JPH02182975A - Stain-proofing polyethylene fiber cloth having high strength and elastic modulus - Google Patents

Abstract

PURPOSE:To obtain the subject cloth imparted with durable stain resistance, hydrophilic property and antistaticity by applying specific amounts of a specific block copolymer and a binder resin composed of a thermosetting resin, etc., to a polyethylene fiber cloth having a specific physical property and heat- treating the cloth. CONSTITUTION:A cloth containing a polyethylene fiber having a tensile strength of >=20g/d and a tensile modulus of >=500g/d is applied with (A) 0.1-10wt.% of a block copolymer of (i) terephthalic acid or terephthalic acid and isophthalic acid and (ii) an alkylene glycol and a polyalkylene glycol and (B) 0.1-10wt.% of a binder resin selected from a thermosetting resin and a thermoplastic resin (e.g. a polyurethane resin or N-methylol resin) at a ratio (B/A) of 0.01-1 and is heat treated at <=150 deg.C (preferably 90-150 deg.C) to obtain a polyethylene cloth having stain-proofing property and antistaticity resistant to washing 4 without deteriorating the characteristic high strength of the polyethylene fiber.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a polyethylene fiber-based fabric that has stain resistance, high strength, and high elastic modulus, and more particularly, has durable stain resistance, hydrophilicity, and antistatic properties. The present invention relates to a high-strength, high-elastic modulus poly, ethythin fiber-based fabric that has been imparted with properties.

[Conventional technology]

In general, methods for imparting antifouling properties to synthetic fibers include (1) a soil hide property imparting (SH property imparting) method that utilizes the structural light dispersion effect of hollow cross-section fibers, etc.; 4yv-geeing (hydrophobicization) soil that makes it difficult for dirt to stick/stain guard property (SG property imparting) method, (3) Hydrophilic processing to increase the energy on the fiber surface (hydrophilicity) to make it easier to remove adhering dirt. Soil/
A method for imparting stain release properties (imparting SR properties) is known. Among these, it is said that imparting SR properties as described in (3) above is particularly effective as a means of making it easier to remove oily stains.

As one method for imparting such SR properties, a method is known in which a polyester fiber fabric is treated with a block copolymer of terephthalic acid, or terephthalic acid and isophthalic acid, alkylene glycol, and polyalkylene glycol (Japanese Patent Publication No. 46-13197). However, no proposal has been made for imparting the above-mentioned SR properties to a polyethylene fiber fabric having high strength and high modulus of elasticity, as well as imparting stain resistance with excellent washing resistance.

[Problem to be solved by the invention]

When a high strength, high modulus polyethylene fiber fabric is treated with the aforementioned block copolymer of terephthalic acid or terephthalic acid and isophthalic acid, alkylene glycol and polyalkylene glycol, the high modulus and high strength of the polyethylene fibers are treated. , furthermore, light weight, light resistance, i! j
It is possible to impart SR properties without impairing friction properties or chemical resistance, but this only applies to the initial S condition before washing.
It was found that although it was only excellent in R properties, the excellent SR properties were lost by repeated washing, that is, the durability was poor.

Accordingly, an object of the present invention is to provide a high-strength, high-modulus polyethylene fiber fabric that has stain resistance, hydrophilicity, and antistatic properties and is durable even after repeated washing.

[Means to solve the problem]

The present invention has a tensile strength of 2097d or more and a tensile modulus of 50
For fabrics containing polyethylene fibers of 0976 or higher, (
A) a block copolymer of terephthalic acid, or terephthalic acid and isophthalic acid, and alkylene glycol and polyalkylene glycol; and (B) at least one binder resin selected from the group consisting of a thermosetting resin and a thermoplastic resin. , the following formula: % formula % (1) In the C formula, A is the amount of the block copolymer fA) attached to the polyethylene fiber (i amount%), and B is the amount of the binder resin (B) attached to the polyethylene fiber (weight). It is a stain-resistant, high-strength, high-modulus polyethylene fiber fabric that has been heat-treated at a temperature of 150° C. or lower after being applied in the range expressed by %)].

