JP5724521B2 - Nanofiber mixed yarn - Google Patents

Description

  The present invention relates to a nanofiber mixed yarn in which a dispersibility of a nanofiber single fiber is good and a fabric excellent in wiping performance and scratch performance can be obtained.

  Ultrafine fibers (microfibers) having a single fiber diameter of several micrometers are widely used as polishing cloths and wiping cloths against the background of the specific surface area and the fineness of voids. As a technique for easily producing these microfibers, a sea-island type composite fiber containing an island component composed of a hardly soluble polymer in a sea component composed of a readily soluble polymer, or a hardly soluble polymer is an easily soluble polymer. A method using a split fiber type composite fiber partitioned is widely known (see Patent Documents 1 and 2). In these methods, the above-mentioned sea-island type composite fiber or split-fiber type composite fiber is wound up once, and then the resulting composite fiber or a fabric product comprising the composite fiber is immersed in a solubilizer to make it easily soluble. This is a technique that makes it possible to remove a polymer and obtain a microfiber made of a hardly soluble polymer.

  In recent years, ultra-fine fibers (nanofibers) having a single fiber diameter of less than 1 micrometer have been proposed in pursuit of a more delicate touch and soft feeling. In addition to the ultimate softening due to the fiber diameter scale-down, nanofibers have been suggested to have a dramatic increase in specific surface area of single fiber groups and nanosize-specific effects due to fine dispersion of voids. It has the potential to expand beyond fiber and requires early research, development, and stable manufacturing.

  An electrospinning method has been proposed as one method for producing nanofibers. The electrospinning method is a method of taking out nanofibers by discharging into a field while applying a voltage to a solution containing a resin as a solute (see Patent Document 3). However, in this method, since it is difficult to collect the released nanofibers as long fibers, the use thereof is limited to non-woven fabrics such as filters, and it is also difficult to control the fiber diameter and arrangement. It was. In addition, this method has a problem in that there is a risk of electric shock, poisoning, and ignition because a high voltage is required and the solvent is always volatilized.

  In addition, as another method for producing nanofibers, a method based on a combination of a polymer blend technique and a polymer dissolution and removal technique has been proposed (see Patent Document 4). Since the nanofibers produced by this method are short fibers but form an aggregate, the long fibers can be made into a fabric product such as a woven fabric or a knitted fabric. However, in this method, it is difficult to control the single fiber diameter of the nanofibers, and the strength is low because of the aggregate of short fibers, and the wear resistance is low due to fibrillation and dropping, which is practical as a fabric product. There was a problem that it was not.

  As a means of developing long-fiber nanofibers that can be applied to woven fabrics and knitted fabrics, overcoming the inferior durability and quality issues that have been problematic in the above-mentioned conventional technologies, in recent years, the sea-island type composite spinning technology has been deepened. It has been broken.

  As an example, a highly soluble nano-polyester, which is a copolymer of 5-sodium sulfoisophthalic acid and polyethylene glycol, is used, and the island component arrangement in the sea-island type composite monofilament is further defined. A fiber manufacturing method has been proposed (see Patent Documents 5 and 6). However, the nanofibers exemplified in these conventional techniques cause aggregation of single fibers due to the high specific surface area, and as a result, they can only behave as a single fiber group, and the characteristics as nanofibers are sufficient. There was a problem that it could not be demonstrated.

  As a method for solving the above-mentioned problem, a method has been proposed in which high-shrinkage yarns are mixed into nanofibers, thereby causing swelling of the nanofiber single fiber group and improving the dispersibility of the single fiber ( (See Patent Document 7). Certainly, this method greatly increases the specific surface area of the single fiber group, increases the voids of the single fiber group, and improves the softness. However, in this method, since the high shrinkage yarn has a large fineness, the soft feeling peculiar to nanofibers is partially impaired, and the high shrinkage yarn having a large fineness is partially exposed on the surface of the yarn, and wiping is performed. When used as a cloth, there was a problem that the object to be polished may be scratched. In addition, since polyethylene terephthalate copolymerized with isophthalic acid or the like is used as the high shrinkage yarn, the high shrinkage yarn also melts when the sea component polymer is dissolved in an alkali, the strength is greatly reduced, and it can be used as a product. It was not.

Japanese Patent Laying-Open No. 2005-163234 (Claims) Japanese Patent Publication No. 48-28005 (Claims) JP 2007-303015 (Claims) JP 2004-162244 A (Claims) Japanese Patent Application Laid-Open No. 2007-100343 (Claims) Japanese Patent Application Laid-Open No. 2007-1003003 (Claims) JP 2007-262610 A (Claims)

  Accordingly, an object of the present invention is to provide a nanofiber mixed yarn that overcomes the above-described problems of the prior art and that can provide a fabric having excellent dispersibility of nanofiber monofilaments and excellent wiping performance and scratch performance. There is.

The present invention is intended to achieve the above object, and the nanofiber mixed yarn of the present invention is a mixed yarn composed of two or more kinds of polyester long fibers having different yarn lengths. both fiber diameter Ri 50~900nm der a nanofiber combined filament yarn in which the yarn length difference, characterized in 5-100% der Rukoto.

