JPS6144965B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to polyester fibers, specifically polyester fibers for manufacturing artificial animal hair, which have quality and performance similar to natural animal hair, particularly those of high-quality animals such as marten and weasel used for writing brushes and painting brushes. Relating to a manufacturing method. [Prior art] In recent years, the availability of animal hair used for brushes, paint brushes, makeup brushes, furs, etc. has been significantly reduced due to the drastic decrease in the number of surviving animals such as raccoon dogs, weasels, martens, and foxes, and from the perspective of protecting natural animals. This has become difficult, and various artificial animal hairs have been proposed as alternatives. However, most of these conventional artificial animal hairs are simply fibers with artificially sharpened tips, and in terms of quality and performance, natural animal hairs, especially marten and weasel hair, which are known as high-quality products, are better. There are almost no known products that satisfy these characteristics. For example, natural animal hair used for writing brushes, painting brushes, etc. (1) Not only does the tip gradually become thinner (tapered), but the bundled tip of the brush converges into a single point when used, creating a fine touch. What makes it possible. (2) It has excellent water retention and ink retention properties, so it can hold a sufficient amount of paint, ink, etc. into the brush during use, allowing for a sufficient length of brushstrokes. (3) Since animal hair itself has strong elasticity and excellent flexibility, it is easy to obtain a brush with elasticity, and there is less chance of deformation or breakage during use. However, conventional proposals have not yet found artificial animal hair that fully satisfies these characteristics. That is, one of the reasons why artificial animal hair is not close to natural animal hair is that the densification form is significantly different from that of natural animal hair. That is, the conventional means for imparting shrinkage include the commonly used two-dimensional shrinkage method using a staff box, and the well-known method for imparting three-dimensional shrinkage described in the above-mentioned Japanese Patent Application Laid-Open No. 116742/1983. However, with these methods, it is difficult to provide the curl that natural animal hair has, that is, the curl with a small number of ridges and a large angle (gentle curl close to a straight shape). In addition, the undrawn fiber used for artificial animal hair has a thick denier and has ridge lines on the side of the thread, making it difficult to draw it uniformly.As a result, the thread tends to be uneven in thickness and curl, making it difficult for the brush to form a painting brush. There was a drawback that the convergence of each fiber was poor. [Problems to be Solved by the Invention] As a result of intensive studies by the present inventors to overcome the drawbacks of the prior art and improve the performance of the brush as a whole, the present inventors have found that:
It has been possible to provide a method for producing yarn for artificial animal hair fibers that is comparable to animal hair. [Structure of the Invention] The object of the present invention is to provide an undrawn yarn which is a polyester in which 90 mol% or more of the structural units are composed of butylene terephthalate, has an intrinsic viscosity of 0.60 to 1.3, and has a cross-sectional shape of 5 to 12 lobes. 50℃
Stretching is carried out in the above liquid bath to obtain a drawn yarn of 40 to 400 deniers, and then the drawn yarn with a water content of 2.0 or more is drawn at a winding angle of 2 to 20 degrees and 0.01 g/d to 0.5/dg.
This can be achieved by a method for producing raw yarn for animal hair-like polyester fibers, which is characterized in that it is wound onto a bobbin with a diameter of 100 mm or more with the following winding stress and subjected to crimp processing for 2 hours or more. The polyester used in the present invention can be produced, for example, by the following method. An esterification reaction is carried out between terephthalic acid and butylene glycol using a conventional catalyst, followed by a polycondensation reaction under reduced pressure. After the polycondensation reaction continues until the intrinsic viscosity reaches 0.6 to 1.3, the product is discharged and cooled. solidify. In the transesterification reaction, the esterification reaction may be carried out using a monohydric alcohol such as methanol and terephthalic acid, and then the transesterification reaction may be carried out using butylene glycol. Further, the polycondensation reaction may be carried out either batchwise or continuously. In the case of a continuous polycondensation reaction, the polymer may be supplied to a spinning machine in a molten state without being cooled and solidified after the polycondensation reaction. In the polyester of the present invention, 90 mol% or more of the structural units are butylene terephthalate, and the intrinsic viscosity is 0.60 or more and 1.3 or less. Compared to polyester terephthalate, polybutylene terephthalate fiber is preferable because it has good alkali resistance and is easy to process when sharpened, and has appropriate stiffness especially when used as a brush. The polybutylene terephthalate of the present invention is preferably homobutylene terephthalate in terms of ease of processing and product stiffness, but it may be replaced