JP5369016B2 - Nylon crimped yarn for nibs and nibs using the same - Google Patents

Description

  The present invention relates to a nylon crimped yarn for a nib and a nib using the same.

  Conventionally, synthetic fibers have been widely used as members constituting the pen tip. Advantages of using synthetic fibers include, for example, nylon 6 fiber and nylon 66 fiber, which is advantageous in that it has a soft writing feeling because it is flexible, and also has excellent wear resistance, so it is durable. This is advantageous for constructing a nib having a characteristic. Acrylic fibers are excellent in solvent resistance and are therefore suitable for oil-based pens. Polyester fibers are relatively inexpensive and are effective in reducing costs.

  On the other hand, nylon 6 fiber and nylon 66 fiber are inferior in solvent resistance and chemical resistance, and therefore have a drawback that they are difficult to apply to oil-based pens. In the case of an acrylic fiber, there are drawbacks that sufficient durability and good writing feeling are difficult to obtain, and that uncomfortable noise is likely to occur during writing. Furthermore, in the case of a polyester fiber, there are defects such as poor chemical resistance in addition to durability and writing feeling.

  As described above, the nib using synthetic fibers has various advantages, but there are many problems to be solved, and several improvements have been proposed so far. As one of them, Patent Document 1 discloses a technique for improving the performance of the entire nib by integrating two types of fibers into a core-sheath shape and assigning the functions to the respective fibers.

JP 2000-135887 A

  In the technique described in the above document, since the pen tip is composed of two types of fibers, an improvement in performance as a whole pen tip is recognized for the time being. However, with the nib, the disadvantages of the individual fibers have not been solved, and since the fibers are arranged in a core-sheath shape, the fibers are firmly integrated via a resin to prevent peeling. As a result, there is a problem that the writing feeling becomes hard. Furthermore, since the process for integrating the fibers into a core-sheath shape is complicated, there are problems such as high cost and unstable quality.

  In recent years, plant-derived fibers have attracted attention from the viewpoint of environmental protection. However, there is no mention of the use of such fibers in the above document, and there is still room for improvement including this point. Yes.

  The present invention eliminates the disadvantages of the prior art as described above, is composed of plant-derived fibers, has excellent wear resistance and solvent resistance, and can be expected to have a good writing feeling. It is a technical problem to provide a nylon crimped yarn and a nib using the nylon crimped yarn.

  The inventors of the present invention have intensively studied to solve the above problems, and have reached the present invention.

  That is, the first invention is a crimped yarn made of nylon 11 fiber, and has a crimp elongation of 30 to 70% measured based on the DIN method. As a preferable embodiment, the Young's modulus of the crimped yarn is 20 to 40.

  A second aspect of the invention is a nib formed by using the above-described nylon crimped yarn for a nib.

  According to the present invention, by using a crimped yarn made of nylon 11 fibers (hereinafter sometimes referred to as nylon 11 crimped yarn), excellent wear resistance and solvent resistance and good writing feeling can be expected. A new crimped nylon nib crimp yarn can be provided. And since nylon 11 is a plant-derived material, it can provide a crimped yarn in consideration of environmental problems and a nib using the crimped yarn.

  Hereinafter, the present invention will be described in detail.

  The nylon crimped yarn for a nib of the present invention is made of nylon 11 fiber. Nylon 11 is obtained by polycondensing 11-aminoundecanoic acid produced based on castor oil extracted from the seeds of castor (castor bean). 11-aminoundecanoic acid is therefore a plant-derived component, and as a result, nylon 11 can be said to be a material in consideration of environmental problems.

  Nylon 11 fibers have nylon-specific flexibility and excellent wear resistance. Therefore, if used as a nib, a soft writing feel can be achieved, and unpleasant noise is unlikely to occur during writing. Moreover, since nylon 11 fiber is excellent in solvent resistance, it can be applied to a pen tip used for an oil-based pen as well as an aqueous pen.

  The nylon 11 fiber in the present invention may be copolymerized with other polyamide-forming monomers such as ε-caprolactam and hexamethylene diammonium adipate as long as the effect is not impaired. The polyamide may be blended. Specifically, the content ratio of these third components in the nylon 11 is preferably 40 wt% or less, and if it exceeds this range, the effects of the present invention may be impaired.

