JPH04214438A - Blended woven fabric of acrylic fiber and wool - Google Patents

Abstract

PURPOSE:To produce the subject woven fabric having excellent heat resistance and soft touch by blending wool with acrylic fibers containing a small amount of 2-acrylamido-2-methylpropane sulfonic acid (salt) polymer units in the AN polymer units. CONSTITUTION:Wool is blended with acrylic fibers having an elongation of <=10% at 260 deg.C and produced from an AN copolymer containing 0.4-1.5mol% of 2-acrylamido-2-methylpropane sulfonic acid (salt) polymer units and having a polymerization degree of 600-1500.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a blended fabric of acrylic fiber and wool.

More specifically, the present invention relates to a blended fabric of acrylic fiber and wool that has excellent heat resistance, and has excellent fluffiness and drapability.

(Conventional technology) Acrylic fibers have traditionally been widely used for clothing such as knitwear and jersey, interior decoration such as carpets and curtains, and bedding such as blankets and sheets due to their vivid coloring and flexible texture. It is being

On the other hand, wool is widely used for textiles, knitted clothing, interior decoration such as carpets, and bedding such as blankets due to its excellent elasticity and calm color development.

Conventionally, blended fabrics of acrylic fiber and wool have not been used because they lack a firm feel.

(Problems to be Solved by the Invention) An object of the present invention is to provide a blended fabric of acrylic fiber and wool.

Another object of the present invention is to provide a novel blended fabric of acrylic fiber and wool that has excellent heat resistance and a soft texture.

Further objects and advantages of the present invention will become apparent from the description below.

(Means and effects for solving the problems) According to the present invention, the above objects and advantages of the present invention are achieved as follows: (A)
, (a) consists essentially of a polymerized unit represented by the following formula (1) and a polymerized unit represented by the following formula (2), where M is a hydrogen atom or one equivalent cation, (b) the polymerized unit represented by the following formula (2) The polymerized unit (2) accounts for 0.4 to 1.5 mol% of the total of the unit (1) and the polymerized unit (2), and (c) the degree of polymerization is in the range of 600 to 1,500. It is made of an acrylonitrile copolymer, and (B) is characterized by containing acrylic fibers whose elongation rate at 260°C is 10% or less in the relationship between temperature and elongation rate measured at elevated temperatures. Achieved by a blended fabric of acrylic fibers and wool.

As mentioned above, the acrylic fiber used in the blended fabric with wool in the present invention is specified by the requirement (A) to specify the polymer forming it and the requirement (B) to specify its elongation rate at high temperatures. Ru.

Regarding requirement (A), the polymer contains polymerized units of the above formula (1) derived from acrylonitrile and 2-acrylamide-
It consists essentially of polymerized units of the above formula (2) derived from 2-methylpropanesulfonic acid (hereinafter abbreviated as AMPS) or a salt thereof.

The ratio of polymerized units (1) and polymerized units (2) is 0.4 to 1.5 mol% of polymerized units (2) (99.6 to 1.5 mol% of polymerized units (1)) based on the total of both polymerized units. The proportion of polymerized units (2) which accounts for 98.5 mol%) is preferably 0.6 to 1.2 mol% (99.4 to 98.8 mol% of polymerized units (1)) based on the same standard. %), polymerized units (2)
If the ratio is less than 0.4 mol%, gelation tends to occur during the polymerization process, and deep color dyeing becomes difficult due to insufficient dyeing seat. Moreover, if it exceeds 1.5 mol%, the heat resistance properties described below will deteriorate.

Furthermore, regarding requirement (A), the above polymer has a degree of polymerization of 600.
~1,500. The preferred degree of polymerization is 800~
It is 1,100.

If it is less than 600, the strength as a normal acrylic fiber cannot be obtained, and if it exceeds 1,500, gelation tends to occur during the polymerization process, and the viscosity is too high for normal wet spinning.