  According to a preferred aspect of the nanofiber mixed yarn of the present invention, at least one kind of the polyester long fibers is a long fiber made of polypropylene terephthalate or polybutylene terephthalate.

  According to the preferable aspect of the nanofiber mixed yarn of the present invention, the elongation elastic modulus at 20% elongation of the nanofiber mixed yarn is 70% or more.

  ADVANTAGE OF THE INVENTION According to this invention, the dispersibility of a nanofiber single fiber is favorable and the nanofiber mixed yarn which can provide the fabric excellent in the wiping performance and the scratch performance can be obtained.

  The nanofiber mixed yarn of the present invention is a mixed yarn composed of two or more kinds of polyester long fibers. Two or more kinds of polyester long fibers constituting the nanofiber mixed yarn of the present invention are required to have a single fiber diameter of 50 to 900 nm.

  By setting the single fiber diameter of the polyester long fiber to 900 nm or less, the wiping performance is greatly improved due to the high frictional force and the high adsorption effect accompanying the increase in the specific surface area. In addition, since the nanofiber mixed yarn of the present invention is a mixed yarn of nanofibers, both the single fiber and the single fiber group consisting of single fibers are excellent in softness, and include the existing thick fine yarn. The scratch performance that could not be achieved can be achieved. In order to obtain further excellent wiping performance and scratch performance, the single fiber diameter is preferably 800 nm or less.

  On the other hand, by setting the single fiber diameter of the polyester continuous fiber to 50 nm or more, it is possible to maintain the strength of the nanofiber single fiber and to obtain a nanofiber mixed yarn excellent in wear resistance. By improving the wear resistance, it is possible to suppress the generation of foreign matters formed by agglomeration of single nanofiber fibers that have fallen off during wiping with abrasive grains and polishing scraps, thereby reducing scratches. A more preferable single fiber diameter is 100 nm or more.

Two or more kinds of polyester long fibers constituting the nanofiber mixed yarn of the present invention are different in the length of each polyester long fiber contained per unit length of the nanofiber mixed yarn . When each polyester long fiber has a yarn length difference, the polyester long fiber having a long yarn length is loosened or swollen, and a dispersion effect is exhibited in the single fiber. Due to the dispersion of the single fibers, the specific surface area of the single fiber group is greatly increased, wiping performance is improved, and excellent scratch performance can be achieved by increasing the softness of the single fiber group.

The yarn length difference is 5 to 100% . By setting the yarn length difference to be 5% or more, the dispersion effect can be expressed in the single fiber. The yarn length difference is more preferably 10% or more. On the other hand, when the yarn length difference is 100% or less, excessive loosening of the single fiber group and single fiber can be suppressed, and a fiber excellent in unwinding property and wear resistance can be obtained. The yarn length difference is more preferably 80% or less. Here, the yarn length difference is a value calculated using the following equation.
(L1-Ls) / Ls × 100
Ll: the length of the longest polyester continuous fiber Ls: the length of the shortest polyester continuous fiber (where Ll and Ls are the lengths of the respective polyesters contained in the nanofiber mixed yarn cut into 10 cm at an arbitrary position) About the fiber, the average value which measured the length of the single fiber 50 points or more is shown.)
As a method for obtaining the above-described difference in yarn length, for example, there are a method of supplying one fiber excessively at the time of fiber mixing, a method of mixing fibers having different shrinkage properties, and performing a shrinkage treatment. Among them, a method of mixing fibers having different shrinkages is preferable because it is excellent in the effect of dispersing single fibers and can be easily mixed from the viewpoint of cost and productivity.

  The polyester for forming the nanofiber mixed yarn of the present invention may be any polyester having fiber-forming properties, and may be a copolyester. In particular, polyethylene terephthalate (hereinafter sometimes referred to as PET) and polypropylene terephthalate (hereinafter referred to as PPT) may be easily formed into fibers by melt spinning, and from the viewpoint of excellent physical properties as fibers. ), Polybutylene terephthalate (hereinafter sometimes referred to as PBT) and copolyesters thereof are preferred, among which polypropylene terephthalate and polybutylene terephthalate are preferably used.

  In addition, inorganic fine particles, organic compounds, and carbon black can be added to the above polyester as matting agents, flame retardants, lubricants, antioxidants, coloring pigments, and the like, if necessary.

The two or more kinds of polyester long fibers constituting the nanofiber mixed yarn of the present invention may be a combination of long fibers made of polyesters having different compositions, or polyesters having the same composition with different intrinsic viscosities and shrinkage rates. You may combine the long fiber which consists of.
Next, examples of combinations of polyester long fibers are listed. For example, by combining a long fiber made of low-shrinkage PET and a long fiber made of copolymerized PET having high shrinkage, a yarn length difference is manifested by the shrinkage treatment, and the nanofiber single fiber has excellent dispersibility. A fiber yarn can be formed easily. The above-mentioned PET may be another polyester, and the above-mentioned copolymerized PET may be a homopolyester imparted with high shrinkage by a method such as low temperature and / or low draw ratio.