The polyethylene fibers forming the t+1 fabric of the present invention have a tensile strength of 20. @/d or more, preferably 30//d or more, and the tensile modulus is 50017d or more, preferably 8009
/d or more, more preferably 1000g/d or more, f!
It is fiber. Because these fibers have high tensile strength and tensile modulus, they are sometimes used in fields such as bulletproof clothing, blade-proof clothing, and blade-proof gloves. In this case, the tensile strength is 2
less than 0.9/d, or the tensile modulus is 50097
If it is less than d, the Ir impact resistance and ballistic resistance will not be sufficient and it will be difficult to obtain a good protective effect, which is not preferable.

The high-strength, high-modulus polyethylene fiber fabric of the present invention may be a knitted fabric or non-woven fabric made only of the long or short fibers of the polyethylene fibers, or may be a fabric made of the polyethylene fibers and other fibers such as cotton or polynosic. Cellulose fibers such as rayon, protein fibers such as wool and silk, nylon 6, nylon 4/6, nylon 6/6, nylon 1
1 grade polyamide fibers, aromatic polyamide fibers such as poly(p-phenylene terephthalate), poly(p-phenylene terephthalate), etc.
-) blended fabrics with aromatic polyester fibers such as unicine terephthalate, glass fibers, and carbon fibers;
It may also be a nonwoven fabric.

As a means for mixing the high-strength, high-modulus polyethylene fibers with the other fibers mentioned above, commonly used known methods such as blending, pulling, plying, fluid agitation processing, interlacing, and weaving can be used.

When used in combination with other fibers, the mixing ratio of high strength, high modulus polyethylene fibers can be selected as appropriate depending on the use of the fabric, but in general, the high strength, high modulus of polyethylene fibers In order to effectively exhibit the advantages of the above, it is desirable that the content be at least 20% by weight or more, preferably 40% by weight or more. In addition, the various fibers mentioned above can be used as the mixed fibers used in the fabric of the present invention, but
Among these, hydrophilic fibers such as cellulose fibers and protein fibers, or hydrophilic synthetic fibers are particularly preferred in terms of the SR effect described below.

The block copolymer (A) used for applying to the above-mentioned fabric according to the present invention includes: terephthalic acid-fluorene glycol-polyalkylene glycol; terephthalic acid-isophthalic acid-fulkylene glycol-polyalkylene glycol; Contains block copolymers such as acid-isophthalic acid-fulkylene glycol-polyalkylene glycol monoether.

In the block copolymer, the acid component may be terephthalic acid alone, or a mixture of isophthalic acid may be used depending on the case. Therefore, the molar ratio of terephthalate units to inphthalate units is preferably 100:0 to 50:50. The molar ratio of the alkylene glycol and polyalkylene glycol is 90=10 to 1.
It is best to set it to 0:90. The molar ratio of the terephthalate units or terephthalate units and isophthalate units to the total of alkylene glycol and polyalkylene glycol is generally 2 to 15:1. Boria)
Vd (the molecular weight of lengelicol is usually 400-6000
Preferably, it is 0.

The alkylene glycol includes ethylene glycol, propylene glycol, tetramethylene glycol, decamethylene glycol, etc., and the polyalkylene glycol includes polyethylene glycol, polypropylene glycol, etc. Polyalkylene glycol monoethers include monomethyl ether, monoethyl ether, etc. of polyethylene glycol, polypropylene glycol, and the like.

The above-mentioned block copolymer and its manufacturing method are described, for example, in Japanese Patent Publication No. 13197/1983. These documents are incorporated herein by reference.

These block copolymers (A) are preferably used after being dispersed in water using an anionic or nonionic surfactant.

The binder resin used in the present invention (Bl is at least one selected from polyurethane resin, N-methylol resin (for example, methylol urea resin, methylol melamine resin, etc.) and epoxy resin, and these are used in the block copolymerization Used by mixing with coalescence (A).