as long as it is less than 10 mol% of the structural units. Copolymerization components include, for example, dicarboxylic acid components such as aromatic dicarboxylic acids and glycol esters such as isophthalic acid and phthalic acid, aliphatic dicarboxylic acids and their glycol esters such as adipic acid and sebacic acid, and glycol components such as ethylene glycol and diethylene glycol. , polyethylene glycol, dibutylene glycol, polybutylene glycol, etc. Further, if desired, a matting agent, a coloring agent, etc. may be added and mixed. When added, it is preferably 3% or less. The solidified polymer is dried and then spun. Naturally, drying is not necessary in the method of continuously feeding the molten polymer as it is to the spinning machine. The intrinsic viscosity needs to be 0.6 or more and 1.3 or less from the viewpoints of silk-spinning properties, processability, and the proper creation of multilobal cross-sectional threads. In spinning, the shape of the spinneret hole is a combination of slits that give the desired multilobed cross section.For example, if you want to obtain a cross section like that shown in Figure 1, use a spinneret like that shown in Figure 2 to spin the yarn. be able to. After the spun yarn is cooled and solidified with a cooling liquid mainly composed of water, it is taken off and the undrawn yarn is wound. Here, it is preferable to use a liquid such as water for cooling.
It may also be a gas such as _N2 . Further, when using a liquid, the take-up speed is preferably relatively low, 300 m/min or less, but may be 300 m/min or more.
Alternatively, a direct spinning/drawing method may be used in which the undrawn material is not wound up but drawn continuously after being drawn. In order to impart good water retention and ink retention properties to single fibers, the cross-sectional shape of the fibers needs to be multilobed with 5 or more lobes, preferably 6 or more lobes, and more preferably 8 or more lobes. be. On the other hand, a multi-lobed type having 13 or more leaves is not preferable since it not only has a small effect on improving water retention and ink retention, but also deteriorates silk-spinning properties. In order to further improve water retention and ink retention, and in terms of bending rigidity, stiffness, spinnability, and quality, it is preferable to use a multi-lobed cross section and at the same time, define the degree of lobality described below as follows. {100(D-40) ^0.8 } D≦Loval degree K (%)≦ {100(D- ⁴⁰ ) ^0.8 }D+30 ^... (1) Preferably {100(D-40) ^{0.8 }} D+5≦K≦ {100 ⁽ D-40) ^0.8 }D+25. Further, the polyester fiber obtained in the present invention needs to have a single fiber fineness of 40 to 400 deniers in order to impart physical properties similar to high-grade animal hair. When the single fiber fineness is large as in the present invention, it is necessary to uniformly heat the fibers and uniformly draw them. Hot pin stretching, hot roll stretching, and liquid bath stretching are generally known as stretching methods, but in the present invention, liquid bath stretching is required from the viewpoint of uniform stretching. The advantages of liquid bath drawing are that especially when the fineness is large, it creates a uniform internal structure of the fibers, resulting in better spinning properties, that the fibers after drawing are less likely to curl, which is three-dimensional shrinkage, and that the cross-sectional shape is It has characteristics such as less distortion. Furthermore, since it is heated with moist heat, it tends to bend after being rolled up. The higher the stretching temperature, the better the stretchability and other characteristics are exhibited. The temperature of the liquid bath must be at least 50℃, preferably 60℃
The temperature is more preferably 70°C or higher. But 95
If the temperature is higher than 95°C, the spinning properties will deteriorate, so it is preferably lower than 95°C. The liquid bath used for stretching is preferably substantially water, but may also contain a small amount of oil or polyethylene glycol. The drawn yarn when winding the bobbin thus obtained was 2.0
% or more of water. In order to create a crimped part in the fiber after winding, it is necessary to soften the fiber and apply an external force, but the plasticizing effect of water is considered to be an effective means of softening the fiber, especially This can be achieved by controlling the amount of water attached to the fibers after liquid bath drawing. The higher the adhering moisture content, the more the plasticization progresses and the faster the plasticization rate becomes. However, if the moisture content exceeds 50%, handling becomes difficult. The preferred moisture content is 5 to 25%. In addition, in the present invention, the winding stress is 0.01g/d.
