material is selected as a gas-based material, or when selecting a metal-based material, the arrangement of the ion source and the metal base material is devised, or vapor deposition is performed several times to form a vapor deposition film with a polymer tube. Process.

Next, about the seven examples preferable as a vapor deposition film of the melt spinning apparatus of this invention, the manufacturing method of the vapor deposition film is shown below.
(1) FHC (floric hard coat): A film is formed by an ion plating apparatus of PVD method. A melt spinning apparatus is set on a rotary table of a vacuum furnace, and is rotated in a fixed direction of either forward or reverse at 30 to 100 rpm. Vacuuming is performed with a vacuum pump to a vacuum degree of 10 ⁻³ to 10 ⁻⁶ Torr, argon gas (Ar) is introduced, and the degree of vacuum is controlled to 10 ⁻² to 10 ⁻³ Torr to perform ion cleaning. CF gas (CF ₄ or C ₃ F ₈ ) is introduced into the vacuum furnace from the introduction nozzle. Plasma is generated by applying voltage or high frequency with a hot filament to ionize the CF gas. Evaporated particles that have become positive ions by applying positive voltages to actively moving thermoelectrons are accelerated and collide toward a melt spinning apparatus biased to a negative DC voltage. The evaporated particles that have reached the surface of the melt spinning apparatus are rapidly cooled and solidified to form a film. Moreover, the temperature of the vacuum furnace at the time of a process is 100-400 degreeC, Preferably it processes at 100-250 degreeC.

