JPH07310204A - Clothing product made of nylon and method for recycling the same - Google Patents

Abstract

PURPOSE:To obtain a clothing product made of nylon comprising a material of cloth and auxiliary parts of clothing substantially made of nylon 6 uniformly, extremely reduced in selecting operation of recovered products, capable of providing a high-purity and high-quality raw material and repeatedly recyclable. CONSTITUTION:This clothing product made of nylon comprises a material of cloth and auxiliary parts of clothing substantially made of nylon 6 uniformly in which >=80wt.% of the whole materials are made of nylon 6. The clothing product is preferably a uniform. The clothing product made of nylon is recovered and depolymerized to recover epsilon-caprolactam, which is purified, polymerized and subjected to melt spinning to give nylon yarn or molded to give a molded article of nylon. The clothing product made of nylon is thus recycled.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a clothing product that can be easily recycled and a method for recycling the same.

[0002]

2. Description of the Related Art In recent years, in order to protect the global environment, effective use of resources, particularly recovery / reuse, so-called recycling, has been carried out. For example, it is established as a business to collect used glass and paper, sort them, and use them as recycled materials. Further, regarding thermoplastic molded articles such as PET bottles, it has been commercialized that used products are collected, sorted, remelted and molded for reuse.

There are many problems to be solved even in such recycling already carried out, and for example, the following problems are involved.

First, a great deal of equipment and labor are required for the collection and selection work. When the original product is manufactured using the recovered and regenerated raw material, a certain level of purity or higher is required. This is because if there are many impurities, the original product or even a similar product cannot be manufactured. Even for items that are relatively easy to sort, such as paper and glass, it takes a lot of effort to sort the items that are collected from an unspecified number of consumers, which increases the cost of collection and sorting, and the problem of recycling business Often becomes.

Secondly, the quality of products made from recovered raw materials cannot be sufficiently enhanced. As described above, even if a large amount of equipment and labor are applied to the selection, it is extremely difficult to obtain the same purity as the original raw material. Therefore, it is unavoidable to mix them with new raw materials little by little or to use them for other products with different quality standards.

Thirdly, since the amount of impurities in the product increases each time recycling is repeated, there is a limit to the number of times recycling can be repeated. Especially in the case of a resin, one recycling is the limit.

Further, some textile products such as clothing products are recycled in the form of reuse as used clothes, reused dismantled fabrics, fibers, and clothing accessories (buttons, etc.). .

[0008]

However, in the case of clothing products, such as paper, glass, and resin molded products, the collected products are returned to the raw materials and reused.

This is because, in addition to the body material which is the main component of the clothing product, many secondary components such as lining,
A wide variety of fabrics and clothing accessories made of different materials, such as fiber materials such as interlinings, sewing threads, name plates, and resin and metal members such as buttons, snaps, fasteners, and clasps. This is because it is not possible to dismantle and sort to a recyclable place, because the cloth and clothing accessories are often mixed with various materials. Furthermore, in the case of ordinary clothing products that are produced in small quantities and in a wide variety of products, it is impossible to put together a recyclable amount even if it takes time to disassemble and sort them.

Since many synthetic fibers derived from petroleum such as polyester fibers and polyamide fibers are used in these clothing products, more effective recycling is required from the viewpoint of effective use of resources for global environment protection. Desired.

[0011] Therefore, it is a main object of the present invention to provide a recyclable clothing product in which the recovered clothing product is returned to a raw material for reuse and a method for recycling the same.

That is, it is an object of the present invention to allow the recovered clothing product to be easily returned to the raw material and to be a raw material of good quality, which can be reused as the raw material.

Furthermore, it is an object of the present invention to provide a clothing product in which the collected clothing products can be recycled substantially without disassembling or sorting, and also to provide a clothing product in which the recycling to the raw materials can be repeated. To do.

[0014]

In order to achieve this object, the present invention provides a clothing product comprising a fabric and a clothing accessory, wherein the material of the fabric and the clothing accessory is substantially nylon 6. After recovering the nylon clothing product and the nylon clothing product, depolymerization is performed to recover ε-caprolactam, the recovered ε-caprolactam is purified, polymerized, and melt-spun into nylon fiber. Or a method for recycling nylon garment products, which is a molded nylon product.

