JP2008031443A - Polymer alloy chip, polymer alloy fiber, microfiber, and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stably provide a microfiber consisting of a polyolefin by the length of at least 0.2-200 mm in the longitudinal direction. <P>SOLUTION: The polymer alloy chip is a chip which comprises a sea-island structure, wherein the sea-island structure comprises a polymer of at least two or more components, the sea component comprises an aliphatic polyester and the island component comprises a polyolefin as a principal component respectively, the island component is continuously connected in the longitudinal direction of the chip in the shape of a fiber, and the average diameter of island component is 0.01-20 μm. The polymer alloy fiber and the microfiber uses the polymer alloy chip. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymer alloy chip in which the island component is made of polyolefin, in particular polypropylene and polyethylene, and the sea component is made of aliphatic polyester, in particular polylactic acid, and a production method thereof, and a polymer alloy fiber, a production method thereof, and a microfiber to a nanofiber The present invention relates to a fiber relating to a superfine yarn leading up to and a method for producing the fiber.

  Super extra fine yarn made of polyolefin, particularly polypropylene and polyethylene, is used for clothing, automobile materials, industrial materials, agricultural materials, sports materials, or medical materials.

  Conventionally, the synthetic fiber ultrafine yarn has a thin fiber diameter of 10 μm, and has been suitably used as a fiber for clothing and industrial materials by taking advantage of its fineness.

  In particular, these ultrafine yarns are also used as abrasives for members that support information technology including semiconductors and hard disks. Moreover, it is used as a lightweight member as sports material. Furthermore, artificial leather such as suede, nubuck and silver has a unique texture and is used for interior materials such as clothing and furniture.

  Furthermore, fibers having a fiber diameter of several hundreds of nanometers have been studied with the aim of improving characteristics such as adsorptivity and hygroscopicity in addition to the above characteristics by increasing the surface area per weight with ultrafine yarns with finer fineness. . Patent Document 1 discloses a sea-island structure fiber composed of at least two types of organic polymers having different solubility, wherein the island component is composed of a hardly soluble polymer, the sea component is composed of an easily soluble polymer, and the average diameter of the island domain is 1. Polymer alloy fibers having a diameter of ˜150 nm and 60% or more of the island domains having a diameter of 1 to 150 nm are described. In Patent Document 1, a polymer alloy fiber is used in which the melting point of the island polymer is −20 to + 20 ° C., which is the melting point of the sea polymer, and the melt viscosity of the sea polymer is 100 pa · s or less.

  Patent Document 1 describes that ultrafine fibers of 1 to 150 nm are obtained by alkaline dissolution of sea components of these fibers.

Further, Patent Document 2 discloses fibers having a single yarn fineness of 1 × 10 ⁻⁷ to 2 × 10 ⁻⁴ dtex and a fineness ratio of 60% or more of the single yarn fineness of 1 × 10 ⁻⁷ to 2 × 10 ⁻⁴ dtex. Are listed.

Furthermore, Patent Document 3 describes that in a polymer alloy fiber having a sea-island structure made of polypropylene and polylactic acid, the fineness of polypropylene as an island component is 50 μm or less in terms of fiber diameter.
JP 2004-169261 A JP 2004-162244 A JP-T-2002-516622

  However, although the fiber diameter of the fiber obtained from Patent Documents 1 and 2 is on the nano level, the fiber length is very short, a few μm, and it drops off after desealing with alkali to maintain and handle its shape as a fiber. Has become difficult. For this reason, when forming into a non-woven fabric or spinning, extra steps of lamination and mixing with other materials have been required.

  Furthermore, since the fiber length is short, there remains a problem that it falls off even after lamination and mixing with other materials, and there is a problem that the function is lowered after commercialization.

  Patent Document 3 discloses only alloy fibers, and among them, the island component is as thick as a fiber diameter of 50 μm or less, and it is not possible to obtain nano-level fibers.

  The inventors of the present invention have solved the above-mentioned problems of the prior art, studied fibers that can stably and easily process ultrafine fibers and methods for producing the same, and have reached the present invention.

  Therefore, it has been a problem that the ultrafine fiber is long in the length direction by at least 0.2 mm, preferably has a length of 1 mm or more, and can be obtained stably.

In order to achieve the object of solving the above-mentioned problem of dropping of ultrafine fibers, the polymer alloy chip of the present invention has the following configuration.


That is, a chip made of a sea-island structure, which has a sea-island structure made of at least two or more polymers, the sea component containing aliphatic polyester, the island component containing polyolefin as a main component, and the island component This is a polymer alloy chip that is continuously connected in a stripe shape in the longitudinal direction of the chip, and the average diameter of the island component is 0.01 to 20 μm.

Such a polymer alloy chip can be obtained by a method for producing a polymer alloy chip that is extruded in a kneader at 190 to 260 ° C., stretched into a wire shape, and then cooled with water.

  Moreover, in order to achieve the said objective, the polymer alloy fiber of this invention has the following structure. That is, it has a sea-island structure, the sea component is aliphatic polyester, the island component is mainly composed of polyolefin, and the island component is striped in the longitudinal direction, and the average fiber diameter of the island component is 0.001 to 5 μm. A polymer alloy fiber.

Such a polymer alloy fiber is produced by spinning the polymer alloy chip described above at 190 to 260 ° C, or kneading an aliphatic polyester and a polyolefin with a kneader and spinning at 190 to 260 ° C. It can be obtained by a method for producing a polymer alloy fiber.

Furthermore, in order to achieve the said objective, the super extra fine fiber of this invention has the following structure. That is, it is an ultrafine fiber that is obtained from the polymer alloy fiber described above, has an average fiber diameter of 0.001 to 5 μm, has a polyolefin as a main component, and has a streak shape.




Such a super fine fiber can be obtained by a method for producing a super fine fiber in which the polymer alloy fiber is eluted with an alkaline aqueous solution of 0.01 to 5% by weight.

