WO2003072618A1

WO2003072618A1 - Synthetic resin for acrylic synthetic fiber, acrylic synthetic fiber formed from the same, and process for producing acrylic synthetic fiber

Info

Publication number: WO2003072618A1
Application number: PCT/JP2003/002009
Authority: WO
Inventors: Toshiyuki Iwabuchi
Original assignee: Kanebo, Ltd.; Kanebo Gohsen, Ltd.
Priority date: 2002-02-26
Filing date: 2003-02-24
Publication date: 2003-09-04
Also published as: JPWO2003072618A1; KR20040086729A; CN1516710A

Abstract

Regular acrylic synthetic fibers which are usable as any of pile fabrics such as a high pile, boa, blanket, mat, and carpet and can impart a bulky feeling to fabrics; a process for producing the fibers; and a synthetic resin for acrylic synthetic fibers which is made mainly from acrylonitrile, characterized by having a thermoplastic ingredient content of 13 to 22 wt.%, a sulfo-containing vinyl monomer content of 0.3 to 2.0 wt.%, and a viscosity-average molecular weight Mη shown by the equation (1) of 43,000 to 60,000. The acrylic synthetic fibers are produced from the synthetic resin. Equation (1) Mη = (S/B-1)×53/6×10000

Description

Description Synthetic resin for acrylic synthetic fiber and method for producing acrylic synthetic fiber and acrylic synthetic fiber comprising the same

The present invention relates to a regular acryl-based synthetic fiber which is used for all pile-like fabrics such as high piles, pores, blankets, mats, pliers and the like, and which can impart a polyyme feeling to the fabric. Background technology ''

When producing high pile fabrics with acrylic synthetic fibers, a mixture of large fineness fibers (usually 17 to 33 dte X flame-retardant fibers) and small fineness fibers (usually about 2.2 to 4.4 dtex) is used as hair. And use. In some cases, these fibers of intermediate fineness (about 7.8 to lldtex) may be mixed. Of these, the use of high shrinkage (dry heat shrinkage of 25% or more, preferably 30% or more) for small fineness fibers can increase the volume of the high pile fabric. This is because in the post-processing process of the high pile fabric (the process of drying the glue for preventing hair loss), the small fine fibers shrink, supporting the large and medium fine fibers, and the large and medium fine fibers are hard to fall. . When non-shrinkage or low shrinkage fiber is used as the small-sized fiber, the fiber cannot support large or medium-sized fiber, or its effect is small, so it easily falls down and lacks the feeling of polish. Unless otherwise specified, “fiber” refers to acrylic synthetic fiber. In addition, using a jacquard knitting machine, a pattern can be drawn on the non-shrinkable fiber fabric with shrinkable fibers, and only the shrinkable fiber portion shrinks in the post-treatment process (drying process of the hair loss preventing glue) to form a three-dimensional pattern. be able to.

High shrinkage fibers of small fineness are often flame-retardant fibers, because the shrinkage, especially the dry heat shrinkage, is easily obtained. However, in general, Ryl-based synthetic fibers contain high specific gravity components such as vinylidene chloride and vinyl chloride as flame-retardant components, so the fiber specific gravity is large and the actual diameter of the fibers is smaller than that of regular (non-flame-retardant) fibers of the same fineness. . This tends to reduce the volume of the dough. If fibers with a large actual diameter are used, the fabric becomes heavy.

Hereinafter, in the present specification, acrylic synthetic fibers that do not contain a flame-retardant component such as a halogenated Bier component are referred to as “regular fibers”.

On the other hand, there are high shrinkage fibers even in Regilla fiber that does not contain high specific gravity components such as vinylidene chloride and vinyl chloride. However, this is a fiber used for blending in pores, blankets, mats, and carpets and has a wet heat shrinkage of about 25%, but a dry heat of 120 to 130 ° C for 1 to 2 minutes. In the usual high pile manufacturing process (drying process of the glue for preventing hair loss), a sufficient dry heat shrinkage (25% or more) cannot be obtained (Japanese Patent Application Laid-Open No. Sho 60-11091). No. 0, JP-A-53-177691).

