JPH11346814A - Stainproof bag fabric and stainproof bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bag which retains stainproof performance without degradation even after long-term use. SOLUTION: This bag consists of a woven fabric composed of core-sheath type composite fibers the sheath component of which consists of a polyester blended with a fluorine-containing polymer and the core component consists of a thermoplastic polymer as warp and or weft. The ratio of the sheath component of the core-sheath type composite fibers is specified to 5 to 60 vol.% and the fluorine content in the sheath component to 0.05 to 10.0 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling bag and an antifouling bag. For more information,
The present invention relates to an antifouling bag and an antifouling bag, which have good antifouling properties and maintain their antifouling properties even after long-term use.

[0002]

2. Description of the Related Art Conventionally, a bag made of a woven fabric has been produced by weaving a bag yarn, heat setting, dyeing, and coating a resin. The resin coating treatment has been required in order to improve the control of bag contamination.

[0003] The conventional resin coating technology has been widely put into practical use because it has a considerable effect on the improvement of the antifouling property required for bags. However, in recent years, customers have been complaining that the conventional resin-coated bag may become conspicuous after long-term use, and further improvements have been required.

[0004] The cause of complaints is that the resin coated on the bag is scratched or scratched during long-term use, so that the resin is peeled off or the initial antifouling property is significantly reduced due to the adhesion of dirt. It was found that the antifouling property was impaired.

The polyester fiber which is not directly related to the antifouling property of the bag of the present invention but is generally suitable for applications requiring antifouling property is a copolymer of polyethylene and tetrafluoroethylene. A polyester fiber having excellent antifouling properties by kneading a fluoropolymer such as the above with a polyethylene terephthalate polymer, and a core-sheath type composite fiber, wherein the sheath component is a polyethylene polymer having a polyethylene terephthalate. JP-A-62-238822 discloses an example of an antifouling polyester fiber in which the core component is polyethylene terephthalate. This technology has excellent smoothness and chemical resistance, that is, stain resistance, and is considered to be optimal for dust-free and aseptic clothing used in manufacturing sites of precision industries, semiconductors, pharmaceuticals, foods, and the like.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to substantially solve the above-mentioned problems in the prior art.
That is, it is an object of the present invention to provide a bag which does not deteriorate in antifouling performance even after long-term use.

[0007] Therefore, a method for imparting the antifouling performance of a bag other than the resin coating treatment of the prior art, that is, a method for imparting the antifouling property to the original yarn for the bag itself, has been intensively studied, and has reached the present invention.

[0008]

In order to solve the above problems, the antifouling bag of the present invention mainly has the following constitution.
That is, the core-sheath composite fiber comprises a polyester blended with a fluorine-containing polymer as a sheath component, and a core-sheath composite fiber comprising a melt-spun thermoplastic polymer as a core component as a warp and / or a weft. Characterized in that the ratio of the sheath component is 5 vol% or more and 60 vol% or less, and the fluorine content in the sheath component is 0.05 wt% or more and 10.0 wt% or less. It is an antifouling bag.

Further, the antifouling bag of the present invention mainly has the following constitution. That is, the core component is made of a polyester blended with a fluorine-containing polymer as a sheath component, and a core-sheath composite fiber made of a thermoplastic polymer whose core component is melt-spinnable.
Or a woven fabric constituted as a weft, wherein the ratio of the sheath component of the core-sheath type composite fiber is 5% by volume or more and 60% by volume or less
When the fluorine content in the sheath component is 0.05% by weight or more,
An antifouling bag characterized by using an antifouling bag having a content of not more than 0.0% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The fibers constituting the warp and / or the weft of the fabric used as the bag fabric of the present invention are core-sheath type composite fibers whose sheath component is a polyester blended with a fluorine-containing polymer.

By providing a core-sheath type composite fiber, a fluorine-containing polymer can be made to function efficiently, so that a bag material having excellent antifouling properties can be provided at low cost without impairing the mechanical properties. Can be. Core-sheath type composite fiber is a composite fiber composed of at least a core component and a sheath component,
When the cross section of the composite fiber is observed, the sheath component is present so as to cover at least 60% or more of the fiber surface, and is preferably present so as to cover 100% of the fiber surface. However, the fiber surface refers to a surface that can come into contact with a contaminant when it is formed into a bag, for example, a surface excluding a hollow portion and a concave portion having a width or diameter of an opening of 1 μm or less. Further, the core component of the core-sheath type conjugate fiber of the present invention refers to a portion other than the sheath component when the cross section of the conjugate fiber is observed.