  ADVANTAGE OF THE INVENTION According to this invention, the raw material which can be processed stably and easily can be provided, without a super extra fine fiber dropping out, and the method of manufacturing a super extra fine fiber can be provided.

  In the present invention, the ultrafine fibers are fibers having an average diameter of 1 to 5 μm and are microfibers, and fibers having a diameter of 0.001 to 1 μm are nanofibers.

  According to a first aspect of the present invention, in a chip comprising at least two or more polymers, the sea-island structure, the sea component is aliphatic polyester, the island component is mainly composed of polyolefin, and the island component is longitudinal, that is, longitudinal. It is a polymer alloy chip that is connected in stripes and has an average island component diameter of 0.01 to 20 μm. Here, the average diameter of the island component is preferably 0.02 to 2 μm, and more preferably the average diameter of the island component is 0.05 to 1 μm.

    As the aliphatic polyester used for the sea component of the polymer alloy chip in the present invention, polylactic acid, polyethylene succinate, polypropylene succinate, polybutylene succinate or a copolymer containing them is preferable, Further, polylactic acid or a copolymer thereof is preferable, and polylactic acid is most preferable.

  The sea component is preferably a biodegradable polymer, more preferably a biodegradable aliphatic polyester. In particular, aliphatic polyesters are preferable from the viewpoint of environmental protection because they are quickly decomposed by alkali, easily recover raw materials, and biodegrade.

The polyolefin used for the island component of the polymer alloy chip is preferably one containing polypropylene, polyethylene, polystyrene, or polyvinylidene as a main component, or a copolymer containing them, more preferably polypropylene or polyethylene or a copolymer thereof. Most preferably.
In particular, polypropylene has a melting point close to that of an aliphatic polyester, which is a sea component, and can be easily spun and a polymer having a desired viscosity is easily available.

  The average length of the island component of the polymer alloy chip is preferably at least 0.05 to 100 mm, more preferably 0.1 to 100 mm, further preferably 0.5 to 100 mm, and most preferably 1 to 100 mm. The longer the island component in the polymer alloy chip, the longer the island component in the longitudinal direction during melt spinning.

The variation in the diameter of the island component of the polymer alloy chip is preferably 5 to 35%, and more preferably 10 to 30%.
If the variation of the island component diameter of the polymer alloy chip is large, the island component diameter tends to increase due to the fusion of the island components during spinning.

The ratio of the sea component of the polymer alloy chip is preferably 20 to 80%, more preferably 30 to 70%. Further, the ratio of the island component is preferably 80 to 20%, and more preferably 70 to 30%.
In the polymer alloy chip, if the proportion of the island component is too small, the island component is easily separated, and if the proportion of the island component is too large, the sea island component is easily reversed.

  The polymer alloy chip is preferably a polymer alloy chip whose polymer viscosity of the island component is 50 to 450 Pa · s higher than the polymer viscosity of the sea component at a kneading temperature of 190 to 260 ° C., more preferably 100 to 250 Pa · s. In the present invention, the kneading temperature refers to the temperature at which the aliphatic polyester and polyolefin are kneaded.

  Further, the polymer viscosity of the island component is preferably 100 to 550 Pa · s, more preferably 150 to 350 Pa · s at the kneading temperature.

  Further, the island component has a polymer viscosity of 100 to 550 Pa · s, preferably 150 to 350 Pa · s at a kneading temperature of 190 to 260 ° C., and the sea component has a polymer viscosity of 190 to 260 ° C. The polymer viscosity of the island component is 50 to 450 Pa · s, preferably 100 to 250 Pa · s at a kneading temperature of 190 to 260 ° C. than the polymer viscosity of the sea component. It is preferable that s is high.

  Such a polymer alloy chip is manufactured by a method of melting at 190 to 260 ° C., extruding with a kneader, drawing into a wire, and then cooling with water.

  By adopting the conditions as described above, the island components of the obtained chip are arranged in a stripe shape in the vertical direction. However, the polymer alloy chip of the present invention can be more stably produced by selecting the polymer type, melting temperature, viscosity, and ratio.

  That is, in the conventional polymer alloy chip, the island component is arranged in the form of particles, whereas in the chip of the present invention, the island component is a continuous polymer. Moreover, the method of manufacturing this chip | tip is obtained by extruding with a kneader, extending to a wire form, and cooling with water.

  At this time, the length of the island component varies depending on the dispersion state of the island component and the length of cutting the chip.

Moreover, the factor which arrange | positions an island component in stripe form is as follows.
In the state where the island component and the sea component are in a molten state, the island component mainly composed of polyolefin is dispersed as particles in the sea component mainly composed of aliphatic polyester. Specific heat is higher than other polyethylene terephthalates and polyamides, making it difficult to cool down. The melting point of polyolefin is 130 ° C for polyethylene, 170 ° C for polypropylene, 255 ° C for polyethylene terephthalate, and 225 ° C for poly (ε-caproamide). Since it is low, once the sea component is melted to a temperature at which it melts, the polymer temperature is unlikely to decrease, so it is difficult to solidify and the time to solidification is long.

  The solidification temperature and specific heat of each polymer are, for example, 3.0 J / g for polyethylene at 130 ° C., 3.5 J / g for polyethylene at 170 ° C., 0.21 J / g for polyethylene terephthalate at 260 ° C., poly (ε− Caproamide) is 2.9 J / g at 225 ° C.

  As a result, the polyolefin is stretched by an extruder and is not easily cooled while being cooled with water, so that the polymer dispersed particles in a molten state move and agglomerate and bond in the longitudinal direction in the stretched direction. In the chip, a polymer alloy chip is formed in which island components are formed in stripes in the vertical direction.