The acrylic fiber used in the blended fabric with wool in the present invention has polymerized units (1) and polymerized units (2) based on the sum of these, as specified in requirement (A). According to the research of the present inventor, the polymerized unit (1) contains the polymerized unit (2) in a proportion of 0.4 to 1.5 mol%.
It has been revealed that the above objects and advantages of the present invention can be maintained even if a slight amount of other polymerized units (3) is further contained under the conditions that the above ratio of polymerized units (2) is maintained.

That is, the acrylonitrile copolymer containing such other polymerized units (3) meets the following requirement (A) instead of requirement (A).
'): (A') (a') Polymerized unit of the above formula (1), the above formula (2)
) and the polymerized unit represented by the polymerized unit (3) which is different from the polymerized unit of the above formula (2) derived from a monomer copolymerizable with acrylonitrile, (b') the above polymerized The polymerized unit (2) accounts for 0.4 to 1.5 mol% of the total of the unit (1) and the polymerized unit (2), and the polymerized unit (3) accounts for 5% by mole based on the polymerized unit (1). % by weight or less, and (c) the degree of polymerization is in the range of 600 to 1,500.

Regarding requirement (A'), polymerized unit (1) and polymerized unit (2)
The ratio of polymerized units (2
) is 0.4 to 1.5 mol% (polymerized unit (1
) is 99.6 to 98.5 mol %), which is the same as requirement (A). Regarding requirement (A'), in addition to the polymerized units (1) and (2), another polymerized unit (3) that is different from the polymerized unit (2) derived from a monomer copolymerizable with acrylonitrile, Based on the polymerized units (1), the polymerized units (3) are preferably present in an amount of not more than 3% by weight, based on the same criteria.

As the polymerized unit (3), preferably, for example, the following formula (
3) where R is a hydrogen atom or a methyl group, and Y is a group of the formula -COOX (wherein X is a hydrogen atom, a sodium atom or a methyl group), -OCOCH3,
Examples include a unit represented by the following, which is a group selected from the group consisting of -CONH2, -C4H5, -CH2SO3Na and -C6H4SO3Na.

The acrylonitrile polymer used in the present invention, a monomer that provides the polymerized unit (1) by cleavage of a double bond, a monomer that provides the polymerized unit (2), and optionally the polymerized unit (3). It can be produced by polymerizing monomers giving the following in predetermined amounts.

The acrylonitrile polymer may be polymerized by any known method such as aqueous polymerization, emulsion polymerization, or solution polymerization.

In addition, with respect to requirement (B), any of the above acrylic fibers used in the present invention has an elongation rate of 10% or less at 260 ° C. in the relationship between temperature and elongation rate measured under elevated temperature. The preferable elongation rate is 6% or less. The acrylic fiber used in the wool-blend fabric of the present invention has excellent heat resistance and less sagging under high-temperature environments compared to conventional acrylic fibers. Because acrylic fibers have this property, in blended fabrics with wool, it is possible to obtain fabrics with excellent looseness and drapability due to the small shrinkage of acrylic fibers due to the difference in heat resistance with wool.

The acrylic fiber used in the wool-blend fabric of the present invention more preferably has the following properties. 210℃
The dry heat relaxation shrinkage rate of is preferably 3% or less, more preferably 1% or less.

Young's modulus is preferably 400 to 700 kgf/mm2, more preferably 500 to 600 kgf/mm2
It is. The tensile strength is preferably 2 to 5 g/d, more preferably 3 to 4 g/d, and the tensile elongation is preferably 35% or more, more preferably 35 to 60%.

The acrylic fibers used in the blended fabric with wool of the present invention are selected from the acrylonitrile polymers specified in (A) or (A') above, for example (1) specified in (A) or (A') above. A spinning dope of the acrylonitrile copolymer obtained is extruded through an orifice of a spinneret to generate a trickle of the spinning dope, (2) the trickle is coagulated and drawn 5 to 10 times to produce a drawn yarn, (3) It can be produced by a method characterized by:) heating the drawn yarn to shrink it by 3 to 25%, and (4) subjecting the obtained shrink yarn to a drying process.

