JPH03220342A - Water-proof web - Google Patents

Abstract

PURPOSE:To provide the subject web having excellent creep resistance and light fastness, etc., by employing a copolymer having specific polymerization units. CONSTITUTION:(A) A acrylonitrile producing polymerization units of formula I is copolymerized with 0.4-1.5mol% of (B) 2-acrylamide-2-methyl-propane sulfonic acid producing polymerization units of formula II (M is cation or H), followed by forming the copolymer into fibers having a polymerization degree of 600-1500 and having an elongation of <=10% at 260 deg.C, from which is provided the objective web.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a waterproof fabric using acrylic fibers. More specifically, the present invention relates to a waterproof fabric using acrylic fibers having excellent creep resistance and light fastness.

(Prior Art) Conventionally, polyester fibers, polyamide fibers, vinylon fibers, etc. have been used as materials for base fabrics for waterproof fabrics such as tents, beach umbrellas, automobile covers, and port covers.

Although acrylic fibers have excellent weather resistance and strength retention, they are only slightly used for the above-mentioned applications because of their poor creep resistance and light fastness.

Therefore, if the above-mentioned drawbacks can be overcome, it is expected that acrylic fibers will be superior to polyester fibers, polyamide fibers, vinylon fibers, etc. as materials for waterproof fabrics.

(Problems to be Solved by the Invention) An object of the present invention is to provide a waterproof fabric using a fabric made of acrylic fibers having excellent creep resistance and light fastness.

Another object of the present invention is to provide an acrylic waterproof fabric with excellent creep resistance and light fastness.

Other objects and advantages of the 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 as follows: (A), (a) a polymerized unit represented by the following formula (1) and the following: Formula (2) % Formula % where M is a hydrogen atom or a -equivalent cation, (b) consists essentially of the polymerized unit represented by (b) the sum of the polymerized unit (2) and the polymerized unit (2). On the other hand, the polymerized unit (2) occupies 0.4 to 1.5 mol%, and (c) the polymerization degree is in the range of 600 to 1,500, and (B) consists of an acrylonitrile copolymer.
In the relationship between temperature and elongation rate measured under elevated temperature, 2
This is achieved by a waterproof fabric characterized by having a fabric made of acrylic fiber as a base fabric and having an elongation rate of 10% or less at 60°C.

As mentioned above, the acrylic fiber used in the waterproof fabric of the present invention is a novel material characterized by the requirement (A) to specify the polymer forming it and the requirement (B) to specify its elongation rate at high temperatures. It is acrylic fiber.

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-methyl-propanesulfonic acid (hereinafter abbreviated as AMPS) or a salt thereof.

The ratio of polymerized units (1) to 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 repolymerized units. 98.5 mol%). The polymerized units (2) preferably account for 0.6 to 1.2 mol % (99.4 to 98.8 mol % of the polymerized units (1)) based on the same basis. Polymerization unit (2)
If the ratio is less than 0.4 mol %, gelation tends to occur during the polymerization process, and because there is insufficient dyeing seat, it becomes difficult to dye deep colors. 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 is likely to occur during the polymerization process, and in order to carry out normal wet spinning,
Viscosity is too high.

As specified in requirement (A), the acrylic fiber used in the waterproof fabric of the present invention has a polymerization unit (1) and a polymerization unit (2) based on the sum of the polymerization unit (1) and the polymerization unit (2).
2) in a proportion of 0.4 to 1.5 mol%. According to the research of the present inventor, polymerized unit (1) and polymerized unit (2)
), other polymerized units (
It has been found that the above objects and advantages of the present invention can be maintained even if 3) is further contained in a small amount.

That is, the acrylonitrile copolymer containing such other polymerized units (3) meets the following requirement (A) instead of requirement (A).
'): (A') (a') The polymerized unit of the above formula (1), the polymerized unit of the above formula (2), and the polymerized unit of the above formula (2) derived from a monomer copolymerizable with acrylonitrile. is substantially composed of polymerized units represented by different polymerized units (3), and (b') the above polymerized units (2) are 0.4 to 1 with respect to the total of the above polymerized units (1) and (2). .5 mol% and said polymerized unit (3) accounts for not more than 5% by weight based on said polymerized unit (1), and (C) the degree of III degree is in the range of 600-1,500(7). be satisfied.