It is important that the clothing product of the present invention is made of nylon 6 for the purpose of being recyclable. That is, nylon 6 is most suitable for recycling to return to the raw material as follows.

First, nylon 6 is a raw material (monomer).
It is the only mass-produced polymer that can be easily decomposed and purified to high purity. When nylon 6 is heated in the presence of a depolymerization catalyst, ε-caprolactam, which is a raw material before polymerization, is depolymerized. Furthermore, this ε-caprolactam has a boiling point of about 140 under reduced pressure (about 10 mmHg).
Since it is ℃, it can be easily separated and purified by distillation. Therefore, ε-caprolactam obtained by depolymerization can be easily purified to the same degree of purity as new lactam by precision distillation or crystallization purification method, and can be reused as a polymerization raw material.

On the other hand, nylon 66 is difficult to depolymerize into a monomer and further difficult to purify the monomer, and therefore it is difficult to recycle it to the polymerization raw material. Further, although polyesters can be depolymerized to monomers, it is difficult to industrially carry out purification to a sufficiently high degree of purity, and thus it is difficult to form fibers again and repeatedly recycle them. Acrylic fibers are practically incapable of depolymerizing into monomers. Furthermore, although natural fibers such as wool and cotton can be recovered, they cannot be reduced to the raw materials (for example, protein and cellulose) and fibrillated again.

Secondly, nylon 6 is one of the mass-produced resins that has the most excellent function and can be easily formed into fibers and molded, and has strength and beauty as fibers,
It also has toughness as engineering plastics. That is, nylon 6 can be widely manufactured from fibers to resin molded products such as gears and buttons. By using nylon 6, other materials such as fibrous fabrics to clothing accessories such as buttons and fasteners can be practically used. Can be manufactured without using. Therefore, with nylon 6, it is possible to make up a clothing product that is entirely made of the same material.

The clothing product comprises fabrics such as body cloth, lining and interlining, and clothing accessories such as sewing threads, name plates, buttons, snaps, fasteners and clasps. In the nylon garment product of the present invention, it is preferable that substantially all of the fabrics and clothing accessories constituting the nylon garment product are made of nylon 6, but other materials may be used as long as the amount is a small amount that does not adversely affect the depolymerization / purification process. May be used. However, it is preferable that the amount of other materials is as small as possible, and at most 20% by weight or less, preferably 10% by weight, of the whole clothing product.
It is more preferably 5% by weight or less.

Therefore, the clothing product of the present invention includes a sewing thread,
As many constituents as possible, including clothing accessories such as nameplates, buttons, snaps, fasteners and clasps, may be made of nylon 6. Furthermore, the amount of other materials added to these constituent members and the amount of other materials added by processing may be reduced as much as possible.

For example, a woven fabric, a knitted fabric, or a non-woven fabric made of only nylon 6 single fibers is used as a cloth such as a body cloth, a lining, and an interlining, and a sewing thread and a name plate are made of nylon 6 single fibers, and buttons, Nylon 6 molding may be used for the snaps, fasteners, and clasps.

The nylon 6 used in the present invention may be any polymer obtained by polymerizing ε-caprolactam by a conventional method. The degree of polymerization is preferably in the range of 2.0 to 4.0 in terms of relative viscosity of a 98% sulfuric acid solution.
The nylon 6 polymer may contain a small amount of other types of nylon (copolymer) or additives such as titanium oxide and a heat-resistant agent as long as they do not hinder the depolymerization process. However, it is preferable to reduce the amount of these other materials as much as possible, and it is within a range that does not adversely affect the depolymerization / purification process.

This nylon 6 is spun into a nylon 6 fiber having a predetermined thickness by a conventional method. For example, there may be mentioned a method of melt-spinning and stretching to obtain a fiber, and a method of forming a fiber without substantially stretching by high-speed spinning. These fibers may be further processed such as crimping,
It may be staple.

The obtained nylon 6 filaments or staples are formed into filament yarns, spun yarns or the like, and knitted or woven by a usual method to obtain a predetermined cloth. This yarn or cloth may be mixed with other fibers, such as polyurethane fiber, nylon 66 fiber, natural fiber, etc., as long as it does not interfere with the depolymerization / refining process. Good.