Japanese Patent Application Laid-Open Publication No. Hei 8-74191 has an example of a dry heat high shrinkage regular fiber for high pile use. According to this, after spinning and drawing, after drying and densification, it shrinks by more than 30% under 110 to 150 ° C., preferably 11 to 135 ° C. pressurized steam, and then heats up to 100%. It is stretched 1.6 to 2.2 times at ~ 140, but it is difficult to shrink by more than 30% at this temperature with a normal polymer with a small amount of thermoplastic and a continuous method that is usually performed. is there. In addition, since the amount of the plastic component is small, it is difficult to stretch by this amount after shrinkage. Also, the method for measuring the dry heat shrinkage rate is far from the actual heating process at 130 ° C for 10 minutes.

On the other hand, large fineness fibers are also often flame retardant fibers. This is because the flame-retardant fiber is usually more flexible than the regular fiber, and the crimp is easily removed. However, as in the case of shrinkable fibers, the specific gravity of the fibers is large, and the actual diameter (cross-sectional area) of the fibers is smaller than that of regular (non-flame-retardant) fibers of the same fineness. Therefore, the volume of the fabric tends to be insufficient. The cross section is often flat. This is fiber This is because it is difficult to get tangled, and it is easy to obtain a dough with a smooth texture. However, flat fibers, on the other hand, have the disadvantage that the fibers tend to fall down, making it difficult to obtain a polish feeling. Although it is a flame-retardant fiber with excellent declamping properties, when dyed, the fibers shrink and become immobilized, deteriorating the declamping properties. In order to improve the declamping property at the time of dyeing, JP-A-2001-189269, JP-A-2001-189337, JP-A-200 According to the method described in JP-A-1-181927, the residual shrinkage (shrinkage generated during thermal processing such as dyeing) of acryl fibers is minimized by performing a sufficient relaxation process before applying the crimp. Although the fiber obtained by this method is excellent in the declamping property, the effectiveness of the conventional regular fiber in which the polymer constituting the fiber itself is hard is low.

For pores, blankets, mats, etc., fibers are mixed and spun, then dyed, knitted and processed into products. At this time, if the wet heat shrinkable fiber is mixed, the shrinkable fiber shrinks at the time of dyeing, the non-shrinkable fiber is wrapped into a panel shape, and the feeling of polish increases. Conventionally, the shrinkage rate of the heat-shrinkable fibers used in such spun yarns has been about 20 to 25%, and although a polish feeling can be obtained, it is not strong. The inventors have found that if the wet heat shrinkage ratio is increased to 30% or more, a strong voluminous feeling can be imparted to the pile, and if it exceeds 40%, on the contrary, the fabric becomes too hard.

The velor carpet is dyed with 5.5 to 17 dtex non-shrinkable fibers, mixed with undyed shrinkable fibers, spun, and knitted. The post-processing after knitting is almost the same as for high piles, and shrinks the mixed shrink fibers in the drying process of the glue for preventing hair loss. For this reason, when the shrinkage rate of the shrinkable fiber is 25% or more, preferably 30% or more, the non-shrinkable fiber can be effectively supported, and a sense of volume can be imparted.

In the case where fibers with a dry heat shrinkage of 25% or more, mainly used for high piles described above, are used in pores, blankets, mats, etc., excessive (50% or more) in the dyeing process of spun yarn. Shrinks and product texture becomes too hard. Although the shrinkage can be suppressed to some extent by adjusting the stretching ratio, etc. However, it is difficult to make it within an appropriate range (wet heat shrinkage ratio: 30 to 40%). For this reason, fibers that are used mainly for high piles and shrink by dry heat and fibers that are mainly used for pores, blankets and mats and shrink by wet heat (dyeing) are conventionally made of different polymers.

The above-mentioned pores, blankets, mats, and velour-force pets use large and / or medium-sized fibers simultaneously with shrinkable small-sized fibers, but these are often legilla-fibers. This is because these products are subject to significant pressure, such as walking or sleeping on them, and in particular require a sense of plumage. As mentioned several times, the flame-retardant fiber is easy to remove the crimp and improves the texture, but tends to lack the volume. Disclosure of the invention

An object of the present invention is to provide a fiber having excellent fast shrinkage property and high shrinkage property (25% or more, preferably 30% or more) against dry heat, which can give a feeling of polymer to the entire piled fabric; Similarly, a moderate heat and heat shrinkage rate (30 to 40%, preferably 35 to 40%) for obtaining pores, blankets, mats, carpets, etc. that is also excellent in volume and not too hard It is an object of the present invention to provide a fiber having excellent sensation of volume and a crimp-removing property combined with these, and a method for producing these from the same polymer. The rapid shrinkage (rate) referred to in this specification refers to the shrinkage (rate) within a passing time of 1 to 2 minutes in the drying step (tenter) of the paste for preventing hair loss in the high pile manufacturing process. Point. Therefore, the dry heat shrinkage rate described in Examples and Comparative Examples refers to quick shrinkage (rate).