  In addition, the diameter of the island component of the chip obtained is controlled by the viscosity and viscosity difference of each of the sea component and the island component, the blending ratio, the shape of the kneader shaft, the rotational speed, the temperature, the discharge amount, and the degassing method. The In particular, the larger the viscosity difference between the island component and the sea component is, the smaller the diameter of the island component is, but the temperature, compounding ratio, kneader shaft shape, rotational speed, temperature, discharge amount, deaeration method, etc. Controlled.

  The length of the island component is also controlled by the viscosity of each of the sea component and the island component, the blending ratio, the shape of the kneading machine shaft, the rotation speed, the temperature, the discharge rate, and the degassing method, so that the kneading rotation speed is high. The finer the dispersion of the particles, the longer the fiber is pulled when the kneading machine extrudes faster.

  Further, the polymer alloy fiber of the present invention is a fiber composed of a polymer of at least two components, and has a sea-island structure, the sea component is aliphatic polyester, the island component is mainly composed of polyolefin, and the island component is streaked in the longitudinal direction. The average fiber diameter of the island components is 0.001 to 5 μm. The average fiber diameter of the island component is preferably 0.002 to 0.5 μm, and more preferably the average fiber diameter of the island component is 0.01 to 0.1 μm.

Further, the sea component of the polymer alloy fiber preferably contains polylactic acid, polyethylene succinate, polypropylene succinate, polybutylene succinate as a main component, or a copolymer containing them, more preferably polylactic acid or a copolymer thereof. Most preferred is lactic acid. Furthermore, the sea component is preferably a biodegradable polymer, more preferably a biodegradable aliphatic polyester.
In particular, aliphatic polyesters are preferable from the viewpoint of environmental protection because they are quickly decomposed by alkali, easily recover raw materials, and biodegrade.

The polyolefin that is an island component of the polymer alloy fiber is preferably one containing polypropylene, polyethylene, polystyrene, or polyvinyl as a main component or a copolymer containing them, more preferably polypropylene or polyethylene or a copolymer thereof. Is most preferred.
In particular, polypropylene has a melting point close to that of an aliphatic polyester, which is a sea component, and can be easily spun and a polymer having a desired viscosity is easily available.

Furthermore, the average length of the island component of the polymer alloy fiber is preferably at least 0.1 to 200 mm, more preferably 0.2 to 200 mm, further preferably 1 to 200 mm, and further preferably 2 to 200 mm.
If the island component in the polymer alloy fiber is not long, the ultrafine fiber after sea removal will not be long.


Furthermore, the variation in the diameter of the island component of the polymer alloy fiber is preferably 5 to 35%, and more preferably 10 to 30%.
If the variation of the island component diameter of the polymer alloy chip is large, the island component diameter tends to increase due to the fusion of the island components during spinning.

Furthermore, the ratio of the sea component of the polymer alloy fiber is preferably 20 to 80%, more preferably 30 to 70%. Further, the ratio of the island component is preferably 80 to 20%, and more preferably 70 to 30%.
In the polymer alloy fiber, when the proportion of the island component is too small, it is easily separated, and when the proportion of the island component is too large, the sea island component is easily reversed.

  Further, a polymer alloy chip having an island component polymer viscosity of 50 to 450 Pa · s higher than the polymer viscosity of the sea component of the polymer alloy fiber at a blending temperature of 190 to 260 ° C. is preferable, and a polymer alloy chip higher by 100 to 250 Pa · s is more preferable.

  The polymer viscosity of the island component is preferably 100 to 550 Pa · s, more preferably 150 to 350 Pa · s at a kneading temperature of 190 to 260 ° C.

  Furthermore, the polymer viscosity of the island component is 100 to 550 Pa · s, preferably 150 to 350 Pa · s at a kneading temperature of 190 to 260 ° C., and the polymer viscosity of the sea component is 190 to 260 ° C. 50 to 500 Pa · s, preferably 50 to 250 Pa · s, and the polymer viscosity of the island component is 50 to 450 Pa · s, preferably 100 to 250 Pa · s at a kneading temperature of 190 to 260 ° C. than the polymer viscosity of the sea component. High is preferred.

  This polymer alloy fiber is manufactured by melting and spinning the polymer alloy chip at a melting temperature of 190 to 260 ° C.

  At this time, the fiber diameter, dispersion variation state, and fiber length of the island component are specified from the state of the island component in the chip to be used. Further, by re-kneading with an extruder or the like at the time of spinning, the fiber diameter and dispersion state of the island components are changed, and the fibers can be made longer.

  In addition, the above-described polymer alloy fiber can be produced by kneading an aliphatic polyester and a polyolefin with a kneader directly connected to an extruder or the like, and directly spinning without using a polymer alloy chip.

  The method for spinning the polymer alloy fiber in the present invention is preferably melt spinning such as staple, filament, spunbond, and melt blow. Furthermore, in the polymer alloy fiber obtained by filament, spun bond, and melt blow, the fiber is not cut, so that the island component can be longer than 200 mm.

  In addition, the factor that the island components are arranged in stripes in the vertical direction is the same as that of the alloy chip. In other words, when the alloy fiber spun from the die is stretched by drawing and cooled, the polymer dispersed particles in the molten state move and longitudinally move in the stretched direction if the island component is a polymer that does not cool easily. In the polymer alloy fiber, the island component becomes a streaky polymer alloy fiber in the polymer alloy fiber.

  That is, the ultra-fine fiber of the present invention has an average fiber diameter obtained from the polymer alloy fiber of 0.001 to 5 μm, is mainly composed of polyolefin, and has a stripe shape. Furthermore, the diameter of the fiber is preferably 0.002 to 0.5 μm, and more preferably 0.01 to 0.1 μm.