The cloth is water-repellent / oil-repellent, antistatic, water-absorbent / moisture-absorbent,
Finishing with a processing agent for antibacterial / deodorization may be performed. For example, coating with acrylic resin or polyurethane. In this case also, it should be within the range that does not hinder the depolymerization and purification process.

Of the members constituting the garment, the members made of fibers, for example, the body cloth, the lining, the interlining, the sewing thread, the name plate and the like are preferably made of the above nylon 6 fiber, but depolymerized. -Other fiber products may be included as long as they do not interfere with the refining process.

Further, it is preferable that the members other than the fibers constituting the garment, such as fasteners, snaps, buttons, and clasps, are also made by molding from nylon 6, but in the depolymerization / purification process. Other materials may be included as long as there is no hindrance. Of these accessories, buttons that are relatively easy to remove from clothing products,
The snaps, clasps, etc. may be removed before being subjected to depolymerization.

The nylon 6, snaps, buttons, and clasps may be manufactured in the same manner as in ordinary nylon 6 molded products. Further, the fastener may be manufactured from nylon 6 fiber and nylon 6 resin by an ordinary method.

Among the materials constituting the garment, the total weight of the materials other than nylon 6 introduced in the above-mentioned steps is at most 20% by weight or less, preferably 10% by weight or less. The materials should be limited to substances that do not adversely affect the decomposition and recovery process.

For example, substances such as inorganic pigments, metals, and chemically stable organic compounds that do not change in the depolymerization process from the recovered nylon 6 to ε-caprolactam remain as reaction residues and can be removed by a separate treatment. Is. In addition, volatile organic substances by-produced in this depolymerization step can be separated and removed from ε-caprolactam by means such as purification.

However, a volatile compound (especially ε-caprolactam) generated during the depolymerization reaction of nylon 6
Substances which have a boiling point close to, or which generate a compound that flows out by azeotropic distillation, or substances which corrode the material of the apparatus are not preferable because the depolymerization / purification process becomes complicated.

Specifically, polyester is not preferable because it generates a large amount of low-boiling compounds such as ethylene glycol and acetaldehyde at the decomposition temperature of nylon, and is preferably not contained as much as possible. In addition, substances such as vinylidene chloride and vinyl chloride that generate corrosive hydrochloric acid gas when decomposed are not preferable and may be contained as little as possible.

Most ideally, nylon 6 is used as all the constituent members from the front material to the lining material, interlining material, sewing thread, fasteners, snaps, buttons and clasps.

In this way, 80% by weight or more of the constituent materials,
Preferably, 90% by weight or more, and more preferably substantially all of nylon 6 is unified with nylon 6 to reduce the load of the recovery step and the depolymerization step, and to separate and collect ε. -Caprolactam can be easily purified, and high-purity ε-caprolactam can be obtained.

The recovered nylon clothing product is disassembled as necessary to remove the material parts other than nylon 6,
Furthermore, after removing stains if necessary, the clothing product is supplied to the depolymerization step in the state of the product. The depolymerization may be carried out by a usual method of adding a depolymerization catalyst while heating and melting to perform depolymerization.

The ε-caprolactam obtained by depolymerization is purified by a conventional purification method such as precision distillation or crystallization purification method to increase its purity. Obtained high purity ε-
Caprolactam is mixed with a new ε-caprolactam (not a recovered product), if necessary, and polymerized by a usual method to produce nylon 6.

The nylon 6 from the recovered lactam thus produced may be again melt-spun into nylon fiber, or may be molded into a molded article such as a button by molding in a usual method.

The recyclable nylon clothing product of the present invention includes any clothing product in which nylon 6 textiles can be used, such as uniforms, rainwear, sportswear,
It is applicable to outerwear, innerwear, stockings, swimwear, leotards, etc., but is particularly suitable for clothing products in which a large number of similar clothing products are produced and used.

Among them, uniforms are uniforms adopted by government offices, companies, etc., uniforms for infants, children, and students that are not worn by renewal or graduation after wearing for a certain period of time. In addition, since collection / sorting operations are relatively easy and contamination of foreign matter can be suppressed, it is most effective to promote recycling by applying the present invention.