The fluorine-containing polymer used in the present invention is blended with a polyester. In contrast to blending with a polymer other than polyester, blending with polyester further improves antifouling properties. In addition, excellent functions such as mechanical properties and wet dimensional stability can be exhibited as additional effects.

As the polyester as the sheath component of the core-sheath type composite fiber used in the present invention, those mainly composed of polyethylene terephthalate (hereinafter referred to as PET) and polybutylene terephthalate are preferable, and PET is more preferable. . Other preferable polyesters include polyethylene naphthalate and polycyclohexane dimethylene terephthalate. Part of the carboxylic acid component may be replaced with isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dimer acid, sulfonic acid metal salt-substituted isophthalic acid, or the like. A part of the glycol component may be replaced by diethylene glycol, neopentyl glycol, 1,4-cyclohexanediol, or the like. By copolymerizing these components, the dye can easily enter the fiber during the dyeing process, and low-temperature low-pressure dyeing can be performed, so that the dyeing cost can be reduced. In addition, when a sulfonic acid metal salt-substituted isophthalic acid or the like is copolymerized, a cationic dye can be used, the occupation in the dyeing seat and the interaction with the polymer are increased, and the transfer sublimation is suppressed. It is preferable because it can be performed. Further, a small amount of a chain branching agent such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid and boric acid can be used in combination. These are preferably used because the presence state of the fluoropolymer in the sheath component can be controlled.

The intrinsic viscosity [η] of the polyester as the sheath component of the core-sheath type conjugate fiber used in the present invention is preferably 0.6 or more, more preferably 0.7 or more. By increasing the intrinsic viscosity, the fluoropolymer in the sheath component can be finely dispersed, so that the antifouling property and mechanical properties can be improved. From the viewpoint of easy dyeability, the intrinsic viscosity [η] of the polyester is more preferably 0.9 or less.

It is necessary that the ratio of the sheath component of the core-sheath type composite fiber used in the present invention is not less than 5% by volume and not more than 60% by volume. When the ratio of the sheath component is less than 5% by volume, the antifouling property of the bag becomes insufficient, especially the antifouling durability becomes insufficient, and it may be difficult to produce a normal core-sheath composite fiber. Conversely, if the ratio of the sheath component exceeds 60% by volume, the mechanical properties become insufficient.

[0016] The fluorine content of the sheath component of the core-sheath type conjugate fiber of the present invention is from 0.05% by weight to 10.0% by weight. When the fluorine content is less than 0.05% by weight, the antifouling property of the bag becomes insufficient. On the other hand, if the content is 10.0% by weight or more, the effect is saturated, so that it becomes unnecessary.

The fluorine-containing polymer to be blended with the sheath component polyester of the core-sheath type conjugate fiber used in the present invention is a random copolymer (hereinafter referred to as ETFE) containing tetrafluoroethylene and ethylene as main components, and polychlorotriethylene. Fluoroethylene (hereinafter referred to as PCTFE),
Polyvinylidene fluoride (hereinafter, referred to as PVdF), vinylidene fluoride / tetrafluoroethylene copolymer (hereinafter, referred to as 2F / 4F), polytetrafluoroethylene (hereinafter, referred to as PTFE), tetrafluoroethylene / perfluoroalkylvinyl Selected from ether copolymers (hereinafter referred to as PFA) and terpolymers mainly comprising ethylene tetrafluoride, propylene hexafluoride and vinylidene fluoride (hereinafter referred to as fluorine-based terpolymers) Preferably, at least one kind is used.

As the ETFE, components other than tetrafluoroethylene and ethylene include monochlorotrifluoroethylene, perfluoroacrylate, perfluoroalkyl acrylate, and perfluoroalkyl vinyl ether.
One or more components selected from ter, hexafluoropropylene, vinylidene fluoride, etc.
Copolymers of about% by weight may be used. Also, ETFE
The upper limit of the fluorine atom content is 69% by weight in the case of a 1: 1 copolymer of ethylene and tetrafluoroethylene. In order to obtain the high antifouling property which is the object of the present invention,
It preferably contains at least 40% by weight or more of fluorine atoms. More preferably, when ETFE containing at least 46% by weight of fluorine atoms is used, a fiber excellent in antifouling properties, which is the object of the present invention, can be obtained.

As the fluorine-based terpolymer, it is sufficient that three components of ethylene tetrafluoride, propylene hexafluoride and vinylidene fluoride are copolymerized.
5-80 mol% of fluorinated ethylene, propylene hexafluoride 2
Fluorinated terpolymers of from 35 to 35 mol% and from 5 to 90 mol% of vinylidene fluoride are preferred, from 30 to 70 mol% of ethylene tetrafluoride, of propylene hexafluoride 10
-30 mol% and vinylidene fluoride 10-50 mol%
Is more preferable.