Further, this ultrafine fiber has a polyolefin as a main component, and as the polyolefin, one containing polypropylene, polyethylene, polystyrene, polyvinyl as a main component or a copolymer containing them is preferable, and further polypropylene or polyethylene or a copolymer thereof. Polymerization is preferred, with polypropylene being most preferred.
Polyolefin is difficult to be decomposed in an alkaline solution, and thus is easily left as a fiber by sea removal treatment.

  The average length of the ultrafine fibers is preferably at least 0.1 to 200 mm, more preferably 0.2 to 200 mm, further preferably 1 to 100 mm, and further preferably 2 to 100 mm. Furthermore, since the polymer alloy fiber obtained by filament, spun bond, and melt blow is not cut, the ultrafine fiber can be longer than 200 mm.

  Furthermore, the variation in the fiber diameter of this fiber is preferably 5 to 35%, and more preferably 10 to 30%. A smaller dispersion of island components in the polymer alloy fiber is preferable because the island components are less likely to increase.

Further, at a kneading temperature of 190 to 260 ° C., the polymer viscosity is preferably 100 to 550 Pa · s, more preferably 150 to 350 Pa · s.
This is an appropriate viscosity for arranging the island components in the polymer alloy fibers in the form of streaks in the longitudinal direction, and the viscosity of the ultrafine fiber after sea removal is substantially equal to the viscosity of the island components in the polymer alloy fibers.

This fiber is produced by a method in which the polymer alloy fiber is eluted with 0.01 to 5% by weight alkaline aqueous solution. The alkaline aqueous solution is preferably a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, or an ammonia aqueous solution.
Moreover, 20-100 degreeC may be sufficient as aqueous alkali solution, Preferably 40 to 80 degreeC is preferable.

  Moreover, the time until elution is controlled by the type, concentration, and temperature of the alkaline aqueous solution. In particular, if the concentration of the aqueous alkali solution is too low, the sea removal rate is slow and inefficient, and if it is too high, the sea removal rate is fast and the ultrafine fibers may become brittle.

  The ultra-fine fibers obtained by the present invention are used for clothing, automobile materials, industrial materials, agricultural materials, or medical materials. Further, it can be used for sports applications, material applications, and automobile interior materials, and in particular, mirror polishing of semiconductor parts, mirror polishing of hard disk storage materials, liquid filters, air filters, battery separators, capacitors, catalyst holders, and the like. Examples of sports applications include sports equipment as a lightweight member.

The present invention will be specifically described below with reference to examples.
In the present invention, each characteristic can be measured as follows.
<Polymer viscosity>
The melt viscosity of the polymer is measured using a melt flow viscometer. The polymer storage time from the introduction of the polymer to the start of measurement is 10 minutes. In the examples, Toyo Seiki Capilopirograph 1B was used as the melt flow viscometer.
<Average diameter of island component of polymer alloy chip, average diameter and average fiber diameter of island component of polymer alloy fiber>
A section of the sample cooled to −20 ° C. is cut in the fiber cross-sectional direction and measured with a scanning electron microscope (SEM) apparatus. What measured the diameter of the island component and 100 fibers, and calculated | required the average value is the average diameter of the island component of a polymer alloy chip | tip, the average diameter of the island component of a polymer alloy fiber, and an average fiber diameter. In the examples, Hitachi S-4000 type was used as the SEM apparatus.
<Average length of island component of polymer alloy chip, average length of island component of polymer alloy fiber, and average fiber length>
A section of the sample cooled to −20 ° C. is cut in the longitudinal direction of the fiber and measured with an SEM apparatus. The average length of the island component and 100 fibers is measured and the average value obtained is the average length of the island component of the polymer alloy chip, the average length of the island component of the polymer alloy fiber, and the average fiber length. In the examples, Hitachi S-4000 type was used as the SEM apparatus.
<Variation of island component of polymer alloy chip, variation of fiber diameter of island component of polymer alloy fiber, and variation of fiber diameter of fiber>
The standard deviation is obtained from 100 pieces of data used for calculating the average diameter. The variation is represented by the standard deviation of diameter / average diameter × 100 Example 1
Polypropylene having a viscosity of 500 Pa · s at 220 ° C. and polylactic acid having a viscosity of 150 Pa · s at 220 ° C. The ratio of polypropylene to polylactic acid is 40% by weight of polypropylene and 60% by weight of polylactic acid. The polymer alloy chip 1 is obtained by kneading at 220 ° C. while degassing at 0.001 MPa with a φ25 mm biaxial vent extruder, stretching the extruded polymer into a wire shape, cooling it with water, and then cutting it. Was obtained (FIG. 1).
The obtained polymer alloy chip consists of an island component 2 made of polypropylene and a sea component 3 made of polylactic acid around it. The average diameter of the island component 2 made of polypropylene in the obtained polymer alloy chip is 0.1 μm, the average length of the island component 2 is 5 mm, and the variation of the diameter of the island component 2 is 7%.

  This polymer alloy chip 1 was melted at 220 ° C. with a general pressure melter type melting device, and the single-hole discharge amount was 1 through a spinneret having a hole diameter of 0.35 mm, a discharge hole length of 0.70 mm, and 300 holes. Spinning was performed at a polymer temperature of 230 ° C. at a rate of 0.0 g / min, the yarn was cooled with a cooling air of 20 ° C., and once placed in a can at a take-up speed of 1200 m / min, an undrawn yarn was obtained. The obtained undrawn yarn was subjected to two-stage drawing at a draw ratio of 2.7 times using a warm bath at 80 ° C., and the obtained drawn yarn was machined at 8 to 15 pieces / 25 mm using a stuffing box. Crimping was applied, oil was applied by spraying, and the obtained tow was dried at a temperature of 90 ° C. for 10 minutes and cut to a length of 50 mm to obtain a polymer alloy fiber 4 having a fiber length of 5 dTex and a length of 50 mm (see FIG. 2). As shown in the enlarged view of FIG. 2, the obtained polymer alloy fiber 4 has an average fiber diameter of 0.02 μm of the island component 2 of polypropylene, an average length of the island component 2 of 22 mm, and is a fiber of the island component 2 The variation in diameter is 8%, and the sea component 3 is made of polylactic acid.