Uniforms are often composed of a combination of parts such as outerwear, pants, middlewear, and underwear,
The present invention may be applied to all of them, or may be applied to a part of them. Also, special work clothes that are sometimes used as uniforms, for example,
Application to white coat, explosion-proof clothing, dust-free clothing, sports trainers, etc. is also effective.

[0041]

【Example】

[Example] [epsilon] -caprolactam containing 0.4% by weight of titanium oxide as a matting agent was polymerized by a conventional method to obtain nylon 6 having a 98% sulfuric acid viscosity of 2.70. This nylon 6 was melt-spun by a conventional method to obtain nylon 6 fiber having 70 denier 24 filaments or 70 denier 40 filaments.

As the outer material of the uniform woven fabric, nylon 6 fibers of 70 denier 24 filaments are used as warp yarns, and 70
A plain weave fabric was woven by using two weft-supplied Taslan-processed yarns of nylon 6 fibers of denier 24 filaments and nylon 6 fibers of 70 denier 40 filaments as weft yarns. After dyeing the surface material with a normal acid dye, a fluororesin (“Asahi Guard” AG-710 (Asahi Glass Co., Ltd.)
Manufactured)). The total amount of the dye and water repellent applied was 1.5% by weight (vs. fiber).

For the lining, a plain weave taffeta was woven using nylon 6 fibers of 70 denier 24 filaments as warp and weft, and dyed and finished by a usual method.

As the interlining material, nylon 6 knit interlining material (product number 31594 manufactured by Toray Industries, Inc.) was used.

A nylon 6 resin containing no titanium oxide (CM1001 manufactured by Toray Industries, Inc.) was used, and the diameter was 1 cm.
Buttons and fasteners were molded.

These members were sewn by a usual method to produce a work jacket. The amount of substances (dyes, processing agents, etc.) other than nylon 6 in the obtained outerwear was about 2% by weight.

The obtained jacket was worn for 6 months and then collected.

The recovered outerwear was put into a nylon depolymerization facility without being disassembled, and was melted at 290 ° C. to be decomposed by adding a phosphoric acid catalyst, and the produced ε-caprolactam was distilled and cooled to be collected. Almost 90% of the charged raw material could be recovered as ε-caprolactam. The unrecovered residue was an additive other than nylon 6, a treating agent, a carbide generated in the depolymerization step, a gel, and the like.

The recovered ε-caprolactam further comprises
Purification was carried out by an ordinary rectification equipment to obtain ε-caprolactam of high purity which was substantially the same as new ε-caprolactam from petroleum raw materials.

When the characteristics of the obtained recovered / purified ε-caprolactam were analyzed, as shown in Table 1, it was almost the same as the characteristics of the new ε-caprolactam, and it was an excellent quality that could be used like a new article. Each characteristic of ε-caprolactam was measured by the following methods.

Permanganic acid value (PMV): Potassium permanganate was added to a 3 wt% aqueous solution of ε-caprolactam, and the time (seconds) until the purple color of the mixed solution coincided with the standard color tone was measured. The longer this time, the less impurities.

Color tone (APHA): JIS-K-41
In accordance with No. 01, the color tone of a 50 wt% aqueous solution of ε-caprolactam is measured by a method of comparing with the color tone of a standard solution.

Amount of free acid (FA) and free base (FB): Free acid (FA) and free base (FB) obtained by the method of neutralization titration of a 20 wt% aqueous solution of ε-caprolactam.
And the amount are expressed as the amount (milliequivalent) per 1 kg of ε-caprolactam.

Amount of Volatile Base (VB): An aqueous solution of ε-caprolactam is subjected to boiling distillation in the presence of caustic soda, and the entire amount of volatile base is absorbed in a liquid of a known amount of acid. The solution is subjected to neutralization titration to determine the amount of acid consumed by the volatile base, and the amount is expressed as the amount per 1 kg of ε-caprolactam (milliequivalent).

Ultraviolet absorption rate (UVA): 50% by weight aqueous solution of ε-caprolactam, when irradiated with ultraviolet rays of 290 nm, the transmittance (%) at an optical path length of 1 cm.
Ask for.