According to the present invention, the block copolymer (A) and the binder resin (B) are expressed by the following formula % formula % (1) (wherein and B are as described above) with respect to the polyethylene fiber fabric. Granted within the range expressed by .

10 to the polyethylene fiber of the block copolymer (A)
If it is applied in excess of fii%, the retention rate of the block copolymer (A) during washing will be significantly reduced, although this is related to the amount of binder resin (B) applied, and the abrasion fastness of fabrics mixed with other types of fibers will be reduced. It turns out that there is a drawback that the amount becomes large. Furthermore, if the amount of N applied to the block copolymer is less than 0.1i%, the antifouling effect against various oily stains will be small, and a good SR effect will not be obtained.

If the amount of the binder resin (B) applied exceeds 10% by weight, the antifouling properties of the block copolymer (Al) will decrease, making it impossible to achieve the SR effect. In this case, the antifouling property and washing resistance achieved by the block copolymer (A) will be insufficient, which is undesirable.

Also, if the ratio of the amount of the binder resin CB) attached to the amount of the block copolymer (A) attached, that is, the value of B/A, is greater than 1, the stain resistance will be poor, and if it is less than 0.01, the wash resistance will be poor. This is not preferable because the layer properties deteriorate.

The block copolymer (A) and binder resin (B)
In applying this to polyethylene fibers, a mixed aqueous dispersion (this will be described later) of both the above components (A) and (B) is prepared, and this is passed through the spinning process of high strength, high modulus polyethylene fibers. , for example, before and after the stretching process, by applying it in advance by a guide oiling method or a touch roll oiling method,
After being heat treated as described below, the applied fibers can be made into a fabric, or if necessary, mixed with other fibers as described above.

Alternatively, a fabric made of the above-mentioned high-strength, high-elasticity polyethylene fiber, or made of this and other fibers, is made in advance,
This fabric may be applied by immersing it in an aqueous dispersion bath containing both components (A) and CB).

The above-mentioned aqueous dispersion usually has a pH of 2 to 6, preferably 3.0.
It is preferable to adjust the acidity level to 3.6°C and apply the liquid at a temperature of 60 to 90°C, and the treatment time is usually 10 to 30 minutes.

Alternatively, a two-step method may be used in which only the block copolymer (A) is applied in advance and then the binder resin (B) is applied.

After applying the block copolymer (A) and the binder resin (B) to the polyethylene:a male as described above, 90~
Heat treatment is performed at a temperature of 150°C for 10 seconds to 5 minutes. If the temperature at this time exceeds 150°C, the physical properties such as the strength and elasticity of the high-strength, high-modulus polyethylene fibers will decrease, which is undesirable, and if the temperature is below 90°C, the stain resistance and washing resistance will decrease. So I don't like it.

[Effect]

According to the present invention, the block copolymer (A) and/<
(Polyethylene fiber fabrics that have been given with an interresin (Bl) do not lose their original properties of high strength and high elasticity, and are extremely durable, with particularly excellent stain resistance and antistatic properties, and excellent washing resistance.) , has hydrophilicity.

〔Example〕

The present invention will be explained below with reference to Examples.

The measurement method used to evaluate the effects of the present invention is as follows.

(1) Water permeability: The time (in seconds) it takes for a drop of water to fall onto a fabric from a height of 10 dew and for this droplet to be completely absorbed into the fabric.

(2) Using a triboelectric rotary static raster, at a temperature of 20°C,
Electrostatic voltage (unit: V) after rubbing against a cotton cloth (shirting) for 2 minutes at a relative humidity of 65%.

(3) Re-staining property Immerse in a contaminated solution consisting of 0.01 parts by weight of carbon black, 0,515 parts by weight of beef tallow, 0.1 parts by weight of soap, and 100 parts by weight of water at 70'C for 30 minutes to determine the degree of contamination according to JIS. Determined by pollution gray scale.