ETFE and a fluorine-based terpolymer are more preferred as a fluorine-containing polymer which is easily melt-spun in a stable manner by blending with a polyester, and has high antifouling properties and high durability. Is particularly preferred.

The effect of preventing the bag from being stained can be estimated from the contact angle with decalin (oil-resistant substance contamination) and the contact angle with water (water-soluble substance contamination) measured on the surface of the bag yarn. it can.

That is, the core-sheath type conjugate fiber used in the present invention preferably has the following characteristics.

Contact angle with water ≧ 80 ° Contact angle with decalin ≧ 25 ° When the contact angle with water is 80 ° or more, more preferably 85 ° or more, it is difficult to adsorb water, so that water-soluble contaminants It is preferred because it is hardly contaminated by the When the contact angle with decalin is 25 ° or more, and more preferably 35 ° or more, it means that it is difficult to absorb an oily substance, and it is generally preferable that it is not easily contaminated by a lipophilic substance.

The core component of the core-sheath type composite fiber used in the present invention may be any thermoplastic polymer, for example, polyolefin such as polyethylene and polypropylene, nylon 6, nylon 6
And polyesters such as polyethylene terephthalate. Among them, polyesters are preferably used because they are excellent in durability of mechanical properties because they can suppress peeling from a sheath component. Also,
In this case, high wet dimensional stability is obtained. The same polyester is generally used for the core component and the sheath component, but different types of polyesters may be used in combination.

When both the core and sheath components are polyester, the intrinsic viscosity [η] of the whole core-sheath type composite fiber used in the present invention is 0.1.
A value of 80 or more is preferably adopted from the viewpoint of improvement of mechanical properties as a bag and abrasion resistance. The higher the strength of the core-sheath composite fiber, the more advantageous in terms of the strength as a bag and the abrasion resistance. The strength of the core-sheath composite fiber used in the present invention is preferably 7.5 g / d or more.
More preferably, the strength is at least 0 g / d.

The core-sheath type composite fibers used in the present invention include various inorganic particles such as titanium oxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin, zirconate, crosslinked polymer particles, and the like. Particles such as metal particles, also conventionally known antioxidants, sequestering agents,
An ion exchange agent, a coloring inhibitor, a weathering agent, a flame retardant, an antistatic agent, various coloring agents, wax silicone oil, and the like may be added.

The core-sheath type conjugate fiber used in the present invention is preferably composed of a multifilament having a single fiber fineness of 3 denier or more and 30 denier or less. The single fiber fineness is advantageously 3 denier or more from the viewpoint of abrasion resistance as a bag, but is preferably 30 denier or less from the viewpoint of appropriate flexibility.

The cross-sectional shape of the monofilament of the core-sheath type conjugate fiber used in the present invention may be any cross-section such as a round, flat, hollow, T-shaped, cross-shaped, three-leaf, eight-leaf, etc. Among them, a round section or a flat section is preferred because of its high antifouling effect.

The core-sheath type composite fiber used in the present invention is used as a warp and / or a weft, preferably a warp and a weft, constituting a woven fabric. Thereby, a bag having high antifouling property, which is the object of the present invention, can be obtained.

The core-sheath type composite fiber used in the present invention described above is produced, for example, by the following method.

As the core component polymer of the core-sheath type composite conjugate fiber used in the present invention, the above-mentioned polymer is used, and the above-mentioned polyester and a fluorine-containing polymer are blended and used as the sheath component. As the polyester and the fluorine-containing polymer, a polymer kneaded in advance may be used, or the polyester may be blended in a molten state immediately before spinning, or may be mixed and spun by a master batch method.

The polymer for the core component and the polymer for the sheath component are melted by separate melt spinning machines, respectively, introduced into a composite spinning pack, each polymer is filtered, and then spun as a core-sheath composite fiber through a composite spinneret. The yarn spun from the composite die is passed through a heating zone, or immediately cooled and solidified with cold air, applied with a spinning oil agent, wound around a roller rotating at a predetermined speed, and taken up. The take-up speed is 500 m / min or more and 2500 m / min for productivity and high strength.
Minutes or less is preferred.