  Among them, it is preferable to use a long fiber made of PPT or PBT having stretch properties as at least one kind of polyester long fibers, and a long fiber made of PPT or PBT imparted with high shrinkage to other polyesters such as PET. By blending the resulting long fibers and subjecting them to a shrinking treatment, a blended yarn in which looseness and swelling are expressed in the long fibers made of PET is obtained. Thereby, against the weak external stress such as bending and twisting, the long fiber side made of PPT or PBT can absorb the external stress due to the stretch property, and the long fiber side made of PET can absorb the external stress by loosening, A nanofiber mixed yarn having excellent softness and scratching performance can be obtained. On the other hand, against strong external stresses such as scratching and pulling, the slackness of the long fibers made of PET is extended, and the excellent strength of the long fibers made of PET improves the form stability and wear resistance. Excellent nanofiber mixed yarn. In order to obtain the yarn length difference, it is preferable to combine polyester long fibers having a difference in boiling water shrinkage of 5 to 50%.

  It is preferable that the number of filaments of the two or more types of polyester long fibers constituting the nanofiber mixed yarn of the present invention is 3000 or more. By setting the number of filaments to 3,000 or more, a large number of filaments can be mixed closely with each other during mixing, so that an excellent dispersion effect can be obtained. More preferably, it is 6000 or more, more preferably 10,000 or more.

  Moreover, it is preferable that the polyester long fiber which comprises a nanofiber mixed fiber is contained 20 mass% or more, respectively. By setting the blend ratio to 20% by mass or more, the characteristics of each polyester long fiber can be expressed. A more preferable fiber mixing ratio is 30% by mass or more.

  The nanofiber mixed yarn of the present invention is composed of two or more kinds of polyester long fibers. According to the mixing ratio, the number of the polyester long fibers is preferably 2 to 5, more preferably 2 to 3.

  The nanofiber mixed yarn of the present invention preferably has a stretching elastic modulus at 20% elongation of 70% or more. By setting the elongation modulus to 70% or more, excellent softness due to stretch properties is expressed, and the fiber has excellent scratch performance. The elongation elastic modulus at 20% elongation is more preferably 80% or more.

  The nanofiber constituting the nanofiber mixed yarn of the present invention preferably uses a sea-island type composite fiber as a precursor from the viewpoint of yarn production stability and quality. Further, the nanofiber mixed yarn can be produced by mixing in the state of the sea-island type composite fiber and then performing a sea removal treatment to remove sea components. When nanofibers are mixed with each other after the sea-island type composite fiber is desealed, quality deterioration such as reduced yield and fluff is likely to occur due to deterioration of process passability. By doing so, the quality abnormality can be suppressed.

  It is important for the combination of the sea component and island component polymer of the sea-island type composite fiber so that the difference in dissolution rate in the dissolving agent used for sea removal treatment is as large as possible, and the island component polymer is completely dissolved in the dissolving agent. It is preferable that the dissolution rate of the sea component is not less than 5 times the dissolution rate of the island component. By making the dissolution rate difference 5 times or more, the dissolution and removal of the sea component is executed smoothly, and the difference in the contact time of the island component solubilizer at the surface / core portion of the sea-island composite single fiber is reduced. Can obtain nanofiber mixed yarn with small size. A more preferable dissolution rate difference is 20 times or more.

  As the polyester constituting the island component, it is preferable to use a homopolyester excellent in dissolution resistance and decomposition resistance from the viewpoint that strength reduction during sea removal treatment can be suppressed.

  On the other hand, as the polymer constituting the sea component, polyethylene, polypropylene, polystyrene, sodium sulfoisophthalic acid, polyethylene glycol, etc. are used because they have chemical properties that are more soluble and degradable than the polyester that constitutes the island component. It is preferable to use copolymerized polyester, polylactic acid, thermoplastic PVA resin, thermoplastic cellulose resin, or the like as a copolymerization component.

  As the solvent for dissolving the sea component, when the sea component is polyethylene, polypropylene and polystyrene, an organic solvent such as toluene or trichloroethylene is used. When the sea component is a copolymerized polyester or polylactic acid, sodium hydroxide or the like is used. An aqueous alkali solution can be used. Further, when the sea component is a thermoplastic PVA resin or a thermoplastic cellulose resin, the sea component can be dissolved using hot water. Among these, a copolyester and polylactic acid are preferable as the sea component because both the spinning performance and the ease of sea removal treatment can be achieved.