Regarding requirement (A'), polymerized unit (1) and polymerized unit (2)
The ratio of polymerized units (2) to the total of these repolymerized units is
) 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 ('l) and (2), there is another polymerized unit (3) that is different from the polymerized unit (2) derived from a monomer copolymerizable with acrylonitrile. , based on the polymerized unit (1),
Present at up to 5% by weight. Polymerized units (3) are preferably present in an amount of 3% by weight or less based on the same criteria.

As the polymerized unit (3), preferably, for example, the following formula (
3) % Formula % (3) Here, R is a hydrogen atom or a methyl group, and Y is a group represented by the formula -COOX (where X is a hydrogen atom, a sodium atom or a methyl group), −〇〇 〇
CH3, CON Hz, -CsHs, -CHz SO
Examples include a unit represented by the following, which is a group selected from the group consisting of sNa and -C, H, 5OsNa.

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

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

Furthermore, regarding requirement CB), all of the above acrylic fibers used in the present invention have 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 fibers used in the waterproof fabric of the present invention have excellent heat resistance and less sagging in high-temperature environments than conventional acrylic fibers.

In addition, the acrylic fiber used in the waterproof fabric of the present invention generally has favorable properties regarding light fastness, and the light fastness (carbon arc fade meter black panel temperature 63°C - JIS LO842) is preferably at least grade 4, More preferably at least 5th grade, particularly preferably at least 6th grade. For this reason, the acrylic fibers of the present invention are preferably solution colored. The acrylic fiber used in the waterproof fabric of the present invention is further unique in that it exhibits such excellent light resistance compared to conventional acrylic fibers.

The acrylic fiber used in the waterproof fabric of the present invention more preferably has the following properties. The dry heat relaxation contraction rate at 210°C is preferably 3% or less, more preferably 1
% or less. Young's modulus is preferably 400-700
kgf/+nm', more preferably 500 6
00 kgf/mm”.The tensile strength is preferably 2
-5 g/d, more preferably 3-4 g/d. The tensile elongation is preferably 35% or more, more preferably 3
It is 5-60%.

The acrylic fiber used in the waterproof fabric of the present invention is the above-mentioned -(
From the acrylonitrile-based polymer specified in A) or (A'), for example, (1) spinning a spinning dope of the acrylonitrile-based copolymer specified in (A) or (A') above is extruded from an orifice of a spinneret. producing a trickle of the stock solution, (2) drawing the trickle by 5 to 10 times while coagulating it to produce a drawn thread, (3) heating the drawn thread to shrink it by 3 to 25%, and (4) ) It can be produced by a method characterized by subjecting the obtained shrinkable 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 hexamer from the polymerization solution.

When coloring the acrylic fiber used in the present invention with a stock solution, for example, after adding and mixing a dye solution dissolved in a solvent or a pigment dispersion dispersed in a solvent to a spinning stock solution,
Perform spinning. The above-mentioned dye solution or pigment dispersion can be added to and mixed with the spinning dope, for example, while preparing the spinning dope, or it can also be carried out using a stationary mixer installed just before the spinneret.

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, and for example, wet spinning is described in Japanese Patent Publication No. 167.410/1982, Japanese Patent Application Laid-Open No. 167.411/1982, Japanese Patent Application Laid-open No. 210/1982,
The method disclosed in Japanese Patent Application Laid-open No. 011, Japanese Patent Application Laid-open No. 57-112410, or Japanese Patent Application Laid-Open No. 58-132107 is adopted. Regarding the dry method, for example,
The method described in JP-A No. 1,665 or JP-A-59-21-711, and the wet-dry method described in JP-A-51-92316 are employed.