It is necessary to do more than that. Here, in order to provide a crimp characteristic of 150≦C≦178 degrees, it is necessary to have a moisture content of 2.0% or more and a winding stress of 0.01 g/d or more. The higher the winding stress, the smaller the crimp angle becomes, but in order to provide the above crimp characteristics, a winding stress in the range of 0.01 to 0.5 g/d is required. If it is less than 0.01 g/d, the shrinkage angle will be large and it will not be possible to impart sufficient shrinkage to the product. On the other hand, if the winding stress exceeds 0.5 g/d, the curling angle becomes too small and natural curling does not occur, resulting in poor convergence of the product brush, which is not preferable. The preferred winding stress is 0.02 to 0.3 g/d, more preferably 0.03 to 0.2 g/d. Further, in the method of the present invention, the diameter of the winding bobbin must be 100 mmφ or more. The fibers wound up in a plasticized state are fixed in their shape, so if they are wound onto a bobbin with a small diameter, they will form small curls, making handling after unwinding very difficult. Here, the larger the diameter, the greater the curvature of the curl, and although it is preferable, the bobbin diameter for winding should be 100 mmφ or more to obtain a size that does not pose a practical problem. The diameter of the bobbin is preferably 120 mm or more, more preferably 130 mm or more. Here, the twill angle at the time of winding is an important factor that determines the Ken reduction number, and 2 to
It needs to be 20 degrees. Preferably it is 2 to 18 degrees, more preferably 3 to 15 degrees. Next, in the present invention, the yarn wound onto a bobbin at the above-mentioned moisture content and winding stress is subjected to a shrinking process while being wound on the bobbin for 2 hours or more. In order to impart sufficient and durable crimp, it is necessary to crimp until the applied crimp becomes stable, and for this purpose it is necessary to crimp for 2 hours or more after winding. Preferably 10 hours or more, more preferably
More than 24 hours. [Example] The present invention will be explained in detail in Examples below, and the measurement method is as follows. A Intrinsic viscosity: Value measured at 25℃ in orthochlorophenol B Roval degree K (%): As shown in Figure 1, draw a tangent to the adjacent lobals and let the length be a, and from the tangent to the valley. Take a perpendicular line, take the longest length of the perpendicular line as b, and find it using the following formula. K (%) = b / a × 100 C Ken shrinkage angle (degrees): Arbitrarily sample 5 single fibers with a fiber length of 30 cm, copy the bending state on paper with a copying machine, and calculate the bending angle of the arbitrary bending part. Measure at 20 points and find the average value. D. Number of folded folds T (ko/100mm): Copy the measurement of the folded angle on paper in the same manner, measure the number of folded folds existing in 100 mm for 5 samples, and use the average of the 5 samples. E Twill angle (degrees): This is the winding angle of the raw yarn with respect to the circumferential direction of the bobbin when the drawn yarn 2 is wound onto the bobbin 1, and is d shown in FIG. 3. Examples 1 to 3, Comparative Example 1 Dry polybutylene terephthalate chips with an intrinsic viscosity of 0.88 were melted at 265°C, and the slit width was 0.07.
The yarn was spun at a spinning temperature of 265° C. and a discharge rate of 2.3 g/min from a spinneret hole consisting of 8 mm, slit length 0.4 mm, and 8 slits, and the yarn was introduced into water at 65° C. 5 cm below the spinneret and cooled. The surface temperature of the cap at this time was 260°C. Following the water cooling section, the yarn was taken up by rollers at a speed of 50 m/min, and liquid bath stretching was continuously performed without winding up the undrawn yarn. The stretching ratio at this time was 4.12 times, and the stretching temperature was 80°C. In addition, the intrinsic viscosity of undrawn yarn is 0.86
It was hot. The stress when winding the drawn yarn is 0.005,
The values were changed to 0.01, 0.05, and 0.2 g/d and left for 24 hours after winding. This fiber was cut into 120 mm pieces, sharpened with a caustic soda aqueous solution, and made into a brush for product evaluation. These results are shown in Table 1. As is clear from this table, the winding stress of 0.005 g/d resulted in poor shrinkage, and therefore the brushes produced as products could not be used. 0.01, 0.05, 0.2
The g/d value was good with the presence of shrinkage, but among these, the one with 0.05 g/d was the best. Comparative Example 2 Silk was produced under the same conditions as in Example 1 except that the diameter of the winding drum was changed to 80 mmφ. Due to the small diameter of the winding drum, curls were present in the yarn after unwinding, making it difficult to handle, and the yarn had no value as a product due to poor convergence due to the curl (Table 1). Example 4 Spinning and drawing were carried out under the same conditions as in Example 1 except that the slit width of the spinneret hole was changed to 0.07 mm and the slit length was changed to 0.27 mm. The degree of globalization was low, and the ink retention of the product brush was somewhat insufficient (Table 1). Examples 5 and 6 The discharge rate was set to 1.15 g/min hole, and the liquid was cooled 4 cm below the mouthpiece (Example 5). Spinning and drawing were carried out in the same manner as in Example 1 except that (Example 6). Both had good spinning properties and good product evaluations. Comparative Example 3 Spinning and drawing were carried out in the same manner as in Example 1, except that the mouth hole slit width was changed to 0.11 mm and the slit length was changed to 0.32 mm. As shown in Table 1, the ink retention property decreased significantly.
I couldn't make long enough strokes. Comparative Example 4 After spinning and stretching under the same conditions as in Example 1 except that the moisture content after stretching was changed to 1.6%, the fibers were left to stand for 24 hours and evaluated in the same manner as in Example 1. Measurement could not be performed because the shrinkage was extremely low. Moreover, the brush did not have any bulge, and it lacked value as a product.