It is preferable that any of the polyester long fibers constituting the nanofiber mixed yarn of the present invention has a sea-island type composite fiber as a precursor. When sea components of mixed yarn of sea-island type composite fibers are desealed, the sea-island type composite fibers are subjected to sea-sealing treatment according to the longest sea-season completion time among the sea-island type composite fibers that are composed. It is preferable that the difference in the sea removal completion time is 20% or less. By setting the difference in seawater removal completion time of each sea-island type composite fiber to 20% or less, dissolution of island components can be suppressed, and a nanofiber mixed yarn having high fiber strength with small fiber diameter variation can be obtained. . On the other hand, when the seawater removal completion time difference exceeds 20%, or the mixed fiber component is a single yarn, the island component is dissolved, the fiber diameter variation is large, and the mixed fiber is remarkably reduced in strength. A more preferable difference in the sea removal completion time is 10% or less. Here, the sea removal completion time difference is a value calculated using the following equation.
_{(T l -t s) / t} s × 100
t ₁ : The longest seawater removal completion time t _s : The shortest seawater removal completion time (however, in the present invention, the time required to reduce the weight by multiplying the sea component ratio of the sea-island type composite fiber by 1.1 times) And the sea removal completion time.)
The single fiber fineness of the sea-island type composite fiber used in the present invention is preferably 1.5 dtex or less. When the single fiber fineness of the sea-island type composite fiber is 1.5 dtex or less, each fiber can be finely mixed when mixed in the state of the sea-island type composite fiber. Increases the dispersion effect. In addition, the cooling spots on the surface / core part of the sea-island type composite fiber can be reduced, and the specific surface area of the sea-island type composite fiber can be increased to increase the dissolution rate of sea components. Since the difference in the contact time of the island component with the solubilizer at the core portion is reduced, a single fiber diameter variation is small, and a high-strength nanofiber mixed yarn can be obtained. Furthermore, in order to obtain a nanofiber mixed yarn having a high dispersion effect of the nanofiber single fiber, little variation in fiber diameter, and little reduction in strength, the single fiber fineness is preferably 1.0 dtex or less, and stable yarn production. In order to maintain the properties, it is preferable that the single fiber fineness is 0.3 dtex or more.

  The number of islands in the single fiber in the sea-island composite fiber used in the present invention is preferably in the range of 30 to 400 islands. When the number of islands is 30 or more, the island components can be arranged in the sea component without gaps, so that the shape stability of the sea-island type composite fibers and the productivity of the nanofibers are increased. Further, by setting the number of islands to 400 or less, it is possible to avoid the island component fusion defect, and further, there is a difference in the contact time of the dissolving agent at the surface / core portion of the sea-island type composite single fiber at the time of sea component dissolution removal. Therefore, it becomes possible to obtain a nanofiber mixed yarn having a small fiber diameter variation and high strength. A more preferable range of the number of islands is 60 to 300 islands.

  The island component ratio of the sea-island composite fiber of the present invention is preferably in the range of 50 to 90% by mass. By setting the island component ratio to 90% by mass or less, fusion between island components can be prevented, and a high-strength and high-quality fabric can be obtained. Moreover, if an island component ratio is 50 mass% or more, it is possible to shorten sea component melt | dissolution removal time, and the productivity of nanofiber is also high. A more preferable range of the island component ratio is 55 to 80% by mass.

  Next, a preferable production method for obtaining the nanofiber mixed yarn of the present invention will be described.

  The nanofiber of the present invention preferably uses a sea-island type composite fiber as a precursor. Sea-island type composite fiber is not only a two-step method in which the discharged polymer is once wound as an undrawn yarn and then drawn, but also any process such as a direct spinning drawing method or a high-speed spinning method in which spinning and drawing steps are performed continuously. Can also be manufactured. When yarns are produced by the two-step method, any known drawing method can be used in addition to hot roll-hot roll drawing or drawing using a hot pin. The heat setting temperature in the stretching step is preferably 120 to 200 ° C. in order to obtain a low shrinkage fiber, and preferably 90 to 120 ° C. in order to obtain a highly shrinkable fiber.

  The nanofiber mixed yarn of the present invention is preferably premixed in the state of a sea-island type composite fiber before sea removal treatment. The blending method may be a spinning blend that is blended simultaneously with spinning, or may be a post-blend after each sea-island type composite fiber is taken up separately. As post-mixing, an air-mixing method such as interlacing or Taslan processing is suitable. An interlace is particularly suitable for a combination of fibers having different shrinkages. The number of entanglements is preferably 10 to 60 / m.

  The obtained mixed yarn of sea-island type composite fibers is subjected to sea removal treatment using a solubilizer, and then subjected to shrinkage treatment using hot water or hot air, whereby nanofiber mixed yarn can be obtained. In that case, although a solubilizer changes with sea components, it is preferable to use an aqueous solution system such as an alkaline aqueous solution from the viewpoint of reducing environmental burden. In addition, the shrinking treatment may be performed at any timing after the fiber mixing, but is preferably performed simultaneously with the seawater removal treatment or after the seawater removal treatment, so that the nanofiber single fibers can be effectively dispersed. is there.

  By such a production method, a nanofiber mixed yarn excellent in dispersibility of single fibers can be obtained.

  A fabric such as a woven fabric or a knitted fabric obtained from the nanofiber mixed yarn of the present invention is suitably used as a polishing cloth for a substrate such as a hard disk or a silicon wafer, a wiping cloth such as an electronic device or glass.

  Next, the present invention will be described in more detail with reference to examples. The physical property values in the examples are measured by the following methods.