The above purpose is that the thermoplastic component containing acrylonitrile as a main component is 13 to 22% by weight, the sulfonic acid group-containing vinyl monomer is 0.3 to 2.0% by weight, and the viscosity average molecular weight M-7 is 43. After wet-spinning and washing the polymer of 000 to 600,000, it shrinks to 0.85 to 0.95 times in the dry densification process, and then 1.3 to 2 by dry heat. Achieved by stretching 7 times. Create fibers used as spun yarn such as pores, blankets, mats, and carpets. If necessary, the same polymer is subjected to wet spinning, washing with water, dry densification step or, after that, shrinking and stretching by 0.9 to 1.3 times by dry heat. Furthermore, the fiber with excellent crimp removal properties is dried and densified, stretched 1.1 to 2.0 times with wet heat, and then contracted 0.6 to 0.9 times with wet heat.

In this specification, the shrinkage ratio or the stretching ratio indicates the ratio of the exit speed to the entrance speed in the process. For example, a stretching ratio of 1.4 indicates that the exit speed from the process is 1.4 times the entrance speed, and a shrinkage ratio of 0.8 indicates that the exit speed from the process is relative to the entrance speed. , 0.8 times. More specifically, if the fiber bundle entering the drawing process at 1 Om / min is shrunk 0.8 times immediately after drawing 1.4 times, the output speed of the drawing process is 14 m / min, and the shrinking process immediately after Is 0.8 times higher than this speed, and the final speed is 11.2 m / min. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail. The synthetic resin of the present invention contains acrylonitrile as a main component, contains 13 to 22% by weight of a thermoplastic component, 0.3 to 2.0% by weight of a vinyl monomer containing a sulfonic acid group, and has a viscosity average component. The child quantity Μ τ? Is 4 3 0 0 0 to 6 0 0 0 0.

If the thermoplastic component is less than 13% by weight, the flexibility of the polymer constituting the fiber is reduced, and the stretchability during spinning and the shrinkage of the product, as well as the removability of the crimp, are deteriorated, and the texture is reduced. . If the content exceeds 22% by weight, the flexibility of the polymer is increased, and the removability of the crimp and the texture are improved, but the fibers are strongly adhered to each other and it is difficult to convert the fibers. Further, it is preferably 15 to 18% by weight, more preferably 15 to 17% by weight. As the amount of the thermoplastic component copolymerized is restricted, the stretchability during spinning, the shrinkage of the product, and the adhesion of the fibers are balanced, which is preferable.

As the thermoplastic component, acrylic acid, methacrylic acid or their alkyl esters, vinyl acetate, and the like can be used, but are not limited thereto, but acrylic acid or its alkyl esters, biel acetate, etc. However, methyl acrylate is more preferred because of its cost and ease.

A vinyl monomer having a sulfonic acid group is copolymerized in an amount of 0.3 to 2.0% by weight for imparting dyeability. If the amount is less than 0.3% by weight, the dyeing properties will be insufficient, and if it exceeds 2.0% by weight, the dyeing properties (dye adsorption) will be strong, and the dyeing will be remarkably fast, and staining spots will occur. Examples of the sulfonic acid group-containing biel monomer include, but are not limited to, sodium arylsulfonate, sodium methallylsulfonate, sodium styrenesulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, and the like. Sodium methallyl sulfonate and sodium 2-acrylamide 2-methylpropanesulfonate are used in combination from the viewpoint of polymer molecular weight, fiber whiteness, cost, polymerization operability, etc., and the weight ratio is preferably 1: 3 to 5 .