No matter which spinning method is used, the spinning dope is processed in step (1).
In the process, the spinning dope is extruded from the spinneret to form a trickle of spinning dope. In wet spinning, the rivulet is forced into a coagulation liquid, in dry spinning, the rivulet is forced into a hot gas atmosphere, and in the wet-dry process, the rivulet is forced into a gas atmosphere and then into a coagulation 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 the 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. If the stretching ratio is less than 5 times, the tensile strength of the fibers will be insufficient, and if it exceeds 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.

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 when the spinning in step () is performed by wet spinning.
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 thus obtained acrylic fiber used in the waterproof fabric of the present invention is cut into a predetermined length using a cutter.

The base fabric of the waterproof fabric of the present invention is made of the above-mentioned acrylic fiber fabric. Fabrics include sheet-like structures such as ordinary woven fabrics, knitted fabrics, and nonwoven fabrics. These sheet-like structures can be manufactured by methods known per se.

The waterproofing of the sheet-like structure is carried out according to methods known per se and using waterproofing agents known per se.

As the waterproofing agent, for example, fluororesin, silicone resin, etc. are preferable in the case of breathable waterproof fabric.
In the case of a non-breathable waterproof cloth, for example, acrylic resin, vinyl chloride resin, etc. are preferably used.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples. Note that unless otherwise specified, parts and percentages are 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 1) When the polymer unit formula (3) did not have -5o or M, the following method was used.

NH-C-CH, -5O,M C.I.

M: The proportion a+ [wt%] of hydrogen atoms or -equivalent cations in the polymer was determined by the following measurements and calculations. First, Polymer A [gl (about Ig) 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 separated using a glass filter. Furthermore, the above oral fluid was collected in a potentiometric titration device (Hiranuma Sangyo C0M-101 model).
. Titrated with N NaOH. Further, a blank test was conducted under the same conditions and corrections were made.

Eight! However, A1: Polymer amount [gl, B l'/s, N Na OH sample titer [ml]
Cr + '/soN Na OH Blank Test Titration [
ml] DI; Molecular weight f of polymer unit formula (2); '/*oN titer of NaOH ii)
R R; hydrogen atom or methyl group Y; C00X, -0COCH3, -CON Hz
, -CsHs First, add 0.5 g of polymer to dimethyl sulfoxide (JI
S special grade) to make a 50 g/ff solution. Ca
An infrared spectrophotometer (Takashi Seisakusho IR-43) was used with dimethyl sulfoxide as a control.
0 type) 2.500-1,850 cm-' and 1.8
An infrared spectrum was recorded in the region of 50 to 1.500 cm-''.The polymer unit formula (
3) absorbance (1,500 if Y has -CO-
~1.800 cm-' C=O stretching vibration absorption band, -C,
H, 1.500 to l.

The ratio of the absorbance of the =C-H out-of-plane bending vibration absorption band at 700 cm-' and the absorbance of the 2.240 cm-' absorption band of the polymerization unit formula (1) is determined in advance using the polymerization unit formulas (1), (3). ) were mixed in various proportions and determined from the calibration curve of the absorbance ratio determined by the above method.

1ii) The proportion [wt%] of the polymerization unit formula (1) in the polymerization units is γ, = 100−(σ1+β1), and using these, the polymer composition [molar ratio] was calculated according to the following formula.

11'/β1'/α+=(K+γ, 153.06)/(
Klβl/E+)/K, a r/D+)
However, 11' and γ1; the polymerization unit formula (1
) [mol %] and f weight %] β1' and β,: proportion in the polymer Proportion of unit formula (3) [mol %] and [weight %] ~σ1' and σ1; polymer proportion in the polymer Unit formula (2)
Ratio [mol %] and [weight %] El; Molecular weight of polymer unit formula (3) Dl: Molecular weight of polymer unit formula (2) +; l/((γ, 153.06) + (βl/El) +
(αr/Dl)) 2) When Y in the polymerization unit formula (3) is -CH, SO, Na or -C@H, SO3Na, the following method was used.