The drawn undrawn yarn is drawn continuously without being wound once. Stretching is performed in one stage or in two or more stages. In particular, in order to stably obtain a high strength of 7.5 g / d or more, multi-stage stretching of two or more stages is preferable. Usually, a hot stretching method is adopted, and the film is stretched 2.5 times or more, usually 4 times or more by applying a temperature of 70 ° C. or more to the polymer melting point.
The heat treatment temperature of the yarn with the final drawing roller is to prevent the structure fixation of the fiber and the bleeding of the fluoropolymer-derived material.
Preferably, it is performed at 150 ° C or higher and 220 ° C or lower, more preferably at 170 ° C or higher and 200 ° C or lower. The heat-drawn yarn is subjected to a relaxation heat treatment at a temperature similar to that of the above-mentioned heat drawing while giving an appropriate relaxation of 1% or more and 20% or less, and is wound up. The winding speed is at least 2000 m / min, preferably at least 3000 m / min.

By the above method, the core-sheath type conjugate fiber used in the present invention can be obtained, and the fiber can be used as it is as a raw yarn for a bag. Although the core-sheath type composite fiber used in the present invention can be used for both the warp and the weft of the bag, the effect of the present invention can be obtained even if it is used only for the warp or the weft emerging on the surface of the bag. The bag of the present invention can be processed in the same manner as the conventional bag manufacturing processes, that is, weaving, heat setting, dyeing, antifouling processing, and sewing. Cost can be reduced.

Further, in order to improve the initial antifouling property, a solution or dispersion of a cross-linkable synthetic resin such as a conventional polyacrylic resin, polyvinyl chloride resin, polyurethane resin, chlorosulfonated polyethylene resin or the like is used. It is preferable that the initial antifouling effect can be improved by coating, drying and curing to impart waterproofness, or by laminating and treating with a waterproof synthetic resin.

The bag of the present invention may be provided with a post-processing agent for improving a water repellent, an antibacterial agent, antistatic property, flame retardancy, weather resistance, lubricity, gloss and the like. it can. These post-processing agents can be firmly adhered to the fabric by processing the above-mentioned coating layer before forming a complete crosslinked structure. In particular, it is preferable to process the water repellent since the initial antifouling effect can be further improved.
As the water repellent, a fluorine-based water repellent or a silicon-based water repellent is preferably used.

[0037]

Next, the present invention will be described in more detail with reference to the following examples. The definitions of the elongation and antifouling properties and the measuring methods used in the examples are as follows.

(1) Intrinsic viscosity [η] It was measured at 25 ° C. using an orthochlorophenol with an Ostwald viscometer.

(2) Strong elongation The yarn length 25c is determined by the method specified in JIS L 1017.
m and the tensile speed were 30 cm / min.

(3) Antifouling property The contact angle with water (distilled water) and the contact angle with decalin on the surface of the fiber were measured using a goniometer manufactured by Elma Optical Co., Ltd.
Using a contact angle measuring device, the measurement was performed under the following conditions.

Droplet volume: 5 μl Measurement temperature: 20 ° C. The larger the contact angle, the higher the water / oil repellency.

[0042]

EXAMPLES Examples 1 to 5 and Comparative Examples 1 to 3 As terpolymers mainly composed of ethylene tetrafluoride, propylene hexafluoride and vinylidene fluoride as sheath components, the copolymerization ratio of each was as follows. 30, 40, 30% by weight of a fluorine-containing polymer (hereinafter referred to as FP1) was added to polyethylene terephthalate having an intrinsic viscosity [η] of 0.71 in an amount shown in Table 1. Further, polyethylene terephthalate having an intrinsic viscosity [η] of 1.2 was used as the polymer of the core component,
Each component of the core and the sheath was individually melt-extruded by an extruder, and each molten polymer was supplied to a composite spinning machine. In the compound spinning machine, the molten polymer is individually weighed, supplied to the compound spinning pack, and after each component is filtered, a compound stream is formed in the compound spinneret. The hole diameter is 0.7 mmΦ and the number of holes is 96 holes. , And spun as core-sheath composite fibers having a core-sheath composite ratio shown in Table 1.

The spun yarn was passed through a heating zone heated to a temperature of 310 ° C. by attaching a 20 cm heating cylinder directly below the spinneret. The in-cylinder ambient temperature is a position 10 cm below the surface of the base and 1 mm from the outermost thread.
This is the ambient temperature measured at a distance of 1 cm.

A 10 cm long heat insulating cylinder is installed under the heating cylinder, and a 120 cm long uniflow type chimney is placed under the heating cylinder.
The yarn was cooled at 25 ° C. by blowing cold air at a rate of 30 m / min at right angles to the yarn, and the cooling air in the upper 25 cm was sucked on the opposite side. Next, after applying the oil agent, the yarn speed is controlled by a take-off roll rotating at a speed of 500 m / min.
The film was continuously stretched at 4.9 times without winding.