Acrylonitrile, a sulfonic acid group-containing vinyl monomer, and a vinyl monomer other than a thermoplastic component may be copolymerized within a range that does not impair the fiber-forming ability, operability, and shrinkage.

Further, the viscosity average molecular weight ττ needs to be from 43,000 to 600,000. Preferably it is 470,000 to 500,000. If it is less than 430, stretchability during spinning, product shrinkage and crimp removal properties are good, but agglutination becomes strong.If it exceeds 600, agglutination is reduced, but stretching during spinning. The properties, shrinkage of the product and the removability of the crimp are reduced, and the desired fiber cannot be obtained. In addition, the viscosity of the polymer solution at the time of polymerization becomes too high, which makes it difficult to handle. If the concentration is reduced due to the decrease in viscosity, the polymerization efficiency will decrease. Generally, the molecular weight is increased when the amount of the thermoplastic component is large, and is decreased when the amount is small. The molecular weight is adjusted by the amount of polymerization initiator, monomer concentration, polymerization temperature and time, the type of sulfonic acid group-containing vinyl monomer, and the amount of copolymerization.

The polymer is fiberized by a known wet spinning method. That is, the above polymer is dissolved in a solvent such as dimethylformamide (DMF), an aqueous solution of rodan salt, or dimethyl sulfoxide at a concentration of 23 to 32% by weight, and the solution is mixed with a spinning solution. I do. However, the solvent is not limited to these. At this time, additives such as an antibacterial agent, a pigment, and a light-proof agent may be added to the spinning dope within a range that does not impair spinning operability, fiber-forming ability, and stretchability. The spinning solution is spun from a spinneret into water (coagulation bath) containing a solvent. The spun and gelled tow is stretched 3 to 7 times, preferably 4 to 6 times in a several-stage stretching bath in which the solvent concentration decreases, washed with water and oiled, and dried and densified. .

In the case of producing fibers having a dry heat shrinkage of 25% or more used for high pile, etc., the fibers are first shrunk by a factor of 0.85 to 0.95 in a dry densification step. If it is less than 0.85 times, the fiber tends to sag, making operation difficult. If it exceeds 0.95 times, the dry heat shrinkage of the final product will decrease.

Then, it is stretched 1.3 to 2.7 times by dry heat. If the ratio is less than 1.3 times, the shrinkage rate decreases. If the ratio exceeds 2.7 times, the shrinkage rate hardly increases, or fiber cutting occurs, making operation difficult. Within this range, it is easy to achieve both product shrinkage and operability. The stretching temperature is set so that the tow temperature is about 120 ° C. When the temperature is extremely low, the shrinkage ratio is improved at the same stretching ratio, but the operability (stretchability) is deteriorated. If it is high, the operability is good, but the shrinkage decreases at the same draw ratio.

On the other hand, since it is used as spun yarn such as pores, blankets, mats, carpets, etc., if a wet heat shrinkage of 30 to 40% is required, it is necessary to wash it and dry it after applying oil. In the dry heat stretching (shrinkage) step, shrink or stretch by 0.9 to 1.3 times. Preferably, the stretching temperature is set so that the tow temperature is about 120 ° C.

In addition, in order to obtain fibers having excellent crimp removal properties, the fibers are washed with water, dried and densified, stretched 1.1 to 2.0 times, and then shrunk to 0.6 to 0.9 times. If it is less than 0.6 times, the crimp removal property is improved, but the tow tends to sag and the operability deteriorates. If it exceeds 0.9 times, the crimp removability will be insufficient. This is because if the relaxation treatment is inadequate, shrinkage (residual shrinkage) occurs during dyeing, and the clamp is fixed.

After that, an oil agent is applied as needed, to prevent shrinkage in the drying process. Therefore, it is desirable not to apply oils or to minimize the amount of water even if they are used. After applying the oil agent, apply the crimp, cut, and package it to make it a product. For the same reason, it is desirable that crimping be performed at a temperature as low as possible. Example

Hereinafter, the present invention will be described specifically with reference to Examples. The dry heat shrinkage was determined by treating the single fiber with no load in a dry heat atmosphere at 130 ° C for 1 minute. The wet heat shrinkage was determined by treating the single fiber with boiling water (100 ° C) without load. After 30 minutes, the length of the fiber before and after the treatment was measured and calculated by Equation 2. The viscosity average molecular weight Μ τ? Was determined by the following (Equation 1).