(2) CFC (fluorinated carbon coating): film formation is performed by a CVD P-CVD apparatus. A melt spinning apparatus is set on a rotary table of a vacuum furnace, and is rotated in a fixed direction of either forward or reverse at 30 to 100 rpm. A vacuum pump is used to reduce the vacuum to 10 ⁻³ to 10 ⁻⁶ Torr, argon gas (Ar) is introduced, and the vacuum is controlled to 10 ⁻² to 10 ⁻³ Torr to perform ion cleaning. A CF-based gas (CF ₄ or C ₃ F ₈ ) and a CH-based gas (C ₆ H ₆ , C ₂ H ₂ or CH ₄ ) are introduced into the vacuum furnace from the introduction nozzle. A high frequency or DC voltage of 13.56 MHz or 27.12 MHz is applied to the melt spinning apparatus, or a high frequency is applied to the electrode, and a DC voltage is further applied to the melt spinning apparatus to generate plasma around the melt spinning apparatus to generate CF. The gas and CH gas are ionized. The CF gas and the CH gas are accelerated by an electric field toward a melt spinning apparatus biased to a negative DC voltage and go straight. The evaporated particles that have reached the surface of the melt spinning apparatus are rapidly cooled and solidified to form a film. Moreover, the temperature of the vacuum furnace at the time of a process is 100-400 degreeC, Preferably it processes at 100-250 degreeC.
(3) DLC (Diamond Like Carbon): There are a method of forming a film using a PVD ion plating apparatus and a method of forming a film using a CVD P-CVD apparatus. First, film formation is performed by the PVD ion plating apparatus. A melt spinning apparatus is set on a rotary table of a vacuum furnace, and is rotated in a fixed direction of either forward or reverse at 30 to 100 rpm. Vacuuming is performed with a vacuum pump to a vacuum degree of 10 ⁻³ to 10 ⁻⁶ Torr, argon gas (Ar) is introduced, and the degree of vacuum is controlled to 10 ⁻² to 10 ⁻³ Torr to perform ion cleaning. A CH gas (C ₆ H ₆ , C ₂ H ₂ or CH ₄ ) is introduced into the vacuum furnace from the introduction nozzle. Plasma is generated by applying voltage or high frequency with a hot filament to ionize CH gas. Evaporated particles that have become positive ions by applying positive voltages to actively moving thermoelectrons are accelerated and collide toward a melt spinning apparatus biased to a negative DC voltage. The evaporated particles that have reached the surface of the melt spinning apparatus are rapidly cooled and solidified to form a film. Moreover, the temperature of the vacuum furnace at the time of a process is 100-400 degreeC, Preferably it processes at 100-250 degreeC. Next, in a method of forming a film with a CVD P-CVD apparatus, a melt spinning apparatus is set on a rotary table of a vacuum furnace, and is rotated at 30 to 100 rpm in either a forward or reverse direction. A vacuum pump is used to reduce the vacuum to 10 ⁻³ to 10 ⁻⁶ Torr, argon gas (Ar) is introduced, and the vacuum is controlled to 10 ⁻² to 10 ⁻³ Torr to perform ion cleaning. A CH gas (C ₆ H ₆ , C ₂ H ₂ or CH ₄ ) is introduced into the vacuum furnace from the introduction nozzle. A high frequency or DC voltage of 13.56 MHz or 27.12 MHz is applied to the melt spinning apparatus, or a high frequency is applied to the electrodes, and a DC voltage is further applied to the melt spinning apparatus to generate plasma around the melt spinning apparatus. The CF gas and the CH gas are accelerated by an electric field toward a melt spinning apparatus biased to a negative DC voltage and go straight. The evaporated particles that have reached the surface of the melt spinning apparatus are rapidly cooled and solidified to form a film. Moreover, the temperature of the vacuum furnace at the time of a process is 100-400 degreeC, Preferably it processes at 100-250 degreeC.
(4) TiBN (titanium boron nitride): The film is formed by a PVD arc ion plating vapor deposition apparatus (AIP) or a sputtering vapor deposition apparatus. A melt spinning apparatus is set on a rotary table of a vacuum furnace, and is rotated in a fixed direction of either forward or reverse at 30 to 100 rpm. Vacuuming is performed with a vacuum pump to a vacuum degree of 10 ⁻³ to 10 ⁻⁶ Torr, argon gas (Ar) is introduced, and the degree of vacuum is controlled to 10 ⁻² to 10 ⁻³ Torr to perform ion cleaning. When a voltage is applied to the electrode, glow discharge occurs, and argon (Ar) is used as a sputtering gas, and a boron (B) and titanium nitride (TiN) metal target is used, or TiB (titanium boron) or TiBN (titanium nitride). Boron) metal target is used. When the plasma is vigorously sputtered on the surface of the metal target, the atoms of the metal target are ejected and the vapor deposition particles become ions. Nitrogen gas is introduced there. The temperature in the vacuum furnace is 200 to 400 ° C, preferably 200 to 250 ° C. Using this, a negative electric charge is caused to flow to the melt spinning apparatus by using a strong potential energy, and atoms are attracted to the surface of the metal substrate at a high speed to form a film on the surface of the melt spinning apparatus.
(5) CrBN (Chromium Boron Nitride): The film is formed by PVD arc ion plating vapor deposition (AIP) or sputtering vapor deposition. A melt spinning apparatus is set on a rotary table of a vacuum furnace, and is rotated in a fixed direction of either forward or reverse at 30 to 100 rpm. Vacuuming is performed with a vacuum pump to a vacuum degree of 10 ⁻³ to 10 ⁻⁶ Torr, argon gas (Ar) is introduced, and the degree of vacuum is controlled to 10 ⁻² to 10 ⁻³ Torr to perform ion cleaning. When a voltage is applied to the electrode, glow discharge occurs, and argon (Ar) is used as the sputtering gas, a boron (B) and chromium nitride (CrN) metal target is used, or CrB (chromium boron) or CrBN (titanium nitride). Boron) metal target is used. Alternatively, when the plasma is vigorously sputtered on the surface of the metal target using a boron (B) and chromium (Cr) target, the atoms of the metal target are ejected and the vapor deposition particles become ions. Nitrogen gas is introduced there. The temperature in the vacuum furnace is 200 to 400 ° C, preferably 200 to 250 ° C. Using this, a negative electric charge is caused to flow to the melt spinning apparatus by using a strong potential energy, and atoms are attracted to the surface of the metal substrate at a high speed to form a film on the surface of the melt spinning apparatus.
(6) SiBN (Silicon Boron Nitride): A film is formed by a PVD arc ion plating vapor deposition apparatus (AIP) or a sputtering vapor deposition apparatus. A melt spinning apparatus is set on a rotary table of a vacuum furnace, and is rotated in a fixed direction of either forward or reverse at 30 to 100 rpm. Vacuuming is performed with a vacuum pump to a vacuum degree of 10 ⁻³ to 10 ⁻⁶ Torr, argon gas (Ar) is introduced, and the degree of vacuum is controlled to 10 ⁻² to 10 ⁻³ Torr to perform ion cleaning. When a voltage is applied to the electrode, glow discharge occurs, argon (Ar) is used as the sputtering gas, boron (B) and silicon nitride (SiN) metal are used as targets, or SiB (chromium boron) or SiBN (silicon nitride). Boron) metal target is used. Alternatively, when the plasma is vigorously sputtered on the surface of the metal target using boron (B) and silicon (Si) targets, the atoms of the metal target are ejected and the deposited particles become ions. Nitrogen gas is introduced there. The temperature in the vacuum furnace is 200 to 400 ° C, preferably 200 to 250 ° C. Using this, a negative electric charge is caused to flow to the melt spinning apparatus by using a strong potential energy, and atoms are attracted to the surface of the metal substrate at a high speed to form a film on the surface of the melt spinning apparatus.
(7) CrN (chromium nitride): The film is formed by a PVD arc ion plating vapor deposition apparatus. The vacuum degree of the vacuum furnace is set to 10 ⁻⁶ to 10 ⁻⁷ Torr, and nitrogen gas is introduced therein. The temperature in the vacuum furnace is 200 to 400 ° C, preferably 200 to 250 ° C. Chromium is placed in the center of the vacuum furnace, and Cr is melted locally by an arc power source. The molten chromium is vaporized in a vacuum environment, and the positively charged chromium atoms are made into an ionic state, and this is used to flow a negative charge to the melt spinning apparatus at a high speed on the surface of the metal substrate using high potential energy. The atoms are attracted and deposited on the surface of the melt spinning apparatus.

