JP2969494B2 - Method for producing short flat fiber product, and glove having uniform dyeability and conductivity - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dyed and / or conductive-treated short flat fiber product such as antistatic gloves, socks and arm covers used in a clean room.

[0002]

BACKGROUND OF THE INVENTION a large number of gloves, socks, short, such as a handkerchief
When collectively dyeing a long flat-plate fiber product, if the fiber products are put into a rotary dyeing machine or a dyeing machine with a stirrer one by one in a state of being separated, the dyeing is performed uniformly. However, it was troublesome to take out, and moreover, it was rotated or agitated more than necessary in a water tank, so that the dyed fiber product was liable to wrinkle or fray at the end.
Therefore, a method is known in which fiber products are collectively packed in a net-like bag and dyed by a rotary dyeing machine or a cheese dyeing machine.

[0003]

However, when packed into a net-like bag and dyed in this way, the fiber product is less damaged, but is packed in a high density state, so that it is easily broken or twisted in a certain state, There was an extremely problem in shape retention, and it was necessary to carry out molding, drying, heat setting, and the like of the textile product after the dyeing process, and uneven dyeing occurred in portions where the textile products overlapped. Also, for example, antistatic gloves used in clean rooms,
The same problem has been encountered in the case of the conductive treatment performed when manufacturing socks and arm covers. The present invention has been made in view of such conventional technology, and has uniform contact and circulation of a dyeing solution and a conductive agent, no unevenness in dyeing and non-uniformity in conductivity, and excellent uniformity in shape retention and workability. High dyeability and conductivity
It is an object of the present invention to provide a short flat fiber product having the same and a method for producing the same.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a thread or string having a length of 1 to 3 times the total thickness of a textile product in a state where 5 to 100 short flat textile products are stacked. connected by, after the connection points was 1-5 points, immersed in the treatment solution, it is circulated and the processing liquid and the short flat plate-like fiber products
Were made and stained and conductive treatment, Oyo uniform dyeability
It is intended to provide a method for producing a short flat fiber product having electrical conductivity . Here, the dyeing and the conductive treatment are performed first.
After dyeing short flat fiber products, conduct electrical treatment
Is preferred. In addition, the present invention provides 5 to 100 gloves.
Threaded length of 1-3 times the total thickness of gloves when superimposed
It is connected by an object or a string, and the connection point is 1 to 5 places
After that , it is immersed in the processing solution to circulate the gloves and the processing solution.
The gloves are dyed and made conductive by ringing.
It provides gloves with excellent dyeability and conductivity.
You .

Examples of the short flat fiber product to which the present invention is applied include a fiber product made of a woven fabric, a knitted fabric, a nonwoven fabric, or the like such as a polyurethane fiber, a polyamide fiber, a polyester fiber, and an acrylic fiber. Examples of varieties include gloves, socks, arm covers and handkerchiefs.

The polyurethane fibers used in the present invention are generally called elastic yarns, and include spandex (manufactured by Fuji Spinning Co., Ltd.) and Espandione (manufactured by Kanebo Co., Ltd.). As the polyamide fiber, nylon 6, nylon 6, 6, nylon 1
2. Synthetic fiber obtained by melt-spinning and stretching nylon 4.

Further, the polyester fiber is a synthetic fiber obtained by spinning a polyester such as a polycondensate of glycol and dicarboxylic acid or a polycondensate of oxycarboxylic acid. The polyester fiber used in the present invention includes: Polyethylene terephthalate fibers are preferred. As the polyester fiber, a fiber made of cationic dyeable polyester can also be used.

Further, as the acrylic fiber used in the present invention, for example, a fiber made of a dyeable acrylonitrile polymer can be used. Here, as the polymerization of acrylonitrile, aqueous suspension polymerization using a redox catalyst is often used. In general, a small amount of a copolymer with other components is used as a fiber raw material in order to enhance the dyeability and bulkiness of the fiber. Styrene sulfonic acid, (meth) acryl sulfonic acid and the like are used as the dyeing seat of the cationic dye, and methyl vinyl pyridine and the like are used for the acid dye. Further, the copolymerization with methyl acrylate, methyl methacrylate, vinyl acetate and the like promotes diffusion of the dye into the fiber. For spinning, wet or dry spinning is used, and any of spun yarn and multifilament can be used.