  Moreover, it is preferable that the nylon 11 fiber in this invention contains the heat-resistant agent. When a heat-resistant agent is contained in the fiber, the spinning temperature can be lowered, and the thickening of the nylon 11 can be suppressed, so that the amount of monomer precipitated during spinning can be reduced. As a result, yarn breakage in the spinning process can be suppressed, and spinning operability can be improved. And it becomes possible to supply undrawn yarn having excellent quality and performance in the subsequent drawing process.

  As the heat-resistant agent that can be used in the present invention, a hindered phenol-based antioxidant is suitable, and as an example, IRGANOX (manufactured by Ciba Japan) is preferably used. Furthermore, it is also preferable to use a phosphorus processing heat stabilizer together with the hindered phenol antioxidant, and an example thereof is IRGAFOS (manufactured by Ciba Japan).

  The content of these heat-resistant agents in the nylon 11 fiber (the total amount when used in plural types) is preferably 0.1 to 1.0% by mass, more preferably 0.2 to 0.8% by mass, -0.6 mass% is especially preferable. When the content of the heat-resistant agent in the nylon 11 fiber is less than 0.1% by mass, the effect of improving the spinning operability described above becomes poor. On the other hand, if it exceeds 1.0% by mass, the effect is not only saturated, but also causes yarn breakage during spinning.

  The nylon 11 fiber may contain various additives such as a plasticizer, a flame retardant, a matting agent, an inorganic filler, a reinforcing agent, a heat-resistant agent, a colorant, and a pigment as long as the effect is not impaired. . In addition, the cross-sectional shape of the nylon 11 fiber is not particularly limited, and can be appropriately selected according to the purpose such as triangular, square, hexagonal, hollow, etc. in addition to a round cross section. Furthermore, the single yarn fineness is not particularly limited, and is preferably 0.1 to 10 dtex, and more preferably 0.5 to 5 dtex, for example, in consideration of ink retention of the pen tip and writing feeling.

  As described above, the crimped yarn of the present invention is composed of nylon 11 fiber. However, when the crimped yarn is not a flat yarn but a crimped yarn, the pen tip has good writing feeling and excellent ink retention. Can be provided. In the process of making the present invention, the present inventors have confirmed that nylon 11 is inferior in affinity with water compared to nylon 6 and nylon 66 and lacks the ability to retain liquid when it becomes a fiber. Surprisingly, it has been found that when nylon 11 fiber is crimped, not only the liquid retention is improved, but also the elasticity suitable for the nib is expressed. It came to the idea that the tip could be provided, and the present invention was made.

  In the present invention, as an index of crimping, the crimp elongation measured based on the DIN method needs to be 30 to 70%, preferably 35 to 65%, and more preferably 40 to 60%. When the crimp elongation rate measured by the DIN method is within the above range, appropriate elasticity is developed in the pen tip. In addition, since many fine gaps are formed in the pen tip, ink retention is improved and excellent writing quality is obtained. In addition, since ink is always collected at the pen tip by capillary action, it can be used without being caught by the writing angle.

  Therefore, in the present invention, when the crimp elongation ratio is less than 30%, the shape becomes close to a flat yarn, so that the ink retention is lowered and the capillary phenomenon is difficult to occur. On the contrary, excessive ink may come out. Further, the elasticity is lowered and the writing feeling is hardened. On the other hand, if it exceeds 70%, the crimp becomes strong, the gap increases, and the ink retention is too high. When it becomes a nib, it becomes too soft and a good writing line may not be obtained.

  Furthermore, in this invention, it is preferable that the crimp elastic modulus measured based on DIN method is 20 to 40%.

  Moreover, in the nylon crimped yarn of this invention, it is preferable that Young's modulus is 20-40, and 22-38 are more preferable. When the Young's modulus is within the above range, the pen tip is not easily deformed when used on the pen tip, and a good writing line can be obtained. Can also be obtained.

  Next, the example of the manufacturing method of the nylon crimp yarn for pen points of this invention is demonstrated.

  In order to obtain a nylon crimped yarn suitable for the nib of the present invention, any of the processing methods such as false twisting method, indentation processing method, twisting-heat fixing-untwisting method, scratching method, etc. can be adopted. On the other hand, a false twisting method that can easily provide crimping at low cost can be preferably employed.