  An example of a method for producing melt spinning using the melt spinning apparatus of the present invention is shown below.

  The spinning temperature in the melt spinning method of the present invention is 220 to 400 ° C. Since the spinning temperature is set to a temperature several tens of degrees C. higher than the melting point of the polymer, it is usually a high temperature of about 300.degree. C., but polyimide, polyether ketone, polyether nitrile and the like are spun at a higher temperature of 320.degree. Therefore, the surface of the melt-spun member that is in contact with the melt polymer of the melt-spinning apparatus is formed of a high-hardness vapor-deposited film, so that it has excellent wear resistance and can retain mold release properties even when exposed to high temperatures for a long period of time. Although it is necessary to have heat resistance, the melt-spun member formed with the vapor deposition film of the present invention has both sufficient release properties and heat resistance.

  Also, some polymer tubes, metering pumps, and spinning packs that are in contact with the molten polymer of the melt-spun member, after spinning is completed or after several times of spinning, the molten polymer remaining in the melt-spun member, the melt In order to remove the pyrolyzate of the polymer, the pyrolyzate of metal, and the deposits in the melt-spun member, cleaning and regeneration are performed. Washing and regenerating methods usually include salt decomposition cleaning, burnout cleaning, hydrolytic cleaning with high-temperature steam, and chemical cleaning with strong acid or strong alkali. Then, in order to further clean the spinning pack parts, the metering pump, etc., methods such as washing with steam, hot water, and pressurized water, or washing with ultrasonic vibration in water are performed. Therefore, the surface of the melt-spun member that is in contact with the molten polymer of the melt-spinning apparatus is a material that is stable to high-temperature treatment and / or strong acid and strong alkali treatment during washing and regeneration, and has durability against repeated operations. There has been a need for a melt-spinning member having this, but the melt-spinning apparatus of the present invention satisfies these requirements.

  The melt spinning method using the melt spinning apparatus in which the surface of the melt spinning member in contact with the melt polymer of the present invention is vapor-deposited is the same as the melt spinning method of ordinary industrial fibers. An example is outlined below.

  When melt spinning with an extruder type extruder using nylon 66 chips having a relative viscosity of sulfuric acid of 3.2 to 3.8, the polymer tube of the melt spinning member, the metering pump, the polymer distribution plate of the spin pack, etc. are melted respectively. A member in which the deposited film of the present invention is formed on the surface in contact with the polymer is assembled.

  The spinning temperature is 280 to 310 ° C., and the spinning pack is filtered using a 15 μm metal nonwoven fabric filter and then spun through a melt spinneret hole.

  The spun yarn is surrounded by a heating cylinder having a length of 10 to 50 cm installed immediately below the melt spinneret, and after passing through a high-temperature atmosphere heated to 270 to 350 ° C., cold air at a normal temperature of 10 to 25 ° C. Solidified by cooling. Next, the yarn is provided with a smoothing agent, an electrostatic agent, and an oil agent mainly composed of a surfactant, wound around a take-up roll, and taken up at a predetermined take-up speed. The take-up speed is 300 to 3000 m / min, usually 500 to 2000 m / min. The take-up yarn is wound around a plurality of pair rolls that are sequentially rotated at a high speed without being wound once, and is drawn by a difference in speed between the pair rolls. Usually, after stretching in two or three stages, it is wound with a relaxation treatment. Stretching is performed at a glass transition temperature or higher, and final stretching and heat setting are performed at a high temperature of 230 to 250 ° C. The draw ratio is 2 to 6 times, and the winding speed is 2000 to 6000 m / min.