(1) Intrinsic Viscosity 0.8 g of sample polymer is dissolved in 10 mL of o-chlorophenol (OCP) having a purity of 98% or more, and a relative viscosity η _r is obtained by the following formula using an Ostwald viscometer at a temperature of 25 ° C. Intrinsic viscosity was calculated. This was measured at three points and the average value was used.
η _r = η / η ₀ = (t × d) / (t ₀ × d ₀ )
Intrinsic viscosity = 0.0242 η _r +0.2634
Where η: viscosity of polymer solution, η ₀ : OCP viscosity, t: solution drop time (seconds), d: solution density (g / cm ³ ), t ₀ : OCP drop time (seconds), d ₀ : Density of OCP (g / cm ³ ).

(2) Single fiber diameter of the polyester long fiber The single fiber diameter of the polyester long fiber was measured by observing the cross section of the single fiber group with a scanning electron microscope (SEM), and randomly extracting 300 or more randomly within the same cross section. Single fiber diameter was measured. This was performed with a group of at least 5 single fibers, and the diameter of a total of 1500 or more single fibers was measured, and the average value was obtained. These measurement positions are preferably performed at a distance of 10 m or more in the longitudinal direction of the fiber from the viewpoint of assuring the uniformity of the obtained fiber product.

(3) Polyester long fiber yarn length difference Nanofiber mixed yarn is cut into 10 cm at an arbitrary location, and for each polyester long fiber contained therein, the length of the single fiber is measured at least 50 points. The average value was defined as yarn lengths L ₁ and L _s . The yarn length difference was calculated from the obtained L ₁ and L _{s according} to the following formula.
(L ₁ −L _s ) / L _s × 100
L ₁ : Length of the longest polyester long fiber L _s : Length of the shortest polyester long fiber.

(4) Elongation elastic modulus The elongation elastic modulus was measured by setting the elongation elastic modulus 8.9B method of JIS L1013 (2010) to 20%.

(5) Boiling water shrinkage after desealing treatment Hot water dimensions specified in JIS L 1013 (2010) 8.18.1B method after sea-island type composite fiber is desealed at a temperature at which shrinkage does not occur. Measured according to the rate of change.

(6) Wiping performance Using a mixed yarn of sea-island type composite fibers, warp knitted fabrics were prepared so that the warp yarn density and the weft yarn density were equal and the total cover factor (CF) was 1900-2100.
Total CF = Vertical CF + Horizontal CF
Warp CF = Warp Yarn Fineness (dtex) ^1/2 x Warp Yarn Density (line / 2.54cm)
Horizontal CF = Weft fineness (dtex) ^1/2 x Weft density (lines / 2.54cm)
Subsequently, it was subjected to sea removal treatment using a 2% by mass sodium hydroxide aqueous solution at a temperature of 80 ° C., then immersed in boiling water at a temperature of 98 ° C., and then dried. A wiping test was carried out using the obtained woven fabric with a glass plate uniformly coated with silicone compound (SC-554 manufactured by Toray Dow Corning) as a wiping sample. Five inspectors visually check the glass plate after wiping, there is almost no wiping residue (4 points), there is little wiping residue (3 points), wiping residue is seen (2 points), many wiping The wiping performance was evaluated in four stages (1 point) where a residue was observed, and the following evaluation was performed according to the average value of each inspector. Rounded to the first decimal place. “◯◯” of 3.5 points or more and “◯” of less than 3.5 points of 2.7 points or more were regarded as passing.
◯: 3.5 points or more ◯: less than 3.5 points 2.7 points or more ×: less than 2.7 points

(7) Scratch performance The woven fabric prepared in the above item (6) is formed into a tape shape having a width of 4 cm, and a free abrasive slurry in which single crystal diamond particles having a primary particle diameter of 1 to 10 nm are clustered with a cluster average diameter of 100 nm is used. A 3.5 inch aluminum substrate was polished. The polishing conditions were a substrate rotation speed of 300 rpm, a tape running speed of 5 cm / min, and a polishing time of 10 seconds. With respect to the substrate surface after polishing, a groove having a depth of 2 nm or more was scratched using an optical surface analyzer. The number of scratches was measured on both surfaces of five substrates, and the scratch performance was evaluated in three stages by the average value of the number. The scratch performance is better when the value is smaller. Less than 50 “◯ ○” and 50 or more “◯” were less than 100.
○○: Less than 50 ○: 50 or more and less than 100 ×: 100 or more.

Example 1
Using PET with an intrinsic viscosity of 0.71 as the island component and PET with 7.3% by mass of 5-sodiumsulfoisophthalic acid having an intrinsic viscosity of 0.55 as the sea component, the number of islands is 127 islands and holes Using a sea-island type composite spinneret having a number of 112, melt spinning was performed under the conditions of an island component ratio of 70% by mass, a spinning temperature of 290 ° C., and a winding speed of 1500 m / min to obtain an undrawn yarn. Subsequently, the obtained undrawn yarn was drawn under conditions of a winding speed of 500 m / min, a preheating temperature of 90 ° C., and a heat setting temperature of 160 ° C. to obtain a sea-island composite fiber (fiber 1) of 75 dtex-112 filaments.