  The obtained polymer alloy fiber 4 was immersed in 0.02 wt% sodium hydroxide aqueous solution at 50 ° C. for 5 hours. The average fiber diameter of polypropylene was 0.03 μm and the average fiber length of polypropylene was 21 mm. An ultrafine fiber 5 having a diameter variation of 15% and a polymer viscosity at 220 ° C. of 490 Pa · s was obtained (FIGS. 3 and 4). From the raw material polypropylene, ultrafine fibers 5 having a fiber diameter of nanofibers were stably obtained with a yield of 93%.

Example 2
In Example 1, polypropylene was changed to polyethylene having a polymer viscosity of 190 Pa · s at 210 ° C., and polylactic acid was changed to polylactic acid having a polymer viscosity of 80 Pa · s at 210 ° C. A polymer alloy chip 1 was obtained in the same manner as in Example 1 except that lactic acid was changed to kneading at 210 ° C. as a proportion of 70% by weight. The average diameter of the island component 2 made of polyethylene of the obtained polymer alloy chip is 0.5 μm, the average length of the island component 2 is 3 mm, and the variation of the diameter of the island component 2 is 30%.

  A polymer alloy fiber 4 having a fiber length of 5 dTex and a fiber length of 50 mm was obtained in the same manner as in Example 1 except that the obtained polymer alloy chip was used and the melting temperature was changed to 210 ° C. As shown in the enlarged view of FIG. 2, the obtained polymer alloy fiber 4 has an average fiber diameter of polyethylene island component 2 of 0.1 μm, an average length of island component 2 of 14 mm, and an island component 2 fiber. The variation in diameter is 31%, and the sea component 3 is made of polylactic acid.

  The obtained polymer alloy fiber 4 was immersed in a 0.1% by weight 30 ° C. aqueous potassium hydroxide solution for 2 hours, the average fiber diameter of polyethylene was 0.1 μm, the average fiber length of polyethylene was 14 mm, and the polyethylene fibers An ultrafine fiber 5 having a diameter variation of 29% and a polymer viscosity at 210 ° C. of 185 Pa · s was obtained. From the raw material polyethylene, ultrafine fibers 5 having a fiber diameter of nanofibers were stably obtained with a yield of 91%.

Example 3
In Example 1, polypropylene was changed to polypropylene having a viscosity of 250 Pa · s at 220 ° C., polylactic acid was changed to polylactic acid having a viscosity of 220 Pa · s at 220 ° C., and 80% by weight of polypropylene and polylactic acid were changed. A polymer alloy chip 1 was obtained in the same manner as in Example 1 except that the ratio was changed to 20% by weight.
The average diameter of the island component 2 made of polypropylene of the obtained polymer alloy chip is 12 μm, the average length of the island component 2 is 19 mm, and the variation of the diameter of the island component 2 is 15%.

  A polymer alloy fiber 4 having a fiber length of 5 dTex and a length of 100 mm was obtained in the same manner as in Example 1 except that the obtained polymer alloy chip was used and the fiber was cut into a length of 100 mm. As shown in the enlarged view of FIG. 2, the obtained polymer alloy fiber 4 has an average fiber diameter of 2.1 μm of the island component 2 of polypropylene, an average length of the island component 2 of 95 mm, and is a fiber of the island component 2 The variation in diameter is 15%, and the sea component 3 is made of polylactic acid.

  The obtained polymer alloy fiber 4 was immersed in an aqueous solution of ammonium at 0.5% by weight at 20 ° C. for 5 hours. The average fiber diameter of polypropylene was 2.2 μm, the average fiber length of polypropylene was 95 mm, and the fiber diameter of polypropylene was An ultrafine fiber 5 having a variation of 16% and a polymer viscosity of 220 Pa · s at 220 ° C. was obtained. The ultrafine fiber 5 having a fiber diameter of microfiber was stably obtained from the raw material polypropylene with a yield of 91%.

Example 4
In Example 1, polypropylene is changed to polyvinyl chloride having a polymer viscosity of 250 Pa · s at 240 ° C., polylactic acid is changed to polylactic acid having a polymer viscosity of 100 Pa · s at 240 ° C., and polyvinyl chloride is 20 A polymer alloy chip 1 was obtained in the same manner as in Example 1 except that the kneading at 240 ° C. was changed to a proportion of 80% by weight of polylactic acid by weight.
The average diameter of the island component 2 made of polyvinyl chloride of the obtained polymer alloy chip is 1.0 μm, the average length of the island component 2 is 0.5 mm, and the variation of the diameter of the island component 2 is 30%.

  A polymer alloy fiber 4 having a fiber length of 5 dTex and a length of 50 mm was obtained in the same manner as in Example 1 except that the obtained polymer alloy chip was used. The obtained polymer alloy fiber 4 has an average fiber diameter of 0.3 μm of the island component 2 of polyvinyl chloride, an average length of the island component 2 of 1.5 mm, as shown in the enlarged view of FIG. The fiber diameter variation of component 2 is 31%, and sea component 3 is made of polylactic acid.

  The obtained polymer alloy fiber 4 was immersed in a 0.1% by weight 30 ° C. aqueous potassium hydroxide solution for 2 hours. The average fiber diameter of polyvinyl chloride was 0.3 μm, and the average fiber length of polyvinyl chloride was 1. The ultrafine fiber 5 having a fiber diameter variation of 31% at 5 mm and a polymer viscosity at 240 ° C. of 220 Pa · s was obtained. From the raw material polyvinyl chloride, the ultrafine fiber 5 having a fiber diameter of nanofibers was stably obtained with a yield of 83%.