  In order to make the crimp elongation ratio of the crimped yarn 30 to 70%, the production conditions slightly vary depending on the false twisting machine to be used. For example, when a pin false twisting machine generally called a low speed false twisting machine is used The spindle rotation speed may be set to 250,000 to 450,000 rpm, the false twisting coefficient to 23,000 to 35,000, the draw ratio to 1.0 to 1.7 times, and the heater temperature to 140 to 180 ° C.

  When a urethane disk false twisting machine called a high speed false twisting machine is used, the number of disks is 1-4-1 to 1-7-1 with a 9 mm pressure disk, and the ratio between the disk rotation speed and the yarn speed is 1.4 to 2. .3, The heater temperature may be set to 200 to 270 ° C. with a point contact heater. Needless to say, the crimped yarns of the present invention are not limited to those produced by the above-described production method, but include all those that satisfy a crimp elongation rate of 30 to 70%.

The false twist coefficient is K = T × D ^1/2 (K: false twist coefficient, T: false twist number (T / M), D: total fineness (dtex) of the yarn when passing through the twisting device) ).

  And as a manufacturing method of a nib, what is necessary is just to employ | adopt a well-known means, and considering the diameter of the nib obtained, bundle the said nylon 11 crimped yarn, heat-mold with a metal mold | die, Then, it is obtained by immersing it in a resin liquid such as urethane resin, melamine resin, epoxy resin, phenol resin, drying, curing, cutting and polishing. However, since the melting point of nylon 11 is lower than that of nylon 6 or nylon 66, the heat treatment temperature at the time of heat molding or curing is preferably 100 to 180 ° C.

  Hereinafter, the present invention will be specifically described by way of examples. In addition, the physical-property evaluation in an Example and a comparative example is as follows.

(Measurement method of crimp elongation and crimp modulus based on DIN method)
According to the method described in DIN 53840 Part 1, measurement is performed as follows.

1. Preparation of sample Using a measuring machine having a frame circumference of 1.125 m, the crimped yarn is wound into a scissors shape. At this time, the crimped yarn is wound up with a tension of 0.1 cN / dtex until the fineness reaches 2500 dtex. In order to wind so that the fineness is 2500 dtex, the number of twists may be varied depending on the fineness of the crimped yarn used. For example, when the crimped yarn is 74 to 78 dtex, 16 folds may be made, and when 112.5 to 117.5 dtex, 11 folds may be made. This point is described in DIN 53840 Part 1 Tabie 1, and those skilled in the art can make a cocoon of any thickness.
Note that the crimped yarn as a sample is left to stand in an environment of 20 ° C. and 65% humidity for at least 24 hours and then wound into a cocoon shape. After the scissors are taken out, the scissors are taken out of the frame of the measuring instrument and left to stand in an environment of 20 ° C. × 65% humidity for 24 hours without applying a load, and then subjected to various measurements.

2. Crimp expression First, a load of 0.001 cN / dtex is applied to the cocoon, and then introduced into the oven with the load applied, and heated at 120 ° C. for 10 minutes. After heating, remove the load and leave it in a humidity environment of 20 ° C x 65% for 24 hours or more.

3. Determination of straight line length First, a first load (2.5 g) and a second load (497.5 g) are applied to the heel, and the heel length (G) after 10 seconds is measured. Next, the second load is removed, and the length (Z) of the heel after 10 minutes is measured while the first load is applied. Then, with the first load applied, the third load (22.5 g) is applied, and the length (F) of the heel after 10 seconds is measured.

4). Calculation of Crimp Elongation Rate and Crimp Elastic Modulus Calculate the crimp extension rate and the crimp elastic modulus based on the following formulas.
Crimp elongation (%) = [(G−Z) / G] × 100
Crimp elastic modulus (%) = [(G−F) / G] × 100

(Young's modulus)
Based on JIS L1013 Chemical Fiber Filament Yarn Test Method 7.10 “Initial Tensile Resistance”, the Young's modulus is measured at a sample length of 200 mm and a tensile speed of 200 mm / min.

(Abrasion resistance, writing feeling, writing properties, unpleasant noise during writing)
First, a nib is prepared from the obtained crimped yarn, and then the nib is attached to the tip of an oily marker to obtain a pen. Next, using this pen, a spiral pattern measuring about 2 cm in length and width of about 4 cm is repeatedly written on a simulated paper placed on the wall surface for 10 minutes, and the following four items are evaluated from the result.