  On the other hand, melt spinning was performed in the same manner as the fiber 1 except that the island component was PPT having an intrinsic viscosity of 1.14. The obtained undrawn yarn was drawn under conditions of a winding speed of 500 m / min, a drawing temperature of 90 ° C., and a heat setting temperature of 100 ° C. to obtain a sea-island type composite fiber (fiber 2) of 75 dtex-112 filaments. The difference in the sea removal completion time between the obtained fiber 1 and fiber 2 was 8%.

  The obtained fiber 1 and fiber 2 are interlaced and then immersed in a 2% by weight aqueous sodium hydroxide solution at a temperature of 80 ° C. to dissolve and remove the sea component and perform a temporary shrinkage treatment. The shrinkage was completed by immersing and drying in boiling water. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 1 is 550 nm, the fiber diameter of the fiber 2 is 580 nm, the yarn length difference is 10%, and the elongation elastic modulus at 20% elongation is 86%. Met. The resulting nanofiber blended yarn has excellent dispersibility of single fibers, and the resulting woven fabric of nanofiber blended yarn has excellent wiping performance and scratch performance, which is sufficient for use as a product. It had a good performance. The results are shown in Table 1.

(Example 2)
Except that the island component ratio of fiber 1 and fiber 2 was 80% by mass, spinning and stretching were performed in the same manner as in Example 1, and sea-island type composite fibers (fiber 3 and fiber 4) of 140 dtex-112 filaments were obtained. Obtained. The difference in the sea removal completion time between the obtained fiber 3 and fiber 4 was 5%.

  The obtained fibers 3 and 4 were mixed in the same manner as in Example 1 and subjected to sea removal and shrinkage treatment. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 3 is 800 nm, the fiber diameter of the fiber 4 is 850 nm, the yarn length difference is 11%, and the elongation elastic modulus at 20% elongation is 88%. Met. The obtained nanofiber mixed yarn was excellent in dispersibility of single fibers as in Example 1, and the woven fabric made of the obtained nanofiber mixed yarn was excellent in both wiping performance and scratch performance. The results are shown in Table 1.

(Example 3)
Except that the island component ratio of fiber 1 and fiber 2 was 30% by mass, spinning and stretching were performed in the same manner as in Example 1 to obtain sea-island type composite fibers (fibers 5 and 6) of 44 dtex-112 filaments, respectively. Obtained. The difference in completion time of sea removal between the obtained fiber 5 and fiber 6 was 4%.

  The obtained fiber 5 and fiber 6 were mixed in the same manner as in Example 1 and subjected to sea removal and shrinkage treatment. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 5 is 280 nm, the fiber diameter of the fiber 6 is 290 nm, the yarn length difference is 10%, and the elongation elastic modulus at 20% elongation is 85%. Met. The obtained nanofiber mixed yarn was excellent in dispersibility of single fibers as in Example 1, and the woven fabric made of the obtained nanofiber mixed yarn was excellent in both wiping performance and scratch performance. The results are shown in Table 1.

Example 4
After four fibers 6 produced in Example 3 were combined, the fiber 3 produced in Example 2 was mixed with fiber in the same manner as in Example 1 and subjected to sea removal treatment and shrinkage treatment. The difference in the sea removal completion time between fiber 3 and fiber 6 was 15%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 3 is 800 nm, the fiber diameter of the fiber 6 is 290 nm, the yarn length difference is 10%, and the elongation elastic modulus at 20% elongation is 74%. there were. The obtained nanofiber mixed yarn was excellent in dispersibility of single fibers as in Example 1, and the woven fabric made of the obtained nanofiber mixed yarn was excellent in wiping performance. On the other hand, since the difference in the sea removal completion time was larger than that in Example 1, the scratch performance did not reach that of Example 1 due to the dropout of some fibers, but it was sufficient for use as a product. The results are shown in Table 1.

(Example 5)
After four fibers 5 produced in Example 3 were combined, the fibers 4 produced in Example 2 and the fibers 4 produced in Example 2 were mixed in the same manner as in Example 1 and subjected to sea removal and shrinkage treatment. The difference in the sea removal completion time between fiber 4 and fiber 5 was 18%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 4 was 850 nm, the fiber diameter of the fiber 5 was 280 nm, the yarn length difference was 11%, and the elongation elastic modulus at 20% elongation was 89%. . The obtained nanofiber mixed yarn was excellent in dispersibility of single fibers as in Example 1, and the woven fabric made of the obtained nanofiber mixed yarn was excellent in wiping performance. On the other hand, since the difference in the sea removal completion time was larger than that in Example 1, the scratch performance did not reach that of Example 1 due to the dropout of some fibers, but it was sufficient for use as a product. The results are shown in Table 1.

(Comparative Example 1)
Spinning and drawing were performed in the same manner as in Example 1 except that the number of islands of fiber 1 and fiber 2 was 70, the number of holes was 9, and the island component ratio was 80% by mass. Both were 44 dtex-9 filaments Sea-island type composite fibers (fibers 7 and 8) were obtained. The difference in the sea removal completion time between the obtained fiber 7 and fiber 8 was 4%.