Example 5
In Example 1, polypropylene was changed to polystyrene having a viscosity of 300 Pa · s at 260 ° C., polylactic acid was changed to polylactic acid having a viscosity of 260 Pa · s at 110 Pa · s, polystyrene was 20% by weight, and polylactic acid was A polymer alloy chip 1 was obtained in the same manner as in Example 1 except that the kneading at 260 ° C. was changed to a ratio of 80% by weight. The average diameter of the island component 2 made of polystyrene of the obtained polymer alloy chip is 5 μm, the average length of the island component 2 is 0.8 mm, and the variation of the average diameter of the island component 2 is 30%.

  A polymer alloy fiber 4 having a fiber length of 5 dTex and a length of 50 mm was obtained in the same manner as in Example 1 except that the obtained polymer alloy chip was used and melted at 260 ° C. As shown in the enlarged view of FIG. 2, the obtained polymer alloy fiber has an average fiber diameter of 1.1 μm of polystyrene island component 2, a length of island component 2 of 3.6 mm, and a fiber diameter of island component. The sea component 3 is made of polylactic acid.

  The obtained polymer alloy fiber 4 was immersed in an aqueous 0.2% by weight ammonium solution at 30 ° C. for 2 hours. The average fiber diameter of the polystyrene island component 2 was 1.1 μm, and the average fiber length of polystyrene was 3.5 mm. Thus, the ultrafine fiber 5 having a polystyrene fiber variation of 31% and a polymer viscosity at 260 ° C. of 290 Pa · s was obtained. From the raw material polystyrene, ultrafine fibers 5 having a fiber diameter of microfibers were stably obtained with a yield of 85%.

Example 6
In Example 1, polypropylene was changed to polyethylene having a viscosity at 210 ° C. of 280 Pa · s, polylactic acid was changed to polypropylene succinate having a viscosity at 210 ° C. of 130 Pa · s, and 50% by weight of polyethylene was obtained. A polymer alloy chip 1 was obtained in the same manner as in Example 1 except that the composition was changed to kneading at 210 ° C. at a rate of 50% by weight of the nate. The average diameter of the island component 2 made of polyethylene of the obtained polymer alloy chip is 10 μm, the average length of the island component 2 is 1.0 mm, and the variation of the diameter of the island component 2 is 29%.

  A polymer alloy fiber 4 having a fiber length of 5 dTex and a length of 50 mm was obtained in the same manner as in Example 1 except that the obtained polymer alloy chip was used and melted at 210 ° C. As shown in the enlarged view of FIG. 2, the obtained polymer alloy fiber 4 has an average fiber diameter of 2.1 μm of the polyethylene island component 2, an average length of the island component 2 of 2.5 mm, and the island component 2. The fiber diameter variation is 31%, and the sea component 3 is made of polypropylene succinate.

  The obtained polymer alloy fiber 4 was immersed in a 0.2% by weight 30 ° C. aqueous potassium hydroxide solution for 1 hour, the average fiber diameter of polyethylene was 2.1 μm, the average fiber length of polyethylene was 2.5 mm, and polyethylene The ultra-fine fiber 5 having a fiber diameter variation of 29% and a polymer viscosity at 210 ° C. of 270 Pa · s was obtained. From the raw material polyethylene, the ultrafine fiber 5 having a micro-level fiber diameter was stably obtained with a yield of 82%.

Example 7
In Example 1, polypropylene was changed to polyethylene having a polymer viscosity of 180 Pa · s at 190 ° C., polylactic acid was changed to polyethylene succinate having a polymer viscosity of 190 Pa · s at 190 ° C., and 20% by weight of polyethylene. A polymer alloy chip 1 was obtained in the same manner as in Example 1 except that the proportion of polyethylene succinate was changed to kneading at 190 ° C. at a ratio of 80% by weight. The average diameter of the island component 2 made of polyethylene of the obtained polymer alloy chip is 1 μm, the average length of the island component 2 is 5 mm, and the variation of the diameter of the island component 2 is 14%. A polymer alloy fiber 4 having a fiber length of 5 dTex and a length of 50 mm was obtained in the same manner as in Example 1 except that the melting temperature was changed to 190 ° C. The obtained polymer alloy fiber 4 has an average fiber diameter of 0.3 μm for the island component 2 of polyethylene, a length of 15 mm for the island component 2 and a fiber diameter of the island component 2 as shown in the enlarged view of FIG. The sea component 3 is made of polyethylene succinate.

  The obtained polymer alloy fiber 4 was immersed in a 0.1 wt% aqueous solution of potassium hydroxide at 30 ° C. for 1 hour, the average fiber diameter of polyethylene was 0.3 μm, the average fiber length of polyethylene was 14 mm, and the polyethylene fibers The variation in diameter was 15%, and the polymer viscosity at 190 ° C. was 175 Pa. An ultrafine fiber 5 of s was obtained. The ultrafine fiber 5 having a nanofiber diameter was stably obtained from the raw material polyethylene at a yield of 83%.

Example 8
In Example 1, polypropylene was changed to polypropylene having a viscosity of 210 Pa · s at 220 ° C., polylactic acid was changed to polybutylene succinate having a viscosity of 80 Pa · s at 220 ° C., polystyrene was 60% by weight, polyethylene succin A polymer alloy chip 1 was obtained in the same manner as in Example 1 except that the amount of the nitrate was changed to 40% by weight.
The average diameter of the island component 2 made of polypropylene of the obtained polymer alloy chip is 8 μm, the average length of the island component 2 is 1.1 mm, and the variation of the diameter of the island component 2 is 29%. A polymer alloy fiber 4 having a fiber length of 5 dTex and a length of 50 mm was obtained in the same manner as in Example 1 except that the chip was used.
As shown in the enlarged view of FIG. 2, the obtained polymer alloy fiber 4 has an average fiber diameter of 2.5 μm for the island component 2 of polypropylene, the length of the island component 2 is 4.1 mm, and is an island component fiber. The variation in diameter is 29%, and the sea component 3 is made of polybutylene succinate.