It goes without saying that the spinning dope used in step (1) above can be prepared by dissolving the acrylonitrile polymer in a solvent, but it can also be a polymerization solution containing the polymer obtained as a result of polymerization. In the latter case, it is desirable to employ a polymerization reaction system that can be used as a spinning stock solution for wet spinning by simply recovering unreacted monomers from the polymerization solution.

The spinning method in step (1) above may be any known method such as wet spinning, dry-wet spinning, dry spinning, or semi-melt spinning. Wet spinning or dry spinning is particularly preferred.

These spinning methods are known per se; for example, wet spinning is described in Japanese Patent Publication No. 57-167410, Japanese Patent Application Laid-Open No. 57-167411, and Japanese Patent Application Laid-Open No. 57-210011.
The method disclosed in Japanese Patent Application Laid-Open No. 57-112410 or Japanese Patent Application Laid-Open No. 58-132107 is employed. Regarding the dry method, for example,
Regarding the method described in Publication No. 5 or Japanese Patent Application Laid-open No. 59-21711, and the dry-wet method, see Japanese Patent Application Laid-Open No. 51-92.
The method described in Publication No. 316, etc. is adopted.

No matter which spinning method is used, the spinning dope is processed in step (1).
In wet spinning, the rivulet is extruded from the spinneret to form a rivulet of the spinning dope; in wet spinning, the rivulet is extruded into the coagulation liquid;
In dry spinning, the rivulet is extruded into a hot gas atmosphere, and in the wet-dry method, the rivulet is extruded into a gas atmosphere and then introduced into a coagulating liquid.

Next, in step (2), the trickle is stretched 5 to 10 times while undergoing solidification as described above. Stretching can be carried out in one stage or in multiple stages.The stretching ratio of each stage in multi-stage stretching is appropriately selected within a range where the total ratio is 5 to 10 times.The preferred stretching ratio is 6 to 8 times.Stretching ratio If it is less than 5 times, the tensile strength of the fiber will be insufficient, and if it is more than 10 times, single fiber breakage will easily occur and fibrillation will occur.

The drawn yarn obtained in step (2) is then subjected to a washing step (in the case of wet and wet-dry spinning) or oiled, if necessary, and then guided to the heating step of step (3).

In step (3), the drawn yarn is heated to shrink by 3 to 25%. If this shrinkage is less than 3%, the tensile elongation of the fiber will be insufficient;
If it exceeds 5%, high temperature drying becomes necessary, which is not economical.

When the spinning in step (1) is performed by wet spinning, this shrinkage can be carried out using hot water or moist heat before the so-called pre-drying step before subjecting the drawn yarn to a crimper.
Alternatively, it can also be carried out in a pre-drying step.

The resulting shrink yarn is then dried in step (4). If shrinkage is carried out in or before the so-called pre-drying step as described above, this step (4) corresponds to the so-called post-drying carried out after crimping if necessary. The acrylic fibers used in the wool blend fabric of the present invention thus obtained are cut into predetermined lengths using a cutter.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples. Unless otherwise specified, parts and % are parts by weight and % by weight.Analysis methods for various physical property values in the present invention and the following examples-
The measurement method or definition is as follows.

[Polymer composition] 1) When the polymer unit formula (3) did not have -SO2M, the following method was used.

M: The proportion α1 [wt%] of hydrogen atoms or one equivalent of cation in the polymer was determined by the following measurements and calculations. First, Polymer A [g] (about 1 g) was accurately weighed and dissolved in dimethylformamide (JIS special grade).

Next, strong acid type cation exchange resin {50-100 mesh,
After mixing and stirring for 1 hour, the resin was filtered out using a glass filter. Further, the filtrate was titrated with 1/50N NaOH using a potentiometric titration device (Hiranuma Sangyo COM-101 model). Further, a blank test was conducted under the same conditions and corrections were made.