  The obtained fibers 7 and 8 were mixed in the same manner as in Example 1 and subjected to sea removal treatment and shrinkage treatment. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 7 is 2140 nm, the fiber diameter of the fiber 8 is 2240 nm, the yarn length difference is 10%, and the elongation elastic modulus at 20% elongation is 86%. Met. In the obtained nanofiber mixed yarn, a part of the single fiber was dispersed, but the woven fabric made of the obtained nanofiber mixed yarn was inferior in both wiping performance and scratch performance because the single fiber diameter was large. It was. The results are shown in Table 1.

(Comparative Example 2)
The fiber 2 was spun and drawn in the same manner as in Example 1 except that the fiber 2 was not a sea-island type composite fiber but a PPT single fiber having an intrinsic viscosity of 1.14, and a single fiber (fiber 9) of 56 dtex-24 filament was obtained. It was. The obtained fiber 9 was combined with the fiber 1 produced in Example 1, mixed as in Example 1, and subjected to sea removal treatment and shrinkage treatment. The resulting mixed yarn containing nanofibers has a fiber diameter of fiber 1 of 550 nm, a fiber diameter of fiber 9 of 13900 nm, a yarn length difference of 11%, and an elongation modulus at 20% elongation of It was 88%. The resulting mixed yarn containing nanofibers was excellent in dispersibility, but the fabric made of the obtained nanofiber mixed yarn had low softness and part of the fibers 9 were exposed on the surface. The wiping performance and scratch performance were inferior. The results are shown in Table 1.

(Comparative Examples 3 and 4)
The fiber 1 and the fiber 2 produced in Example 1 were each subjected to sea removal treatment and shrinkage treatment individually to obtain nanofibers. In any of the obtained nanofibers, single fibers were not dispersed, and the woven fabric made of the obtained nanofibers was inferior in wiping performance and scratch performance. The results are shown in Table 1.

(Example 6)
Except that the island component of the fiber 2 was PBT having an intrinsic viscosity of 0.88, spinning and stretching were performed in the same manner as in Example 1 to obtain a sea-island composite fiber (fiber 10) of 75 dtex-112 filaments. The obtained fiber 10 was combined with the fiber 1 produced in Example 1, mixed as in Example 1, and subjected to sea removal treatment and shrinkage treatment. The difference in seawater removal completion time between fiber 1 and fiber 10 was 3%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 1 is 550 nm, the fiber diameter of the fiber 10 is 570 nm, the yarn length difference is 7%, and the elongation modulus at 20% elongation is 58%. there were. Since the obtained nanofiber blended yarn and the woven fabric comprising the obtained nanofiber blended yarn have lower dispersibility and softness of the single fiber than in Example 1, the wiping performance and scratch performance are in Example 1. However, it was sufficient for use as a product. The results are shown in Table 2.

(Example 7)
Except that the island component of the fiber 1 was PBT having an intrinsic viscosity of 0.88, spinning and stretching were performed in the same manner as in Example 1 to obtain a sea-island composite fiber (fiber 11) of 75 dtex-112 filaments. The obtained fiber 11 was combined with the fiber 2 produced in Example 1, mixed in the same manner as in Example 1, and subjected to sea removal treatment and shrinkage treatment. The difference in the sea removal completion time between the obtained fiber 2 and fiber 11 was 4%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 2 is 580 nm, the fiber diameter of the fiber 11 is 550 nm, the yarn length difference is 10%, and the elongation elastic modulus at 20% elongation is 91%. there were. The obtained nanofiber mixed yarn was excellent in dispersibility of single fibers as in Example 1, and the woven fabric made of the obtained nanofiber mixed yarn was excellent in both wiping performance and scratch performance. The results are shown in Table 2.

(Example 8)
Except that the island component of the fiber 1 was PPT having an intrinsic viscosity of 1.14, spinning and stretching were performed in the same manner as in Example 1 to obtain a sea-island composite fiber (fiber 12) of 75 dtex-112 filaments. The obtained fiber 12 was combined with the fiber 10 produced in Example 6, mixed as in Example 1, and subjected to sea removal treatment and shrinkage treatment. The difference in seawater removal completion time between the obtained fiber 10 and fiber 12 was 2%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 10 is 570 nm, the fiber diameter of the fiber 12 is 550 nm, the yarn length difference is 5%, and the elongation modulus at 20% elongation is 67%. there were. The resulting nanofiber blended yarn and the woven fabric composed of the nanofiber blended yarn have a single fiber dispersibility and softness lower than those of Example 1, so that the wiping performance and scratch performance are the same as in Example 1. Although it did not keep pace, it was sufficient for use as a product. The results are shown in Table 2.