(Equation 1) Μ 7 = (S ZB— 1) X 5 3/6 X 1 0 0 0 0

(However, Β is the viscosity (seconds) of N, N-dimethylformamide (DMF) measured with a Ostwald viscometer (30 ° C) and S is the same measured value of 0.2 g of polymer as DMF. The viscosity of the solution after dissolving to 50 m 1 (seconds).)

(Equation 2) Dry heat, wet heat shrinkage (%)-(length before shrinkage-length after shrinkage) / length before shrinkage X 100

(However, the length before and after shrinkage is measured with a load of 2.94 mN per tex.)

(Table 1, Examples 1-4, Comparative Examples 1, 2)

The acrylonitrile (AN) Z methyl acrylate (MA) Z sodium methallyl sulfonate (SMAS) / 2—acrylamide was obtained by the solution polymerization method using DMF as a solvent at the copolymerization ratio shown in Table 1. A polymer comprising sodium do-methylpropanesulfonate (SAM) was obtained. The viscosity average molecular weight M77 was in the range of 480 000 to 530 000.

Unreacted monomers were removed from the polymer solution after the polymerization, and the polymer concentration was adjusted to 25% by weight. This spinning stock solution was spun into a DMF 53% aqueous solution from a die having a pore diameter of 0.04 mm and a number of holes of 4000. This The solidified and gelled tow was stretched 4.5 times in a three-stage bath in which the DMF concentration gradually decreased. After that, water washing, oiling and drying and densification were performed. It was shrunk 0.95 times in the drying and densification process. Then, the sheet was heated with a heater roller and dry hot air so that the tow temperature became 120 ° C., and stretched 1.6 times. After the drawing, a crimp was applied and cut to obtain 2.2 dte XX 32 mm fiber.

A mixture of 40% by weight of the dry heat high shrinkage fiber obtained in this way and 60% by weight of a flame-retardant flat acrylic synthetic fiber of 17 dtex X 51 mm with a cross section of 1: 6. - knitting stand and was post processed in a known manner to obtain pile length 2 0 mm, the high-pile fabric of basis weight 6 0 0 g Z m ^2. The paste for preventing hair loss was dried at 130 ° C. for 1.5 minutes.

Fiber adhesion is visually observed on the tow after drying and densification. E: Extremely severe adhesion, D: Intense adhesion, C: Slightly adhesive, B: Good, A: Very good Subsequent operations and product use are at acceptable (passed) level.

The operability was evaluated in three stages: E: bad, C: good, A: very good, based on the presence or absence of fiber cutting and sagging.

The dry heat shrinkage shall be 25% or more. The volume of the high pile was determined by five experts. E: Same as when using non-shrinkable fiber of the same standard (fineness, fiber length), C: Slightly stronger than when using non-shrinkable fiber of the same standard , A: Judgment was made in three stages: the sense of polylife was stronger than C

[table 1 ]

As can be seen from Table 1, Examples 1 to 4 in which the methyl acrylate copolymerization amount as the thermoplastic component is in the range of 13 to 22% by weight have no sticking, good operability, and low dry heat shrinkage. 30% or more. The adhesiveness of the fibers in Examples 3 and 4 is slightly inferior to Examples 1 and 2, but this is also at the same level as in Examples 1 and 2 by the subsequent stretching and crimping. On the other hand, Comparative Example 1, which has a small amount of thermoplastic component, has no problem in fiber sticking and operability, but has a low dry heat shrinkage. Conversely, Comparative Example 2, which had a large amount of thermoplastic components, was strongly agglutinated in the drying and densification process and became a ribbon-like shape, which made subsequent operations difficult and failed to produce fibers. Further, the high pile fabric using the fibers of Examples 1 to 4 having a dry heat shrinkage of 30% or more had a strong polish feeling, but the fiber of Comparative Example 1 having a dry heat shrinkage of 20% was used. The fabric used had almost the same voluminous feel as when non-shrink fibers were used.