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

The measurements and calculations were performed according to the method of i) in l). However, the absorbance of the polymer unit formula (2) was determined using the 1.666 cm-' absorption band, and a homopolymer of the polymer unit formula (2) was used instead of the polymer unit formula (3) in preparing the calibration curve.

M) The proportion β and [weight %] of the polymer unit formula (3) in the polymer were determined by the following measurements and calculations.

Measure and calculate according to method 1).

β2[wt%] = [(('to)xr2xatz-ci
) [mt]xE,
1lC2; '/ soN NaOH blank test titer [m1] E2; molecular weight f 2 i ' of polymerization unit formula (3) / soN NaOH titer ii)
The polymer composition [molar ratio] was calculated by the method of i) in l).

γ,′/β,′/αi−(Kgγ, 153.06)/(
K2β! /E z)/(x, σz/Dz) where γ, ′
and γ3: proportion of polymer unit formula (1) in the polymer [
[mol%] and [weight%] β2' and β2; proportion of polymeric unit formula (3) in the polymer cmol%j and [weight%] β2' and α2; proportion of polymeric unit formula (2) in the polymer Ratio [mol %] and [weight %] E2; molecular weight of polymer unit formula (3), - molecular weight Kz of polymer unit formula (2); l/((γ, 153.06) + (βz/E
x) + (αz/Dz)) [Degree of polymerization] First, 0.2 g of polymer was added to dimethylformamide (JIS
(special grade) was dissolved in approximately 50 ml to prepare a solution of C' [g/a]. 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 Wtel=A/B Specific viscosity v) sp -W rel -1 Viscosity average molecular weight M v -(v sp/C)/1.5x 10
-'P=Mv/Tofu However, average polymerized unit molecular weight m=(53,06Xγ+E×
β+DXff)/100 C [mol/Q] = C'/silkworm where γ; proportion of polymer unit formula (1) in the polymer c mol%] β: proportion of polymer unit formula (3) in the polymer [ mol%] σ; Proportion of polymer unit formula (2) in the polymer [mol%
I E: Molecular weight of polymerization unit formula (3) D: Molecular weight of polymerization unit formula (2) [Relationship between temperature and elongation rate measured under elevated temperature 1 The apparatus used is shown in FIG. 2. Total length of fiber is about 30d and length is 80mm.
Make a 40mm loop (folded in two), 2), hold this using clip 3 inside the heating cylinder which is open to the upper and lower atmosphere, and use a wire to place a load of 25mg under the heating cylinder.
/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. The elongation rate [%] is (load displacement [mm] /40 [m
m] )xl oo.

[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 O, 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 is applied again to the fiber bundle that has been cooled at room temperature, and the mark interval is A [mm].
was measured.

Relaxation contraction rate [%] is ((500-A)1500)X1
Calculated using 00.

[Tensile strength and elongation, Young's modulus I Measured using a constant speed extension type tester (Toyo Baldwin UTM-n type) based on JIS L1015.

[Light fastness] Acrylic fiber cut to a constant length of 51 m/m was spun to 2 inches to obtain a spun yarn with a count of 1/28.3
Circular knitting was obtained using an I/2″, 16G circular knitting machine.

The circular knit was treated with a blue scale using a carbon arc fade meter (black panel temperature: 63° C.), and then discoloration and fading were determined. (JIS Lo 842) Example 1 Yellow pigment (Hoechs) pulverized to an average particle size of about 1 pm.
t Green G G 01 ) was dispersed in dimethylformamide (hereinafter abbreviated as DMF).

After dissolving an acrylic polymer having the composition and degree of polymerization shown in Table 1 in DMF, it was added and mixed with the above pigment dispersion, and the polymer concentration was 25% by weight and the pigment concentration was 2% by weight/polymer spinning. The stock solution was prepared.