Water content: ε-caprolactam is dissolved in methanol to prepare a sample, and the amount of water contained in this sample is determined by a titration method using Karl Fischer reagent.

The ε-caprolactam obtained by the recovery and purification was supplied to a nylon 6 polymerization facility and polymerized by a usual method. As a result, the same high quality nylon 6 as the nylon 6 from the new ε-caprolactam was obtained. . Then, the obtained nylon 6 could be melt-spun again to form a fiber, or could be formed into a molded product by molding.

[0058]

[Table 1]

Comparative Example Commercially available polyethylene terephthalate filament yarn (75 denier 24 manufactured by Toray Industries, Inc.)
Filament, semi-dal type) is used as a warp yarn, and a nylon 6 filament yarn Taslan-processed yarn used in Example 1 is used as a weft yarn to make a cloth similarly woven, and other members are the same as those used in the example. The same processing and sewing were used to produce a work jacket. The ratio of nylon 6 to the entire outerwear obtained was about 70% by weight, and the polyester contained about 28% by weight.

A fabric similarly woven using the nylon 6 fiber of 70 denier 24 filaments used in Example 1 as the warp and the blended yarn of nylon 6 and wool as the weft (mixing ratio of wool 23%, 130 count). The same material as that used in the examples was used as the other material, 7% by weight of the same processing agent as that used in the examples was applied, and sewing was performed to produce a work jacket. The ratio of nylon 6 to the entire outerwear obtained was about 78% by weight, and the wool content was about 10% by weight.

These clothes were directly supplied to the same disassembling equipment used in Example 1 and disassembled in the same manner.

As a result, in the case of an outerwear containing a large amount of polyester, a large amount of polyester decomposition products such as ethylene glycol, acetaldehyde and acetic acid were mixed in the decomposed and simple-distilled ε-caprolactam. It could not be completely removed even in the distillation step, the purity of the recovered ε-caprolactam was significantly lowered, and it was difficult to reuse the polymerization.

Further, in the case of a jacket containing a large amount of wool and a processing agent, the wool and the processing agent therein were hardly decomposed and remained as a residue of the reactor and the discharge pipe was clogged. . Also,
There were many decomposition residuals for disposal.

[0064]

EFFECTS OF THE INVENTION In the clothing product of the present invention, the material thereof is substantially unified with nylon 6 which can be easily returned to the raw material and reused. It can be recycled by returning it for reuse.

Further, by decomposing and purifying the recovered clothing product, a raw material of high purity and good quality (raw material monomer) can be obtained, and thus nylon 6 fiber or A nylon 6 molded product can be manufactured. Further, it can be repeatedly recycled.

Furthermore, the recovered clothing products can be subjected to the recycling process without being disassembled or sorted, and the sorting work of the collected products is significantly reduced.

Therefore, according to the present invention, it is possible to recycle the raw material, the product, and the raw material in a closed system by generating a small amount of waste such as several percent.

In particular, when applied to uniforms produced and consumed in large quantities, collection / sorting operations are relatively easy and foreign substances can be suppressed, so that efficient recycling can be achieved.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C08J 11/00

Claims (7)

[Claims] 1. A nylon garment product comprising a cloth and a garment accessory, wherein the material of the cloth and the garment accessory is substantially unified with nylon 6. 2. The nylon garment product according to claim 1, wherein 80% by weight or more of all materials constituting the cloth and the garment accessory are nylon 6. 3. The nylon garment product according to claim 1 or 2, wherein substantially all the material constituting the cloth and the garment accessory is nylon 6. 4. The nylon garment product of claim 1, wherein the garment product is a uniform. 5. The nylon garment product according to claim 1, 2, 3 or 4 is recovered and then depolymerized to recover ε-caprolactam, and the recovered ε-caprolactam is purified,
A method for recycling a nylon garment product, which comprises polymerizing and melt-spinning into a nylon fiber. 6. The nylon garment product according to claim 1, 2, 3 or 4 is recovered and then depolymerized to recover ε-caprolactam, and the recovered ε-caprolactam is purified, polymerized and molded. A method for recycling nylon garment products, characterized by forming a nylon molded product. 7. The method for recycling a nylon clothing product according to claim 5, wherein the recovered nylon clothing product is subjected to depolymerization without being substantially disassembled.