  The obtained polymer alloy fiber 4 was immersed in a 0.2% by weight 30 ° C. aqueous sodium hydroxide solution for 2 hours, the polypropylene average fiber diameter was 2.4 μm, the polypropylene average fiber length was 4.0 mm, 220 An ultrafine fiber 5 having a polymer viscosity at 200 ° C. of 200 Pa · s and a fiber diameter variation of 30% was obtained. From the raw material polypropylene, the ultrafine fiber 5 having a fiber diameter of microfiber was stably obtained with a yield of 85%.

Example 9
Polypropylene having a viscosity of 350 Pa · s at 220 ° C. and polylactic acid having a viscosity of 180 Pa · s at 220 ° C. The ratio of polypropylene to polylactic acid polymer is 30% by weight for polypropylene and 70% by weight for polylactic acid. A single-hole discharge amount through a spinneret with a hole diameter of 0.35 mm, a discharge hole length of 0.70 mm and a 300 hole while kneading at 220 ° C. while degassing at 0.001 MPa with a φ25 mm biaxial vent extruder Was spun at a polymer temperature of 230 ° C. at 1.0 g / min, the yarn was cooled with a cooling air of 20 ° C., and once put in a can at a take-up speed of 1200 m / min, an undrawn yarn was obtained. The obtained undrawn yarn was subjected to two-stage drawing at a draw ratio of 2.7 times using a warm bath at 80 ° C., and the obtained drawn yarn was machined at 8 to 15 pieces / 25 mm using a stuffing box. Crimping was applied, oil was applied by spraying, and the obtained tow was dried at a temperature of 90 ° C. for 10 minutes and cut to a length of 50 mm to obtain a polymer alloy fiber 4 having a fiber length of 5 dTex and a length of 50 mm (see FIG. 2). As shown in the enlarged view of FIG. 2, the obtained polymer alloy fiber 4 has an average fiber diameter of 0.08 μm of the island component 2 of polypropylene, an average length of the island component 2 of 15 mm, and is a fiber of the island component 2 The variation in diameter is 10%, and the sea component 3 is made of polylactic acid.

  The obtained polymer alloy fiber 4 was immersed in a 0.05% by weight sodium hydroxide aqueous solution at 50 ° C. for 3 hours. The average fiber diameter of polypropylene was 0.08 μm and the average fiber length of polypropylene was 14 mm. An ultrafine fiber 5 having a diameter variation of 11% and a polymer viscosity at 220 ° C. of 340 Pa · s was obtained. From the raw material polypropylene, ultrafine fibers 5 having a fiber diameter of nanofibers were stably obtained with a yield of 93%.

Comparative Example 1
In Example 1, polypropylene was changed to poly (ε-caproamide) having a viscosity at 250 ° C. of 250 Pa · s, polylactic acid was changed to polylactic acid having a viscosity at 250 ° C. of 120 Pa · s, and poly ( Polymer alloy chips were obtained in the same manner as in Example 1 except that kneading was performed at 250 ° C. in a proportion of 50% by weight of ε-caproamide) and 50% by weight of polylactic acid.
The average diameter of the island component made of poly (ε-caproamide) of the obtained polymer alloy chip is 0.8 μm, the average length of the island component is 0.8 μm, and the variation of the diameter of the island component is 29%. A polymer alloy fiber having a fiber length of 5 dTex and a length of 50 mm was obtained in the same manner as in Example 1 except that the polymer alloy chip thus obtained was used and the melting temperature was 250 ° C.

The obtained polymer alloy fiber has an average fiber diameter of the poly (ε-caproamide) island component of 0.25 μm, the length of the island component is 4 μm, and the variation of the fiber diameter of the island component is 30%. The component consists of polylactic acid.

  The obtained polymer alloy fiber was immersed in a 0.2 wt% sodium hydroxide aqueous solution at 40 ° C. for 2 hours, the average fiber diameter of poly (ε-caproamide) was 0.25 μm, and the average of poly (ε-caproamide) The fiber length was 4 μm, the fiber length was very short, and nanofibers with a poly (ε-caproamide) fiber diameter variation of 29% were obtained, and ultrafine fibers having a viscosity at 250 ° C. of 240 Pa · s were obtained. From the raw material poly (ε-caproamide), an ultrafine fiber having a fiber diameter of nanofiber having a long fiber length with a yield of 82% was not obtained.

Comparative Example 2
In Example 1, polypropylene was changed to polypropylene having a viscosity of 100 Pa · s at 230 ° C., and polylactic acid was changed to polylactic acid having a viscosity of 300 Pa · s at 230 ° C. A polymer alloy chip was obtained in the same manner as in Example 1 except that lactic acid was kneaded at 230 ° C. at a ratio of 10% by weight.
The average diameter of the island component made of polylactic acid of the obtained polymer alloy chip is 100 μm, the average length of the island component is 0.1 mm, and the variation in the diameter of the island component is 40%. A polymer alloy fiber having a fiber length of 5 dTex and a length of 50 mm was obtained in the same manner as in Example 1 except that the melting temperature was 230 ° C. The obtained polymer alloy fiber had polypropylene as a sea component and polylactic acid as an island component.

  As a result of immersing the obtained polymer alloy fiber in 0.5% by weight of 30 ° C. aqueous sodium hydroxide solution for 2 hours, the obtained poly (ε-caproamide) is a microporous 3dTex fiber having a fiber length of 50 mm. There was no nanofiber.

Comparative Example 3
In Example 1, polypropylene was changed to polyethylene terephthalate having a viscosity of 450 Pa · s at 290 ° C., and polylactic acid was changed to polylactic acid having 80 Pa · s at 250 ° C. A polymer alloy chip was obtained in the same manner as in Example 1 except that lactic acid was mixed at 290 ° C. at a rate of 40% by weight, but polylactic acid could not be decomposed.