  Next, although an Example and a comparative example are given and this invention is demonstrated concretely, the evaluation method of each characteristic used for the following Examples is shown.

  (1) Thickness of the deposited film: Measured using a “surfcoder” (SE1700) stylus scanning roughness measuring instrument manufactured by Kosaka Laboratory. A part of the test piece is masked and vapor deposition is performed in a vapor deposition vacuum furnace. After the vapor deposition treatment, the test piece was taken out and the step between the vapor deposition part and the masking part was measured with a stylus scanning roughness measuring instrument.

  (2) Contact angle with water: 2.5 cc of distilled water is dropped onto a test piece made of the same material as the melt spinning member or each part of the melt spinning apparatus, and the contact angle is measured with an automatic contact angle measuring device. did. The measurement was performed in an environment with a temperature of 24 ± 2 ° C. and a humidity of 60 ± 5%. As the automatic contact angle measuring device, “ACT-PRODUCTS” (VCA-OPTIMA apparatus) was used.

  (3) Vapor deposition film hardness: The vapor deposition film part was measured by the Vickers hardness test method of JIS-B7734. As the Vickers hardness tester, “MVK-E” manufactured by Akashi Manufacturing Co., Ltd. was used.

  (4) Volume resistivity: The vapor deposition film part was measured by the method of JIS-K7194. The measuring machine used was a low resistivity meter “Lorestar GP-MCP-T600” manufactured by Mitsubishi Chemical Corporation.

(5) Corrosion resistance: A test piece provided with the same vapor deposition film as the melt-spun member was immersed in a 5% aqueous sodium hydroxide solution at room temperature for 200 hours, then taken out and washed, and the surface corrosion state was observed. The ranking was as follows.
○○ ・ ・ No corrosion (discoloration).
○ ... Some corrosion (discoloration).
Δ: Corrosion (discoloration) is partially present.
X: Corrosion (discoloration) is present throughout.

  (6) Spinning member cleaning cycle: Melt spinning was continued, and the cleaning cycle of each melt-spun member was evaluated in the following manner.

  In the polymer tube, a pressure gauge was always installed at the tip of the screw and the inlet of the lightweight pump in FIG. 1, and the pressure difference was detected online. When foreign matter on the inner wall of the polymer pipe is deposited or deposited on the molten polymer flow path or the like, the inner diameter of the pipe is closed, and the passage of the molten polymer is deteriorated, so that the pressure is lowered. The total number of spinning days until the pressure decrease rate reached 40% was calculated and used as the cleaning cycle of the polymer tube. The total spinning days is “spinning days × spinning times”. Note that the effect of the present invention was relatively shown by doubling the lifetime of Comparative Example 2 according to the prior art.

In the metering pump, the total spinning days until the amount of change in the apparent fineness of the drawn yarn reached 3% or more was calculated and used as the metering pump replacement period.
The total spinning days were evaluated by the same evaluation as in (6), and the effect of the present invention was relatively shown by doubling the life of Comparative Example 2 according to the prior art.

  In the spinning pack, a pressure gauge was always installed at the outlet of the metering pump, and the pressure was detected online. The number of days of spinning until the pressure increase rate reached 50% was calculated and used as the replacement cleaning cycle of the spinning pack. The total spinning days is “spinning days × spinning times”. The total number of spinning days was evaluated in the same manner as in (6), and the effect of the present invention was relatively shown by doubling the life of Comparative Example 2 according to the prior art.

  (7) Melt-spun member life: melt spinning a thermoplastic polymer containing an additive containing a high-hardness metal that is easily worn when continuously spun, and spinning until the vapor deposition film partially loses wear The number of days was calculated as the life of the melt-spun member. In addition, the internal wear of the polymer tube was determined by observing the inside with a CCD camera to determine whether or not the deposited film was worn away. Note that the effect of the present invention was relatively shown by doubling the lifetime of Comparative Example 2 according to the prior art.

(Example 1-7, Comparative Example 1 to 6)
A nylon 66 polymer having a sulfuric acid relative viscosity of 3.7 containing 67 ppm of copper acetate as copper, 0.1% by weight of potassium iodide and 0.1% by weight of potassium bromide was melt-spun at a melting temperature of 300 ° C. The spinning device was melted using an extruder-type spinning machine, filtered through a 15 μm metal nonwoven fabric filter in a melt spinning pack, and then spun from the discharge hole of the melt spinneret. The material of the polymer tube attached to the spinning device is SUS316, the material of the metering pump is SKH51, and the spinning pack member is SUS316. 1 is a melt spinning apparatus of FIG. 1 in which a deposited film is formed on the entire surface (portions 4, 5, and 6 in FIG. 1) of a portion that comes into contact with the molten polymer.