However, A1; Polymer amount [g] B1; 1/50N NaOH sample titration amount [ml] C1;
1/50N NaOH blank test titration [ml] D1: Molecular weight R of polymerization unit formula (2); Hydrogen atom or methyl group Y'; -COOX, -OCOCH3, -CONH2, -C6H5 X; Hydrogen atom, sodium, or The proportion β1 [wt%] of methyl groups in the polymer was determined by the following measurements and calculations. First, 0.5 g of the polymer was dissolved in dimethyl sulfoxide (JIS special grade) to prepare a 50 g/l solution. A liquid cell made of CaF2 was used and an infrared spectrophotometer (Shimadzu IR-430 model) was used to measure the range of 2,500-1,850 cm-1 and 1,850-1,500 cm-1 using dimethyl sulfoxide as a control. The infrared spectrum of the area was recorded. Absorbance of polymer unit formula (3)' determined by baseline correction (if Y' has -CO-, C=O stretching vibration absorption band of 1,500 to 1,800 cm-1, -C6H5) If you have one, 1,500 to 1,7
(Using the =C-H out-of-plane bending vibration absorption band of 00cm-1)
and the absorbance of the 2,240 cm-1 absorption band of the polymer unit formula (1) by mixing the homopolymers of the polymer unit formulas (1) and (3)' in various ratios in advance and using the above method. It was determined from the calibration curve of the absorbance ratio that had been determined.

■) Proportion of polymerization unit formula (1) to the polymerization units [wt%
] is γ1=100−(α1+β1), and using these, the polymer composition [molar ratio] was calculated according to the following formula.

γ1'/β1'/α1'=(K1γ1/53.06)/
(K1β1/E1)/K1α1/D1) However, γ1' and γ1; Ratio [mol%] and [weight%] of polymer unit formula (1) in the polymer β1' and β1; Polymer unit formula (1) in the polymer 3)'
Proportion [mol %] and [weight %] α1' and α1; Proportion [mol %] and [weight %] of polymer unit formula (2) in the polymer E1; Molecular weight D1 of polymer unit formula (3)'; Molecular weight K1 of polymerization unit formula (2); 1/{(γ1/53.06)+(β1/E1)+
(α1/D1)} 2) When Y in the polymerization unit formula (3) is -CH2SO3Na or -C6H5SO3Na, the following method was used.

(2) The proportion α2 [wt%] of the polymer unit formula (2) in the polymer was determined by the following measurements and calculations.

Measurements and calculations were carried out according to method 1) (■).

However, the absorbance of the polymer unit formula (2) was determined using the 1,666 cm -1 absorption band, and a homopolymer of the polymer unit formula (2) was used instead of the polymer unit formula (3) to prepare the calibration curve.

(2) The proportion β2 [wt%] of the polymer unit formula (3) in the polymer was determined by the following measurements and calculations.

Measurements and calculations were carried out according to method 1) (■).

β2 [weight%] = [{(1/50) x f2 x (B2-C
2) [ml]×E2×10-3}/A2]×100 However, A2; Polymer amount [g] B2; 1/50N NaOH sample titration amount [ml] C2;
1/50N NaOH blank test titer [ml] E2; molecular weight f2 of polymerization unit formula (3): titer of 1/50N NaOH ■) Calculate the polymer composition [molar ratio] by the method of ■) in 1) did.

γ2'/β2'/α2'=(K2γ2/53.06)/
(K2β2/E2)/K2α2/D2) However, γ2' and γ2; proportion [mol%] and [weight%] of polymer unit formula (1) in the polymer; β2' and β2; polymer unit formula (1) in the polymer; 3) ratio [mol %] and [weight %] α2′ and α2; ratio [mol %] and [weight %] of polymer unit formula (2) in the polymer E2; molecular weight D2 of polymer unit formula (3) ; Molecular weight K2 of polymerization unit formula (2); 1/{(γ2/53.06)+(β2/E2)+
(α2/D2)} [Polymerization degree] First, about 0.2 g of the polymer was mixed with dimethylformamide (JIS
(special grade) was dissolved in approximately 50 ml to prepare a solution of C' [g/l]. Using an Ostwald viscometer in a constant temperature bath maintained at 30° C., the number of seconds A for falling of the solution and the number of seconds B for falling of dimethyl formaldehyde were measured.

The degree of polymerization P was determined by the following calculation.