(4) Oil stain removal carbon black 0.2 parts, beef tallow 40 parts, lard 40 parts, B heavy oil 10 parts, liquid paraffin 9.
A contaminant consisting of 8 parts by weight was applied to the test fabric at a temperature of 50°C in a diameter of 2C1! ! After applying it in a circular shape with the size of Determine the degree of remaining dirt in and around contaminated areas using the JIS pollution gray scale.

(5) Strength and elongation properties According to JIS-L-1103 (1981). Sample length (gauge length) 200. , Crossherad velocity 10 (I
The SS curve was measured under the condition of n/min, and the tensile strength at break and the tensile modulus were calculated. The tensile modulus was calculated from the maximum slope near the origin of the S·S curve.

(6) Using a blade-proof Feather Razor S single-blade (manufactured by Feather Safety Razor Co., Ltd.), the test fabric (two layers) was cut 5 times in a row at a length of 5α, and then the cuttability of the test fabric was visually judged. and 1 to 5 below
Ranked and evaluated.

Grade 1: One fabric surface is cut in all 5 cuts.

Grade 2: One fabric surface is cut up to 4 times.

Grade 3: One fabric surface is cut up to three times.

Grade 4 = One fabric surface is cut up to two cuts.

Grade 5: One cloth surface is cut only once.

In the above tests, each test fabric was measured both at the initial stage, that is, before washing, and after it was washed 10 times under the following conditions.

Washing: Washed in an aqueous solution of Marcel Soap 19/It at 40°C for 10 minutes, rinsed with water, and dried.

Example 1 A processed aqueous dispersion having the following composition was applied to a drawn yarn of 1200 denier, 720 filament, high strength, high modulus polyethylene fiber (HPE) at a concentration of 10% by weight based on the fiber, and then tensioned. The bottom layer was subjected to dry heat treatment at 120° C. for 60 seconds and then wound up.

Block copolymer (A) (1) 5wt% binder resin (B) 3.2wt% water Remaining (1) Terephthalic acid/Isophthalic acid/Ethylene glycol
/I//Polyethylene glycol block copolymer (terephthalate unit/isophthalate unit = 65/35.
Terephthalate unit isophthalate unit/polyethylene glycol unit = 3°5/1. polyethylene glycol
p molecular weight = 1500) (2) Sumitex Resin M-3 (melamine resin manufactured by Sumitex Chemical Co., Ltd.) and Sumitex Accelerator-ACX (
Catalyst manufactured by Sumima Kagaku Co., Ltd.), (melamine resin/catalyst weight ratio = 3
10.2) The amounts of block copolymer (A) and binder resin (B) attached to the wound polyethylene fibers are 0.5% by weight and 0.32% by weight, respectively, and (B) / (A ) was 0.64.

A plain knitted fabric was knitted using the antifouling HPE yarn produced as described above, and measured by the measurement methods described above to determine (1) water permeability, (2) triboelectrostatic properties, and (3) restainability. , (4) oil stain removability, (5) strength and elongation properties, and (6) blade resistance were measured initially and after 10 washes. The results are shown in Table 1 below.
Shown below.

Example 2 A plain knitted fabric was knitted in advance using the HPE drawn yarn of Example 1, and a processing water dispersion having the following composition was applied to this fabric using a mangle so that the pick-up amount was 50% by weight. , and was subjected to dry heat treatment at 110° C. for 5 minutes.

Block copolymer (A) (3' 1% by weight Binder resin (B)" 0.32% by weight (3) Same as block copolymer used in Example 1 (4) Example 1
The resulting fabric was the same as the binder resin used in HP
The amounts of the block copolymer (A) and binder resin (B) attached to the E fabric were 0.5% by weight and 0.16% by weight, respectively (t), and the value of (B)/(A) was 0. It became 32.

Various properties of the fabric processed as described above were measured in the same manner as in Example 1.

The results are shown in Table 1.

Example 3 The processed water dispersion used in Example 1 was applied to HPE drawn yarn of 600 denier and 360 filament at a concentration of 10% to the fiber in the same manner as in Example 1, and then subjected to tension. After dry heat treatment at 120'C for 60 seconds, the film was wound up.