1. Abrasion resistance The projected area is calculated from photographs of the pen tip before and after writing, and the wear resistance is evaluated in the following three stages from the ratio.
○ ・ ・ ・ Projected area ratio before and after writing is 0.9 or more △ ・ ・ ・ Projected area ratio before and after writing is 0.8 or more and less than 0.9 × ・ ・ ・ Projected area ratio before and after writing is less than 0.8 here The projected area ratio before and after writing is a value obtained by dividing the projected area after writing by the projected area before writing.

2. Writing feeling Based on the sensory test by 10 panelists, writing feeling is evaluated in the following three stages.
○ ・ ・ ・ 8 or more panelists judged to have good writing feeling △ ・ ・ ・ 5 to 7 panelists judged to have good writing feeling × ・ ・ ・ 4 or fewer panelists judged to have good writing feeling

3. Writability Based on a sensory test by 10 panelists, writeability is evaluated in the following three stages.
○… 8 or more panelists judged to have good writability (no fading or excessive ink) △ ・ ・ ・ 5 to 7 panelists judged to have good writing performance (no faint or excessive ink) × ・ ・-Four or fewer panelists judged to have good writing properties (no faint or excessive ink)

4). Unpleasant sound at the time of writing Based on the sensory test by 10 panelists, the unpleasant sound at the time of writing is evaluated in the following three stages.
○ ・ ・ ・ 8 or more panelists judged not to have unpleasant noise △ ・ ・ ・ 5 to 7 panelists judged to have no unpleasant sound × ・ ・ ・ 4 or less panelists judged to have no unpleasant sound

Example 1
Using a nylon 11 chip having a relative viscosity (measured with 96% sulfuric acid as a catalyst at a concentration of 1 g / dl and a temperature of 25 ° C.) of 2.01, Irganox 1010 (hindered phenol antioxidant: manufactured by Ciba Japan Co., Ltd.) 05% by mass, Irgafos 168 (phosphorous processing heat stabilizer: manufactured by Ciba Japan) was added by 0.1% by mass, the moisture content was adjusted to 0.05% by mass, and then supplied to an extruder type melt extruder. It was melted at a spinning temperature of 250 ° C. and discharged from a spinneret having 34 spinning holes having a hole diameter of 0.3 mm. The melt-spun yarn was cooled by blowing a cooling air of 15 ° C. to give an oil agent, and then taken up by a first roller (take-off roller: surface temperature 50 ° C.) of 3000 m / min. Subsequently, the yarn taken up by the first roller is taken up by a second roller (heating roller) having a surface temperature of 130 ° C., so that it is drawn at a draw ratio of 1.5 times between the rollers and wound at a winding speed of 4400 m / min. The nylon 11 yarn of 90 dtex 34f was obtained.

  Using the nylon 11 yarn as a supply yarn, using a pin type false twister, false twisting was performed under the conditions of a spindle rotation speed of 325,000 rpm, a false twist number of Z3570 T / M, a draw ratio of 1.20 times, and a heater temperature of 160 ° C., A crimped yarn of the present invention having 78 dtex 34f was obtained.

  Next, 648 crimped yarns were collected and heat-molded with a 175 ° C. mold to produce a 4.1 mm rod-shaped body. Then, this was immersed in a polyurethane resin solution having a solid content of 15%, dried, cured, cut and polished to obtain a pen tip. The obtained pen tip was attached to the tip of the oil marker, and various performances were evaluated. The results are shown in Table 1.

(Example 2)
Nylon 11 yarn of 90 dtex34f in Example 1 was used as a supply yarn, using a pin type false twisting machine, under conditions of spindle rotation speed of 325,000 rpm, false twisting number of Z3200 T / M, draw ratio of 1.20 times, heater temperature of 150 ° C. False twisting was performed to obtain a crimped yarn of the present invention having 78 dtex 34f.

  Next, using the obtained crimped yarn, a nib was produced by the same means as in Example 1, and various performances were evaluated. The results are shown in Table 1.

(Example 3)
110 dtex 24f nylon 11 yarn, except that the take-up speed of the first roller was changed to 3100 m / min, the draw ratio between the rollers was changed to 1.02 times, and the take-up speed was changed to 3200 m / min. Got.