Relative viscosity ηrel=A/B Specific viscosity ηsp=ηrel−1 Viscosity average molecular weight Mη=(ηsp/C)/1.5×10−
4 P=Mη/m However, average polymerized unit molecular weight m=(53.06×γ+E×
β+D×α)/100 C [mol/l]=C'/m where γ: Ratio of polymer unit formula (1) in the polymer [mol%] β: Ratio of polymer unit formula (3) in the polymer Proportion [mol%] α; Proportion of polymeric unit formula (2) in the polymer [mol%] E; Molecular weight of polymeric unit formula (3) D; Molecular weight of polymeric unit formula (2) [measured at elevated temperature [Relationship between temperature and elongation rate] The apparatus used is shown in Fig. 2. Total length of fiber is about 30d and length is 80mm.
Make a loop of mm (40 mm when folded in half, 2), hold it in the heating cylinder 1 which is open to the atmosphere above and below using the clip 3, and place a load of 25 mg/cm under the heating cylinder using a wire.
d (approximately 1,500 mg, 4). Next, the temperature was raised from around 30°C at an average rate of 40°C/min, and the load position was tracked with the camera 5 and recorded together with the temperature. FIG. 1 shows the relationships measured using this method for several acrylic fibers.

Elongation rate [%] is (load displacement [mm]/40 [mm])
Calculated by ×100.

[Relaxation Shrinkage Rate] A fiber bundle of about 600 mm was made with a total of about 9000 d of fibers, and marks were placed at 500 mm intervals under a load of 0.1 g/d (about 900 g) at room temperature.

The unloaded fiber bundle was treated with dry heat at 210° C. for 30 minutes without applying tension. A load of 900 g was applied again to the fiber bundle that had been cooled to room temperature, and the mark interval A [mm] was measured.

Relaxation contraction rate [%] is {(500-A)/500}×10
Calculated using 0.

[Tensile strength and elongation, Young's modulus] Measured using a constant speed extension type tester (Toyo Baldwin UTM-II model) based on J1S L 1015.

Reference Example 1 A spinning stock solution prepared by dissolving an acrylic polymer having the composition and degree of polymerization shown in Table 1 in dimethylformamide (hereinafter abbreviated as DMF) to a polymer concentration of 26.5% by weight was Coagulation bath DMF/water = 60/4 from the orifice of a 50,000-hole spinneret with a circular cross section of 0.06 m/m
0 (weight ratio), extruded at 20°C, spinning draft 0.4
After picking it up, DMF/water = 30/70 (weight ratio),
It was stretched 8 times at 85°C.

Subsequently, after washing with water and applying oil, roller drying was performed at 150° C. while applying 15% shrinkage.

Furthermore, after oil application - crimp application - crimp set (
A 3D acrylic fiber was obtained by post-drying (humid heat at 120°C).

The obtained acrylic fiber had the characteristic values shown in Table 1. Furthermore, FIG. 1 shows the relationship between temperature and elongation rate measured under elevated temperatures in Runs 1 (curve ■), 2 (curve ■), and 5 (curve ■).

The meaning of each note in Table 1 above is as follows.

*1 Abbreviation for sodium 2-acrylamide-2-methylpropanesulfonate (SAMPS), *2 Abbreviation for methyl acrylate, *3 Value at 260°C in the relationship between temperature and elongation measured at elevated temperatures, *4 Dry Heat treatment at 210° C. for 30 minutes. *5 Sodium methallylsulfonate was used in place of SAMPS.

Reference Example 2 A spinning stock solution prepared by dissolving an acrylic polymer having the composition and degree of polymerization shown in Table 2 in dimethylformamide (hereinafter abbreviated as DMF) and adjusting the polymer concentration to 26.5% by weight was Coagulation bath DMF/water = 60/
40 (weight ratio), extruded at 20°C, hereinafter referred to as Reference Example 1
A 2d acrylic fiber was obtained by the same treatment.