(Table 2, Examples 5 to 8, Comparative Example 3)

The same spinning dope as in Examples 1 to 4 and Comparative Example 1 was spun into a DMF 53% aqueous solution from a die having a diameter of 0.54 mm × 0.063 mm and a number of holes of 600. The solidified and gelled toe was stretched 6-fold in a three-stage bath in which the DMF concentration gradually decreased. After that, washing with water, application of oil agent, and drying and densification were performed (no stretching or shrinking). Then, it was heated with steam at 110 ° C and stretched 1.4 times. After stretching, it was heated with steam at 140 ° C. and shrunk 0.7 times. So After that, crimping and cutting were performed to obtain a 17 dte XX 51 mm rectangular fiber having a cross-sectional shape of 1: 7. The obtained fiber was dyed brown at 98 ° C for 30 minutes, and 60% by weight of the dyed cotton and 40% by weight of the dry heat-shrinkable cotton of Example 2 were mixed and knitted. and post-processing in the method to obtain the pile length 2 0 mm, the high-pile fabric of the eye with 6 0 0 g Z m ^2.

The texture of the high pile was judged by five experts in three stages: E: poor, C: about the same as when using the same type of flame retardant fiber, and A: when using the same type of flame retardant fiber. Pass C and A.

The sense of volume in Table 2 was determined by five experts as E: Poor feeling of volume, C: Equivalent to the case of using the same flame-retardant fiber, A: Equivalent to the case of using one fiber of the same standard. , A to pass. The residual shrinkage is the shrinkage in the dyeing process, and the measurement is performed in the same manner as the wet heat shrinkage.

[Table 2]

In Examples 5 to 8 and Comparative Example 3 shown in Table 2, fiber sticking and operability were the same as in Examples 1 to 4 and Comparative Example 1. The residual shrinkage ratio was larger as the amount of thermoplastic MA was higher. The texture was better as the amount of MA was larger, but Examples 5 to 8 were all good. The volume feeling was good in Examples 5 to 8 and Comparative Example 3. In Comparative Example 3, although the residual shrinkage was small, the crimp was difficult to release, and the texture of the high pile fabric was poor. In addition, the polymer of Comparative Example 3 is the same as Comparative Example 1, but as shown in Table 1. High heat shrinkable cotton (shrinkage ratio 25% or more) cannot be made.

(Table 3, Examples 9 to 12, Comparative Example 4)

The same spinning dope as in Examples 1 to 4 and Comparative Example 1 was spun into a DMF 53% aqueous solution from a die having a diameter of 0.04 mm and a number of holes of 4,000. The solidified and gelled tow was stretched 5-fold in a three-stage bath in which the DMF concentration gradually decreased. Thereafter, washing and oiling were performed. In the dry densification process, the film was shrunk or stretched at the magnification shown in Table 3. Then, crimping and cutting were performed to obtain a fiber of 2.2 dtex X 102 mm VC (80 to 120 mm). The obtained fiber (40% by weight) and non-shrinkable fiber (2.2 dtex X102 mm VC) (60% by weight) were mixed and spun (# 28 double yarn) and dyed brown. Stained yarns and warp knit, and post-processing in a known manner, the pile length 1 2 mm, to give a basis weight only 4 5 0 g Z m ² bores fabric.

The volume of the pores was determined by five experts. E: Same as when using conventional shrinkable fibers of the same standard (wet heat shrinkage ratio of about 20 to 25%), C: When using conventional shrinkable fibers of the same standard Judgment was made on a three-point scale, with a slightly stronger sense of polylife, and a stronger sense of polylife than A: C. In Table 3, stretching and shrinkage ratios of less than 1.0 indicate shrinkage, and values of more than 1.0 indicate stretching (1.0 means neither stretching nor shrinkage).

In Examples 9 to 12 in Table 3, the wet heat shrinkage ratio was 30 to 40%, and the feeling of polylum was also strong. On the other hand, in Comparative Example 4, since the shrinkage rate was low, it had the same feeling of pouring as the conventional product. Since the polymer of Comparative Example 4 has a low MA copolymerization amount of the thermoplastic component, the shrinkage does not improve even if the stretching ratio is increased.

[Table 3]

(Table 4, Example 2, Comparative Examples 5, 6)

The polymer of Example 2 and the polymers of Comparative Examples 5 and 6 in Table 4 were fiberized under the same conditions as in Examples 1 to 4, to obtain 2.2 dtex X 32 mm fiber.