The stretching is performed by two pairs of Nelson-type rolls.
After the step stretching, the film was wound with 4% relaxation. The take-up roll temperature was 90 ° C, the first stage of stretching was performed between the take-up roll and the first stretch roll heated to 120 ° C, and the first stretch roll was heated to 185 ° C with the first stretch roll. 2 between stretching rolls
Step stretching was performed. The relax roll was not heated. The first-stage stretching ratio was 80% of the total stretching ratio, and the remainder was stretched in the second stage, and the amount of polymer discharged was adjusted so that the fineness of the drawn yarn was about 500 denier.

Table 1 shows the evaluation results of the composite fiber thus obtained.

[0047]

[Table 1] Example 6 A composite fiber was obtained in the same manner as in Example 1 except that ETFE having a copolymerization ratio of ethylene and tetrafluoroethylene of 50:50 was used as the fluoropolymer.

The evaluation results of the composite fiber thus obtained are also shown in Table 1.

[Examples 7, 8 and Comparative Example 4] The polyester fiber of the present invention obtained in Example 1 and the polyester fiber obtained in Comparative Example 1 were subjected to a conventional method of 65 filaments / inch, weft 53.
After weaving into a plain fabric of book / inch, refining and dyeing (Example 7), the obtained fabric was sewn and tailored into a bag.

A chlorsulfonated polyethylene resin is coated at a coating amount of about 30 g / m 2 on the basis of the dyed cloth as a base cloth, dried at 80 ° C., and dried at 150 ° C. × 1.
Then, the fabric was treated with an aqueous solution of a silicone-based water-repellent and antibacterial agent, dried and cured to obtain a base fabric for a bag (Example 8), and this fabric was sewn to prepare a bag.

Similarly, using the polyester fiber of Comparative Example 1, a fabric not subjected to waterproofing and water-repellent finishing was obtained (Comparative Example 4), and this fabric was sewn to prepare a bag.

Using the doughs of Examples 7 and 8 and Comparative Example 4 as samples, stains were applied using juice, coffee and mud,
Stainability was evaluated by washing with water. As a result, the stain removal property was good in the order of Example 8, Example 7, and Comparative Example 4.

Further, a 1 kg load is connected to a 10 cm wide cloth, and 90 ° contact is made with a 5 mm R metal.
After performing a reciprocating motion of 0 cm at a rate of once per second 500 times, the same evaluation of soiling was performed. As a result, Examples 7 and 8 were comparable, and Comparative Example 4 was the worst in dirt removal.

[0054]

As described above, the bag of the present invention has excellent antifouling properties, and has sufficient antifouling performance even when used repeatedly for a long period of time. That is, even when used repeatedly for a long period of time, the resin on the surface does not fall off as in the conventional bag material, and the antifouling performance does not deteriorate.

Further, as another effect, the core-sheath type conjugate fiber of the present invention itself has better wet dimensional stability than a conventional bag fiber.

In addition to the excellent performance of the above-mentioned bag material, the bag material of the present invention does not require a resin coating step, and thus has an additional effect that the manufacturing cost of the bag material can be reduced.

Claims (8)

[Claims] The core component comprises a polyester blended with a fluorine-containing polymer, and the core component comprises a woven fabric composed of a core-sheath type composite fiber comprising a thermoplastic polymer as a warp and / or a weft. 5% by volume of sheath component
An antifouling bag having a volume content of 60% by volume or less and a fluorine content of the sheath component of 0.05% by weight or more and 10.0% by weight or less. 2. A random copolymer, wherein the fluoropolymer comprises tetrafluoroethylene and ethylene as main constituents, polychlorotrifluoroethylene, polyvinylidene fluoride, vinylidene fluoride / tetrafluoroethylene copolymer, polytetrafluoroethylene One selected from the group consisting of fluoroethylene, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer, and terpolymers mainly composed of ethylene tetrafluoride, propylene hexafluoride and vinylidene fluoride The antifouling bag according to claim 1, wherein: 3. The fluoropolymer is tetrafluoroethylene, 6
3. The antifouling bag according to claim 2, which is a terpolymer mainly composed of propylene fluoride and vinylidene fluoride. 4. The fabric according to claim 1, wherein the fabric is treated with a waterproof synthetic resin and / or a water repellent.
The bag excellent in antifouling property according to any one of the above. 5. The composite fiber has a single fiber fineness of 3 denier or more,
2. The antifouling bag according to claim 1, wherein the multifilament is 30 filaments or less. 6. The antifouling bag according to claim 1, wherein the thermoplastic polymer as the core component is polyester. 7. The antifouling bag according to claim 6, wherein the intrinsic viscosity [η] of the conjugate fiber is 0.80 or more. 8. An antifouling bag using the antifouling bag according to any one of claims 1 to 7.