Example 1 Run No. of Reference Example 1 1 to 5 acrylic fibers in 1
After cutting on a 02 mm bias, card slivers were obtained through a carding machine. Further, the above acrylic fiber sliver and 60''s wool top were mixed in a drawing machine at a ratio of 40% by weight to 60% by weight, and then normal worsted spinning was performed to obtain a spun yarn with a count of 2/48.

Next, the above spun yarn was used for warp and warp, 2/2 twill weave, density warp; 5
Fabrics are made at 2 strands/inch, weft: 55 strands/inch, and then the following steps are performed: boiled carpet, washed carpet, fulling, dry carpet, dyeing, dehydration, dry carpet, brushing, shearing, softening, dry carpet, A blended fabric piece-dyed by steaming was obtained.

For dyeing, acid dyes {Sandolan, S.
a-ndoz Ltd. Migre Girl GWL-422 (Nippon Someka Kogyo Co., Ltd.), Ionet FY104 (Sanyo Kasei Co., Ltd.), mirabilite and 4 in a dyebath adjusted to pH approximately 5 using acetic acid/sodium acetate.
Raise the temperature from 0℃ to 102℃ at a rate of about 2℃/min.
It was carried out for 30 minutes at 02°C. In addition, the softening process was performed using Vinitol FK (manufactured by Nagoya Yuka Co., Ltd.).

Evaluations of the obtained blended fabrics are shown in Table 3.

Example 2 Run No. of Reference Example 2 After cutting 6 to 10 acrylic fibers to a fixed length of 76 mm, they were passed through a carding machine to obtain card slivers. Furthermore, the above acrylic fiber sliver and 6
After mixing 0″s wool top with a drawing machine at a ratio of 40% by weight and 60% by weight, normal worsted spinning is carried out to obtain 1/
A spun yarn of count 48 was obtained.

Next, the above spun yarn was used for warp, 2/1 twill weave, density warp; 9
Fabrics are made with 6 strands/inch, weft: 55 strands/inch, and then the following steps are performed: boiled carpet, washed carpet, boiled carpet, dry carpet, dyeing, dehydration, dry carpet, shearing, softening, dry carpet, steamed carpet. A piece-dyed blended fabric was obtained.

Note that dyeing and softening were carried out in the same manner as in Example 1.

Evaluations of the obtained blended fabrics are shown in Table 4.

(Effects of the Invention) The novel blended fabric of acrylic fiber and wool of the present invention takes advantage of the vivid coloring properties inherent in acrylic fiber, and provides a blended fabric that has excellent heat resistance, fluffiness, and drapability. be able to.

[Brief explanation of the drawing]

FIG. 1 shows the relationship between temperature and elongation for the acrylic fiber of the present invention and a conventional acrylic fiber equivalent.

Claims (2)

[Claims] Claim 1: A blended fabric of acrylic fiber and wool, comprising (A), (a) a polymerized unit represented by the following formula (1) and the following formula (2), where M is a hydrogen atom or one equivalent of a cation. (b) The polymerized unit (2) accounts for 0.4 to 1.5 mol% of the total of the polymerized unit (1) and the polymerized unit (2). (c) consists of an acrylonitrile copolymer with a degree of polymerization in the range of 600 to 1,500, and (B) elongation at 260°C in the relationship between temperature and elongation measured at elevated temperatures. A blended fabric of acrylic fibers and wool, characterized in that it contains acrylic fibers having an acrylic fiber content of 10% or less. [Claim 2] A blended fabric of acrylic fiber and wool, comprising (A') (a') the polymerized unit of the above formula (1), the above formula (2);
) and the polymerized unit represented by the polymerized unit (3) which is different from the polymerized unit of the above formula (2) derived from a monomer copolymerizable with acrylonitrile, (b') the above polymerized The polymerized unit (2) accounts for 0.4 to 1.5 mol% of the total of the unit (1) and the polymerized unit (2), and the polymerized unit (3) accounts for 5% by mole based on the polymerized unit (1). (c) degree of polymerization is 600 to 1,
500, and (C) contains acrylic fibers whose elongation rate at 260°C is 10% or less in the relationship between temperature and elongation rate measured at elevated temperatures. This is a blended fabric of acrylic fiber and wool.