Example 9
Spinning was performed in the same manner as in Example 1 except that the island component of the fiber 2 was PET obtained by copolymerizing 7.1 mol% of isophthalic acid having an intrinsic viscosity of 0.67 and 4.4 mol% of an ethylene oxide adduct of bisphenol A. The film was stretched to obtain a sea-island type composite fiber (fiber 13) of 75 dtex-112 filament. The obtained fiber 13 was combined with the fiber 1 produced in Example 1, mixed in the same manner as in Example 1, and subjected to sea removal treatment and shrinkage treatment. The difference in completion time of sea removal between the obtained fiber 1 and fiber 13 was 6%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 1 is 550 nm, the fiber diameter of the fiber 13 is 590 nm, the yarn length difference is 15%, and the elongation elastic modulus at 20% elongation is 34%. there were. The obtained nanofiber mixed yarn was excellent in dispersibility of single fibers as in Example 1, and the woven fabric made of the obtained nanofiber mixed yarn was excellent in wiping performance. On the other hand, since the softness was lower than that of Example 1, the scratch performance was not as good as that of Example 1, but it was sufficient for use as a product. The results are shown in Table 2.

(Example 10)
Except that the island component of the fiber 2 was PET having an intrinsic viscosity of 0.71, spinning and stretching were performed in the same manner as in Example 1 to obtain a sea-island composite fiber (fiber 14) of 75 dtex-112 filament. The obtained fiber 14 was combined with the fiber 1 produced in Example 1, mixed as in Example 1, and subjected to sea removal treatment and shrinkage treatment. The difference in completion time of sea removal between the obtained fiber 1 and the fiber 14 was 4%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 1 is 550 nm, the fiber diameter of the fiber 14 is 570 nm, the yarn length difference is 7%, and the elongation modulus at 20% elongation is 35%. there were. Since the obtained nanofiber mixed yarn and the woven fabric made of the nanofiber mixed yarn have a dispersibility and softness of single fibers lower than those of Example 1, the wiping performance and scratch performance are the same as those of Example 1. Although it did not keep pace, it was sufficient for use as a product. The results are shown in Table 2.

(Example 11)
The fiber 2 produced in Example 1 and the fiber 12 produced in Example 8 were combined, mixed in the same manner as in Example 1, and subjected to sea removal and shrinkage treatment. The difference in the sea removal completion time between the obtained fiber 2 and fiber 12 was 3%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 2 is 580 nm, the fiber diameter of the fiber 12 is 550 nm, the yarn length difference is 8%, and the elongation modulus at 20% elongation is 93%. there were. The resulting nanofiber blended yarn and the woven fabric comprising the nanofiber blended yarn have a single fiber dispersibility lower than that of Example 1, so that the wiping performance does not reach that of Example 1 but scratch performance. It was excellent for use as a product. The results are shown in Table 2.

(Comparative Example 5)
Implementation was performed except that fiber 2 was not a sea-island type composite fiber, but a PET single fiber copolymerized with 7.1 mol% of isophthalic acid having an intrinsic viscosity of 0.67 and 4.4 mol% of ethylene oxide adduct of bisphenol A. Spinning and drawing were performed in the same manner as in Example 1 to obtain a single fiber (fiber 15) of 40 dtex-12 filament. The obtained fiber 15 was combined with the fiber 1 produced in Example 1, mixed as in Example 1, and subjected to sea removal treatment and shrinkage treatment. In the obtained mixed fiber containing nanofibers, the fiber diameter of the fiber 1 is 550 nm, the fiber diameter of the fiber 15 is 14900 nm, the yarn length difference is 16%, and the elongation elastic modulus at 20% elongation is 31. %Met. The obtained mixed fiber containing nanofibers was excellent in dispersibility of single fibers, but the woven fabric made of mixed fiber containing nanofibers was low in softness, and one of the fibers 15 Since the part was exposed on the surface, the wiping performance and scratch performance were inferior, and the copolymerized PET was damaged by the alkali treatment and could not be used as a product. The results are shown in Table 2.

(Example 12)
The fibers 1 and 2 produced in Example 1 and the fiber 11 produced in Example 7 were combined, mixed in the same manner as in Example 1, and subjected to sea removal and shrinkage treatment. The difference in completion time of sea removal between the obtained fiber 1, fiber 2 and fiber 11 was 4%. In the obtained nanofiber mixed yarn, the fiber diameter of the fiber 1 is 550 nm, the fiber diameter of the fiber 2 is 570 nm, the fiber diameter of the fiber 11 is 580 nm, the yarn length difference is 10%, and 20% The elongation elastic modulus at the time of elongation was 84%. The obtained nanofiber mixed yarn was excellent in dispersibility of single fibers as in Example 1, and the woven fabric made of the obtained nanofiber mixed yarn was excellent in both wiping performance and scratch performance. The results are shown in Table 3.

Claims (3)

A combined filament yarn in which the yarn length is from two or more different polyester filament, one single fiber diameter of the polyester filament is also Ri 50~900nm der yarn length difference of 5-100% der Rukoto Characteristic nanofiber mixed yarn. The nanofiber mixed yarn according to claim 1, wherein at least one of the polyester long fibers is a long fiber made of polypropylene terephthalate or polybutylene terephthalate. The nanofiber mixed yarn according to claim 1 or 2, wherein an elongation elastic modulus at 20% elongation is 70% or more.