As shown in Table 4, the polymer of Example 2 was a sulfonic acid group-containing vinyl monomer, SAM / SMAS, since the copolymerization amount and ratio were appropriate, the molecular weight was 43,000 to 60,000. In the range of 0.00, there is no sticking of fibers during spinning, and the operability is good.In addition, even when fibers made of such fibers are used for high piles and pores, it is possible to improve the feeling of polish and texture compared to conventional fibers of the same standard. did it. On the other hand, in Comparative Example 5 in which the S AMZ S MA S ratio was small (the S SAM was small), the molecular weight exceeded 600, and although there was no fiber sticking, the stretchability was deteriorated and fiberization became difficult. Comparative Example 6 having a large SAM / SMAS ratio (many SAMs) had a molecular weight of less than 43,000, fiber sticking occurred, and subsequent steps (drawing, etc.) became difficult. [Table 4]

(Table 5, Example 2, 13 to 16, Comparative Example? To 10)

Spinning is performed using the polymer and the conditions of Example 2, and a water washing / oiling agent is applied. Thereafter, the fibers were shrunk in the dry densification step under the conditions shown in Table 5, stretched in the dry heat stretching step, and crimped and cut to obtain 2.2 dtex X 32 mm fiber. In Examples 2 and 13 to 16 in which the shrinkage ratio was 0.85 to 0.95 and the subsequent stretch ratio was 1.3 to 2.7 times, both the operability and the dry heat shrinkage ratio were good. Comparative Example 7, which had a low draw ratio, had a low dry heat shrinkage, and Comparative Example 8, which had an excessive draw ratio, could not be operated by fiber cutting. The shrinkage ratio in the drying and densification process is low (excessive shrinkage). In Comparative Example 9, sagging occurred, operation became difficult, and in Comparative Example 10 in which no shrinkage was performed, the dry heat shrinkage ratio was low. .

[Table 5]

(Table 6, Example 17 and Comparative Examples 11 and 12)

The fiber is spun with the polymer and the conditions of Example 2, washed with water, applied with an oil agent, and dried and densified. Then, stretch or shrink by dry heat under the conditions shown in Table 6. After shrinking, the material was crimped and cut to obtain 2.2 dte XX102 mm VC fiber. In Table 6, when the stretching / shrinkage ratio is less than 1.0, shrinkage is shown, and when it exceeds 1.0, stretching is shown (1.0 means neither stretching nor shrinkage).

In Example 17 in which the stretching / shrinking ratio was in the range of 0.9 to 1.3 times, the heat and heat shrinkage ratio was in an appropriate range, the volume feeling of the pore fabric was improved, and it was not too hard. In Comparative Example 11 which was excessively contracted, the contraction rate was low, and the improvement in volume feeling was not large. In Comparative Examples 1 and 2, the stretch ratio was too large, and the shrinkage was too large, and the fabric was too hard.

[Table 6]

Boa dough

Shrinkage Stretching ratio Wet heat shrinkage

Volume

Example 17 1. 0 31 A

Comparative Example 11 0.89 C

Comparative Example 12 1.4.42 E (Table 7, Example 7, Comparative Examples 13 and 14)

Spinning, washing, oiling, and drying and densification were performed under the same conditions as in Example Ί (same as in Example 2). Next, the film was stretched 1.4 times with steam at 110 ° C, and then heated with steam at 140 ° C and shrunk at the magnification shown in Table 7. Thereafter, crimping and cutting were performed to obtain a rectangular fiber having a size of 17 to 65 1111111 and a cross-sectional shape of 1: 7. 60% by weight of the obtained fiber and 40% by weight of the dry heat-shrinkable cotton of Example 2 were mixed and knitted, and post-processed by a known method to give a pile length of 20 mm and a basis weight of 600 g Zm. ² high pile fabrics were obtained.

In Example 18 in which the shrinkage ratio is in the range of 0.6 to 0.9 times, both the texture and the feeling of the polymer are good, but the shrinkage ratio is small (excessive shrinkage). The operation was difficult. On the other hand, the magnification was large (they were hardly shrunk). Comparative Example 14 had a large residual shrinkage, and the fiber became hard at the time of dyeing, and the texture was deteriorated.