The above spinning dope was passed through the orifice of an 80,000-hole spinneret with a circular cross section of 0.055 m/m in diameter into a coagulation bath DMF.
/water = 60/40 (weight ratio), extruded at 20 °C, taken off at spinning draft 0.4, DMF/water - 30/
70 (weight ratio) and stretched 8 times at 85°C.

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

Furthermore, after oil application - crimp application - crimp set (
After drying (humid heat at 120°C), 2d acrylic fibers were obtained.

The obtained acrylic fiber had the characteristic values shown in Table 1.

Example 2 Run Nol acrylic fiber was cut to a fixed length of 51 m/m and spun for 2" to obtain a spun yarn with a count of 2/34. Next, using the above spun yarn, the yarn had a density of 73 yarns/warp. A plain woven fabric with a weft of 73 pieces/inch was obtained.

The above fabric was mixed with 5 parts by weight of Asahi Guard AG-710 (7 resin waterproofing agent, manufactured by Asahi Glass) and 10 parts by weight of Hi-Softer.
(Kusei Kagaku) 1 part by weight, Improper Tool 2 parts by weight,
After immersion in a treatment bath consisting of 92 parts by weight of water, the reduction rate was 50.
I narrowed it down to %. Then, after drying at 100°C, 150°
It was heat-treated at C.

Furthermore, the above fabric was coated with 20 parts by weight of Poron Coat (silicone resin waterproofing agent, Shin-Etsu Chemical Co., Ltd.) and 8 parts by weight of trichlorethylene.
After being immersed in a treatment bath containing 0 parts by weight, the sample was squeezed to a squeezing rate of 40%. Next, it was dried at 100°C and then heat-treated at 160°C.

The obtained waterproof fabric is water repellent too (JISL1092
spray method), water resistance 25.8cm (JIS L
1092 A method (low water pressure method)).

(Effects) The waterproof sheet of the present invention is an unprecedented waterproof sheet that takes advantage of the inherent weather resistance of new acrylic fibers and has excellent creep resistance and light fastness.

[Brief explanation of drawings]

FIG. 1 shows the relationship between temperature and elongation for the acrylic fiber of the present invention and a conventional acrylic fiber equivalent. FIG. 2 is a schematic diagram of the apparatus used to measure the relationship of FIG. 1. 1 other person

Claims (1)

[Claims] 1. (A), (a) The following formula (1) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ ... (1) The polymerized unit represented by the following formula (2) ▲ Numerical formula , chemical formulas, tables, etc. ▼...(2) where M is a hydrogen atom or one equivalent cation, consisting essentially of the polymerized unit represented by (b) the above polymerized unit (1) The polymerized unit (2) accounts for 0.4 to 1.5 mol% of the total polymerized unit (2),
(c) consists of an acrylonitrile copolymer with a degree of polymerization in the range of 600 to 1,500, and (B) in the relationship between temperature and elongation rate measured at elevated temperatures, 260 to 1,500.
A waterproof fabric characterized in that the base fabric is a fabric made of acrylic fiber and has an elongation rate of 10% or less at °C. 2. (A') (a') What is the polymerized unit of the above formula (1), the polymerized unit of the above formula (2), and the polymerized unit of the above formula (2) derived from a monomer copolymerizable with acrylonitrile? It consists essentially of polymer units represented by different polymer units (3), and (b') the polymer unit (2) is 0.4 to 1. and the polymerized unit (3) accounts for 5% by weight or less based on the polymerized unit (1), (c) the degree of polymerization is 600 to 1,
500, and (C) in the relationship between temperature and elongation rate measured at elevated temperatures, 260
A waterproof fabric characterized in that the base fabric is a fabric made of acrylic fiber and has an elongation rate of 10% or less at °C. 3. The waterproof fabric according to claim 1 or 2, wherein the acrylic fibers are dyed with an undiluted solution. 4. A fabric made of the acrylic fiber specified in claim 1 as a base fabric for the waterproof fabric of claim 1. 5. A fabric made of the acrylic fiber specified in claim 2 as a base fabric for the waterproof fabric of claim 2.