A plain knitted fabric was knitted using the obtained stain-resistant HPE yarn and 100% cotton spun yarn at a ratio of 80:20, and various properties of this fabric were measured in the same manner as in Example 1.
The results are shown in Table 1.

Example 4 A flat fabric was knitted in advance using the HPE drawn yarn of Example 1, and a processing water dispersion having the following composition was applied to this fabric using a mangle so that the pick-up amount was 50% by weight. , and was subjected to dry heat treatment at 110° C. for 5 minutes.

Block copolymer, A, (5) 4% by weight Binder resin (B) (6' 3% (5) Same as block copolymer used in Example 1 (6) Example 1
The resulting fabric was the same as the binder resin used in HP
E fabric block copolymer (A) and binder resin (
The adhesion amount of B) is 2.0% by weight and 1.5% by weight, respectively.
The value of (B)/(A) was 0.75.

Various properties of the fabric processed as described above were measured in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 1 A plain knitted fabric was knitted in the same manner as in Example 1 without applying the processing water dispersion used in Example 1 to the HPE drawn yarn used in Example 1, and this fabric was knitted in the same manner as in Example 1. Various properties were measured in the same manner.

The results are shown in Table 1.

Comparative Example 2 In Example 1, the processing water dispersion was treated with H as in Example 1.
After applying it to the PE drawn yarn, dry heat treatment under tension was performed for 16 minutes.
A plain knitted fabric was knitted in the same manner as in Example 1 except that the knitting was carried out at a high temperature of 0°C. Various properties of this fabric were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 In Example 1, the method of Example 1 was repeated using a processing water dispersion containing only 5% of the block copolymer (A) used in Example 1.

Various properties of this fabric were measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 Example 1 was repeated except that the processing water dispersion used in Example 1 was replaced with a dispersion having the following composition.

Block copolymer (A) 5% by weight Binder resin (B) 11% by weight In this case H
The amount of block copolymer (A) attached to PE i fiber is 0.5% by weight, and the amount of attached binder resin (B) is 1.1%.
i amount%, and the value of (B)/(Al) is 22. Various properties of this fabric were measured in the same manner as in Example 1. The results are shown in Table 1.

〔Effect of the invention〕

As is clear from the data in Table 1, according to the present invention, polyethylene G %fl' has extremely long-lasting properties, particularly excellent washing resistance, stain resistance, and antistatic properties without impairing the high strength properties of the fabric. Polyethylene BQ with anti-fouling properties, re-contamination properties, and oil stain removal properties! IF fabric can be obtained.

Claims (1)

[Claims] 1. Tensile strength is 20 g/d or more and tensile modulus is 500 g.
(A) to the fabric containing polyethylene fibers of /d or more.
terephthalic acid, or terephthalic acid and isophthalic acid;
A block copolymer with alkylene glycol and polyalkylene glycol, and (B) at least one binder resin selected from the group consisting of a thermosetting resin and a thermoplastic resin, according to the following formula: 0.1≦A≦10 (1 ) 0.1≦B≦10(2) 0.01≦B/A≦1(3) [In the formula, A is the amount (wt%) of the block copolymer (A) attached to the polyethylene fiber, and B is the binder Antifouling, high strength, and high modulus of elasticity characterized by applying resin (B) to polyethylene fibers in the range expressed by the amount (weight %) shown below, and then heat-treated at a temperature of 150°C or less. Polyethylene fiber fabric. 2. Binder resin (B) is polyurethane resin, N-
The fabric according to claim 1, which is selected from methylol-based resins and epoxy-based resins. 3. Block copolymer (A) and binder resin (B)
The fabric according to claim 1, wherein the polyethylene fiber yarn forming the fabric is heat-treated. 4. The fabric according to claim 1, wherein the heat treatment is carried out at a temperature of 90 to 150°C for 10 seconds to 5 minutes. 5. The fabric according to claim 1, wherein the constituent fibers of the fabric consist only of polyethylene fibers or a mixture of polyethylene fibers and other fibers.