Comparative Example 4
In Example 1, polypropylene was changed to polypropylene having a viscosity of 610 Pa · s at 230 ° C. and polylactic acid was changed to polylactic acid having a viscosity of 40 Pa · s at 230 ° C. Chips were obtained in the same manner as in Example 1 except that lactic acid was kneaded at 230 ° C. at a ratio of 95% by weight.

  The obtained chip was not in a polymer alloy state because polypropylene was separated.

  The ultra-fine fiber having a fiber diameter of nanofiber to microfiber of the present invention is used for clothing, automotive materials, industrial materials, agricultural materials, or medical materials. Further, it can be used for sports applications, material applications, and automobile interior materials, and examples thereof include mirror polishing of semiconductor parts and mirror polishing of hard disk storage materials. Examples of sports applications include sports equipment as a lightweight member.

The schematic perspective view which shows the one aspect | mode of the polymer alloy chip | tip of this invention, and its schematic sectional drawing The schematic perspective view which shows the one aspect | mode of the polymer alloy fiber of this invention, and its schematic sectional drawing Cross-sectional SEM photographic image of the polymer alloy fiber obtained in Example 1 Side SEM photographic image of the ultrafine fiber obtained in Example 1

Explanation of symbols

1: Polymer alloy chip 2: Island component

3: Sea component 4: Polymer alloy fiber 5: Super fine fiber

Claims (23)

  A chip composed of a sea-island structure, which is a sea-island structure composed of a polymer of at least two components, wherein the sea component contains aliphatic polyester, the island component contains polyolefin as a main component, and the island component is a chip. A polymer alloy chip that is continuously connected in a stripe shape in the longitudinal direction and has an average island component diameter of 0.01 to 20 μm.   The polymer alloy chip according to claim 1, wherein the average length of the island components is 0.1 to 100 mm.   The polymer alloy chip according to claim 1 or 2, wherein the aliphatic polyester is at least one selected from polylactic acid or copolymer thereof, and the polyolefin is at least one selected from polypropylene or polyethylene or copolymer thereof.   The polymer alloy chip according to any one of claims 1 to 3, wherein the island component has a diameter variation of 5 to 35%.   The polymer alloy chip according to any one of claims 1 to 4, wherein the ratio of the sea component is 20 to 80% and the ratio of the island component is 80 to 20%.   The polymer alloy chip according to any one of claims 1 to 5, wherein the polymer viscosity of the island component is 50 to 450 Pa · s higher than that of the sea component at a kneading temperature of 190 to 260 ° C.   The polymer alloy chip according to claim 6, wherein the island component has a polymer viscosity of 100 to 550 Pa · s and the sea component has a polymer viscosity of 50 to 500 Pa · s at a kneading temperature of 190 to 260 ° C.   A method for producing a polymer alloy chip according to any one of claims 1 to 7, wherein the polymer is extruded with a kneader at 190 to 260 ° C, stretched into a wire shape, and then cooled with water.   It has a sea-island structure, the sea component contains aliphatic polyester, the island component contains polyolefin as a main component, and the island component has a stripe shape in the longitudinal direction, and the average fiber diameter of the island component is 0.001 to 5 μm. A polymer alloy fiber.   The polymer alloy fiber according to claim 9, wherein the average length of the island components is at least 0.2 to 200 mm.   The polymer alloy fiber according to claim 9 or 10, wherein the aliphatic polyester is at least one selected from polylactic acid or copolymer thereof, and the polyolefin is at least one selected from polypropylene or polyethylene or copolymer thereof.   The polymer alloy fiber according to any one of claims 9 to 11, wherein an island component has a diameter variation of 5 to 35%.   The polymer alloy fiber according to any one of claims 9 to 12, wherein a ratio of the sea component is 20 to 80% and a ratio of the island component is 80 to 20%.   The polymer alloy fiber according to any one of claims 9 to 13, wherein the polymer viscosity of the island component is 50 to 450 Pa · s higher than the polymer viscosity of the sea component at a kneading temperature of 190 to 260 ° C.   The polymer alloy fiber according to claim 14, wherein the island component has a polymer viscosity of 100 to 550 Pa · s and the sea component has a polymer viscosity of 50 to 500 Pa · s at a kneading temperature of 190 to 260 ° C.   The manufacturing method of the polymer alloy fiber which spins the polymer alloy chip | tip in any one of Claims 1-7 at 190-260 degreeC, and obtains the polymer alloy fiber in any one of Claims 9-15.   The manufacturing method of the polymer alloy fiber which knead | mixes aliphatic polyester and polyolefin with a kneading machine, and spins at 190-260 degreeC, and obtains the polymer alloy fiber in any one of Claims 9-15.   An ultrafine fiber obtained from the polymer alloy fiber according to any one of claims 9 to 15, having an average fiber diameter of 0.001 to 5 µm, a polyolefin as a main component, and a stripe shape.   The ultrafine fiber according to claim 18, wherein the average fiber length is 0.2 to 200 mm.   20. The ultrafine fiber according to claim 18 or 19, wherein the polyolefin is at least one selected from polypropylene, polyethylene or a copolymer thereof.   21. The ultrafine fiber according to any one of claims 18 to 20, wherein a variation in fiber diameter is 5 to 35%.   The ultrafine fiber according to any one of claims 18 to 21, wherein a polymer viscosity of the fiber is 100 to 550 Pa · s at a kneading temperature of 190 to 260 ° C.   The manufacturing method of the ultrafine fiber which obtains the ultrafine fiber in any one of Claims 18-22 by eluting the polymer alloy fiber in any one of Claims 9-15 with 0.01-5 weight% alkaline aqueous solution.