The spinning member cleaning cycle and the melt-spun member life were evaluated as described above. The melt spinneret was an outer diameter of 190φ, a discharge hole diameter of 0.25φ, and a 204 hole melt spinneret. The yarn spun from the melt spinneret passes through a high-temperature atmosphere heated to 300 ° C., and is then cooled and solidified by cold air, applied with an oil agent, and wound around a take-up roller that rotates at a predetermined speed. It was. The take-up yarn was continuously drawn by being wound around a Nelson type rotating roller whose speed was increased sequentially. The take-up roller was not heated, the feed roller was 45 ° C., the one-stage stretching roller was 150 ° C., the two-stage stretching roller was 230 ° C., and two-stage heat stretching was performed. The yarn after hot drawing was subjected to 6% relaxation with a relaxation roller heated to 120 ° C., and then wound with a wind-up winder of 3600 m / min . Hand, Comparative Examples 1 to 3 were silk melt spinning the same nylon 66 polymer and Example under the same conditions. As a result, it Example 1-7 none spinning member cleaning cycle as melt spinning member lifetime of interest, as shown in Table 1 and 2, is extended compared with Comparative Examples 4-6 of the prior art I understand. In Comparative Example 4 , as shown in Table 3, although the life of the melt-spun member was greatly improved, the cleaning period of the spun member was inferior to that of Comparative Examples 5 and 6 as the prior art.

It is for description which shows an example of the melt spinning apparatus flow of the present invention.

Explanation of symbols

1: Screw 2: Barrel 3: Cylinder 4: Polymer tube 5: Metering pump 6: Spin pack 7: Thermoplastic polymer supply port

Claims (9)

An apparatus for melt spinning thermoplastic polymer, wherein a polymer tube of a melt spinning member constituting the apparatus, a metering pump, and at least a part of a surface in contact with the molten polymer of a spin pack member are formed of a deposited film, the vapor deposition film surface contact angle with water from 65 to 115 °, vapor-deposited film hardness (room temperature HV) is 1,500 to 6,000, Ri volume resistivity of 10 ⁺⁵ ~10 ⁺¹⁴ Ω · cm der of the deposited film surface, the deposited film FHC (flow Rick hardcoat), CFC (carbon fluoride coat), that Do from TiBN (titanium nitride boron), CRBN (chromium nitride, boron), at least one selected from the SiBN (silicon nitride boron) A melt spinning apparatus characterized by that. The melt spinning apparatus according to claim 1, wherein a thickness of the deposited film is 0.5 to 15 μm. Ion cleaning is performed on at least a part of the surface of the melt spinning member constituting the melt spinning apparatus that contacts the polymer pipe of the melt spinning member, the metering pump, and the spinning pack member, and the acceleration voltage of the substrate is set to −100 to −3 kV under vacuum. And producing a vapor deposition film by ionizing an organic gas component of a CF-based gas or a CH-based gas. The method for producing a melt spinning apparatus according to claim 3, wherein the deposited film is any one selected from FHC (floric hard coat), CFC (fluorinated carbon coat), and DLC (diamond-like carbon). . The method for producing a melt spinning apparatus according to claim 4, wherein the fluorine addition amount of the FHC (floric hard coat) or CFC (carbon fluoride coat) is 2% or more. Ion cleaning is performed on at least a part of the surface of the melt spinning member constituting the melt spinning apparatus in contact with the molten polymer of the melt spinning member, the metering pump, and the spin pack member, and the acceleration voltage of the substrate is set to −50 to −2 kV under vacuum. And at least one metal component selected from B (boron), Ti (titanium), Cr (chromium), and Si (silicon) is ionized and further substituted with nitrogen to form a deposited film. A method for producing a melt spinning apparatus. The method for producing a melt spinning apparatus according to claim 6, wherein the impurity content of B (boron), Ti (titanium), Cr (chromium), and Si (silicon) is 0.01% or less. The deposited film, TiBN (titanium boron nitride), CRBN (chromium nitride, boron), SiBN (silicon nitride, boron), CrN according to claim 7, characterized in that it consists of at least one selected from (chromium nitride) Manufacturing method of melt spinning apparatus. It is a melt spinning method of a thermoplastic polymer, Comprising: Melt spinning of a thermoplastic polymer is performed using the melt spinning member of any one of the said Claims 1-2 , or any one of Claims 3-8. A melt spinning method comprising: producing a melt spinning apparatus by the production method according to the item, and performing melt spinning of a thermoplastic polymer using the apparatus .

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