  Next, this nylon 11 yarn was used as a supply yarn, and a pin type false twisting machine was used, and the false twist was performed under the conditions of a spindle rotation speed of 325,000 rpm, a false twist number of Z3570 T / M, a draw ratio of 1.45 times, and a heater temperature of 160 ° C. The crimped yarn of the present invention having 78 dtex 34f was obtained.

  And using the obtained crimped yarn, the pen tip was produced similarly to Example 1, and various performances were evaluated. The results are shown in Table 1.

(Comparative Example 1)
Using a nylon 6 chip having a relative viscosity (measured at 96% sulfuric acid as a catalyst at a concentration of 1 g / dl and a temperature of 25 ° C.) of 2.41, adjusting the moisture content to 0.05 mass% without adding Irganox 1010 and Irgafos 168, This was supplied to an extruder type melt extruder, melted at a spinning temperature of 255 ° C., and discharged from a spinneret having 34 spinning holes having a hole diameter of 0.3 mm. The melt-spun yarn was cooled by blowing a cooling air of 15 ° C. to give an oil agent, and then taken up by a first roller (take-off roller: surface temperature 50 ° C.) at 3200 m / min. Subsequently, the yarn taken up by the first roller is taken up by a second roller (heating roller) having a surface temperature of 140 ° C., so that the yarn is drawn at a draw ratio of 1.3 times between the rollers and wound at a winding speed of 4200 m / min. A nylon 6 yarn of 78 dtex 34f was obtained.

  Next, using the above nylon 6 yarn as a supply yarn, using a pin-type false twisting machine, the false twisting was performed under the conditions of a spindle rotation number of 325,000 rpm, a false twist number of Z3570 T / M, a draw ratio of 1.06 times, and a heater temperature of 180 ° C. Processed to obtain a 78 dtex 34f crimped yarn.

  And using the obtained crimped yarn, the pen tip was produced similarly to Example 1, and various performances were evaluated. The results are shown in Table 1.

(Comparative Examples 2 and 3)
Nylon 11 yarn of 90 dtex 34f in Example 1 was used as a supply yarn, using a pin type false twister, under conditions of spindle rotation speed 325,000 rpm, false twist number Z2850 T / M, draw ratio 1.20 times, heater temperature 140 ° C. (Comparative Example 2) Spindle speed of 325,000 rpm, false twist number Z4080 T / M, draw ratio of 1.20 times, heater temperature of 175 ° C (Comparative Example 3) were each false twisted to obtain a 78 dtex 34f crimped yarn. It was.

  Next, using the obtained crimped yarn, a nib was produced by the same means as in Example 1, and various performances were evaluated. The results are shown in Table 1.

(Comparative Example 4)
A 4.6 g / m acrylic fiber sliver was heat-molded in a 210 ° C. mold to produce a 4.1 mm rod, then immersed in a melamine resin solution with a solid content of 15%, dried and cured, and cut Polished to obtain a nib. This pen tip was attached to the tip of the oil marker, and various performances were evaluated by the same means as in Example 1. The results are shown in Table 1.

  The nib using the crimped yarn of the present invention (Examples 1 to 3) had good wear resistance, good writing feeling, and no ink fading, excessive amount, or unpleasant noise.

In contrast, the pen tip of Comparative Example 1 had a good writing feeling, but a satisfactory result was not obtained in terms of wear resistance and unpleasant sound, and the crimp was too strong, so that blurring occurred during writing. It was. The pen tip of Comparative Example 2 had good wear resistance and no unpleasant noise, but was too weak to be crimped due to too weak crimp, slightly inferior in writing feeling, and poor in ink retention, writing performance. It was inferior to. The pen tip of Comparative Example 3 had good wear resistance and writing feeling and had no unpleasant noise, but a phenomenon that the writing line was blurred and the writing line was slightly thickened was observed. Furthermore, although the pen tip of Comparative Example 4 had good writing properties, the writing feeling was hard and the wear resistance was poor. In addition, there was an unpleasant noise when writing.

Claims (3)

  A nylon crimped yarn for a nib, which is a crimped yarn made of nylon 11 fiber and has a crimp elongation of 30 to 70% measured based on the DIN method.   The nylon crimped yarn for a nib according to claim 1, wherein the Young's modulus is 20 to 40. A nib formed by using the nylon crimped yarn for a nib according to claim 1 or 2.