【table】

〔Effect of the invention〕

The method of the present invention improves drawability by uniformly drawing irregularly shaped thick fibers, obtains a drawn yarn with no unevenness in thick and thin, and imparts crimpness similar to natural animal hair in the drawing process. This is what was created. Therefore, it can be drawn using a normal drawing machine, which is advantageous in terms of cost and versatility of the drawing machine, and the shrinkage characteristics can be slightly changed depending on the purpose of supplying the raw yarn. In addition, since the crimped form of the polyester fiber obtained by the present invention is extremely similar to natural animal hair, products using the polyester fiber obtained by the present invention, especially brushes, have a high stiffness when writing. The taste is similar to natural animal hair. Therefore, the polyester fiber obtained according to the present invention can be widely applied not only to brushes but also to painting brushes, paint brushes, and the like.

[Brief explanation of the drawing]

FIG. 1 shows the cross-sectional shape of the polyester fiber obtained by the present invention, and FIG. 2 shows the shape of the die for obtaining the polyester fiber of FIG. 1. Further, FIG. 3 is an explanatory diagram for explaining the traverse angle measuring method.

Claims (1)

[Claims] 1. An undrawn yarn that is polyester in which 90 mol% or more of the structural units are butylene terephthalate, has an intrinsic viscosity of 0.60 or more and 1.3 or less, and has a cross-sectional shape of 5 or more leaves and 12 leaves or less, is drawn in a liquid bath at 50°C or more. The drawn yarn with a water content of 2.0% or more is then rolled up into a bobbin with a diameter of 100 mmφ or more with a winding angle of 2 to 20 degrees and a stress of 0.01 g/d to 0.5 g/d. Roll up 2
A method for producing raw yarn for animal hair-like polyester fiber, which comprises subjecting it to shrinkage for a period of time or more.