[Table 7]

(Table 8, Example 6, Comparative Examples 15 and 16)

Comparative Examples 15 and 16 were polymerized to have the compositions shown in Table 8. A fiber was obtained by spinning, washing, applying oil, applying dry densification, stretching, shrinking, applying crimp, and cutting under the same conditions and conditions as in Example 6 except for the unreacted monomer.

The dyeability was determined by adding a black dye to the dye solution at 3% of the fiber weight, dyeing at 98 ° C for 30 minutes, and then visually determining the color of the dye solution. E (failed) indicates coloring (residual dye is present), and A (passed) indicates no coloring to the naked eye. For staining, add a brown dye to the staining solution to 0.5% of the fiber weight, dye at 98 ° C for 30 minutes, and then stain the cotton. Is judged with the naked eye. A without staining spots (pass), E with staining spots

(Failed).

In Example 6, the dyeability was good and there was no spot, whereas in Comparative Example 15 in which the amount of the sulfonic acid group-containing vinyl monomer was small, the dyeability was poor, and the dye remained without being adsorbed. On the other hand, Example 16, which had many stains, had good staining properties, but had many stained spots.

[Table 8]

Industrial applicability

By using the polymer and the production method of the present invention, it is possible to impart a sense of volume to the entire piled fabric.

(25% or more, preferably 30% or more), and a moderate heat and heat shrinkage ratio (%) for obtaining a polyume feeling and not too hard pores, blankets, mats, carpets and the like. 30 to 40%, preferably 35 to 40%), a fiber combined with these, which has both an excellent polish feeling and a high degree of declampability, and a method for producing these from the same polymer. Can be provided.

Claims

The scope of the claims

1. A synthetic resin for acrylic synthetic fibers containing acrylonitrile as a main component, with a thermoplastic component content of 13 to 22% by weight and a sulfonic acid group-containing bimer monomer of 0.3 to 2.0% by weight. A synthetic resin for acryl-based synthetic fibers, characterized in that the viscosity average molecular weight Μ τ? Represented by (Equation 1) is from 430 to 600,000.

(Equation 1) M v = (S ZB-1) Χ 5 3/6 X 1 0 0 0 0

(However, Β indicates the viscosity (in seconds) of N, N-dimethylformamide (DMF) measured with a Ostwald viscometer (30 ° C) and S indicates 0.2 g of the polymer similarly measured in DMF. The viscosity of the solution (seconds) was adjusted to 50 m 1 by dissolving in water.)

2. The synthetic resin for an acrylic synthetic fiber according to claim 1, wherein the thermoplastic component is 15 to 18% by weight.

3. The synthetic resin for acryl-based synthetic fibers according to claim 1, wherein the thermoplastic component is methyl acrylate.

4. The claim 1 wherein the sulfonic acid group-containing Bier monomer is sodium methallyl sulfonate and 2-acrylamide 2-sodium methylpropanesulfonate in a weight ratio of 1: 3 to 5. Item 4. The resin for acryl-based synthetic fibers according to any one of Items 3 to 3.

5. An acrylic resin comprising the resin according to any one of claims 1 to 4, wherein a shrinkage ratio at the time of dry heat 130: xi minute treatment is 25% or more. Synthetic fiber.

6. The resin according to any one of claims 1 to 4, characterized in that the shrinkage after 100 minutes of boiling water 100 ^ X 30 minutes is 30 to 40%. Acrylic synthetic fiber.

7. An acrylic synthetic fiber comprising the resin according to any one of claims 1 to 4, and having a residual shrinkage of 7% or less.

8. When wet spinning the resin according to any one of claims 1 to 4, after washing with water, the shrinkage ratio in the dry densification step is 0.85 to 0.95. Yes, and then a dry heat drawing of 1.3 to 2.7 times is performed.

9. After the resin according to any one of claims 1 to 4 is wet-spun and washed with water, it is 0.9 to 1.3 times in a dry densification step or a dry heat drawing step thereafter. A method for producing an acrylic synthetic fiber, characterized by shrinking or stretching.

10. After wet spinning, washing with water, and drying and densifying the resin according to any one of claims 1 to 4, it is stretched 1.1 to 2.0 times, and then 0.6 to 0. . Method for producing acryl-based synthetic fiber, characterized by shrinking by 9 times