The fibers used in the present invention described above may be used alone or as a mixture of these fibers, and may also contain fibers of vinylon, cellulose, wool, silk, cotton, polyethylene, polypropylene and the like. . In the case of a flat fiber product which has been subjected to a conductive treatment, it is preferable that the product contains at least one of the above-mentioned various fibers in an amount of 50% by weight or more. Further, the form of the fiber itself may be a fiber having a single composition, or a composite fiber such as a sea-island fiber, a core-sheath fiber, a split fiber, a side-by-side fiber, and an alternately arranged fiber.

[0010] Further, as the form of the various fibers,
For example, staple fiber, multifilament, spun yarn and the like can be mentioned. Examples of the form of the fiber product include fabrics such as a woven fabric, a knitted fabric, and a nonwoven fabric. The nonwoven fabric includes all forms such as a needle punching method, a spun bond method, a melt blow method, a stitch bond method, a paper making method, a flash spinning method, and an air ray thermal bond method.

[0011] 5 to 100 of the short flat fiber product
As a thread or string connecting the pieces, for example, cotton,
Twisted yarns such as sewing threads made of natural fibers such as hemp and silk, polyamide fibers, polyester fibers, acrylic fibers, and synthetic fibers such as vinyl fibers, string-like materials such as Lillian yarns, thread-like plastic molded products such as tag pins, and cotton strings And string-like materials such as hemp strings. Threads or cords may have heat shrinkage under use conditions,
For example, a rubber thread or a highly stretched thread may be used, and can be appropriately selected according to a fiber product. Of these, use of a tag pin having a T-shaped drop-off prevention structure provided at both ends in advance improves workability. The length of the thread-like material and the string-like material has a remarkable effect on the uniform circulation of the treatment liquid after connection, but is appropriately selected depending on the surface condition and density of the fiber product. If the length is too long, wrinkles may occur or a problem may occur in shape retention. The length is preferably 1 to 3 times, more preferably about 1.2 to 2 times the total thickness of the fiber product.

As a method of attaching the thread-like material or the string-like material, a sewing needle for clothing or a tatami mat or an automatic needle driving machine can be used. In addition, the places connected by these thread-like or string-like materials differ depending on the form of the textile, but not only one place of the overlapping textiles,
Two to five places may be used as necessary. The ends of these threads or strings may be tied at the other end to prevent them from falling off during processing, or may be knotted alone. Further, the material such as the thread / string or the tag pin is not particularly limited, but is appropriately selected from polyester, polypropylene, polyamide, etc. in consideration of temperature conditions and chemical resistance during the dyeing and / or electroconducting process. Is done. The number of connection in a state superposed short flat plate-like textiles, the bulk density of the fiber products, varies depending on the form, usually 200 or so less easy to handle, and more preferably about 5 to 100 .

In the case of dyeing the above-mentioned short flat fiber product, the dye of polyurethane fiber or polyamide fiber includes, for example, a sulfonic acid group-containing compound. Examples of the sulfonic acid group-containing compound include C.I. I. Acid Blu
e120 (manufactured by Nippon Kayaku Co., Ltd.), C.I. I. Acid Bl
ue 116 (manufactured by Nippon Kayaku Co., Ltd.), C.I. I. AcidOr
acid 7 such as C. angel 7 (manufactured by Nippon Kayaku Co., Ltd.);
I. Acid Violet 56 (manufactured by Nippon Kayaku),
Acid Complex Violet 3R (manufactured by Nippon Kayaku Co., Ltd.), Aizen Opal Violet 3
RL (manufactured by Hodogaya Chemical Co., Ltd.), C.I. I. Acid Vi
olet 58 (manufactured by Nippon Kayaku), C.I. I. Acid
Metal complexes of acidic dyes such as chromium complex of Green 35 (manufactured by Nippon Kayaku Co., Ltd.). As the structure of the dye, any of aminoanthraquinone-based, azo-based and other structures can be used.

As a method of treating with an organic compound having a sulfonic acid group, a method of immersing a fiber product in an aqueous solution of an organic compound is adopted. When an acid dye or a cationic dye is used, the pH of the treatment solution is adjusted. Adjust to the acidic side with acetic acid or the like. Acids used for pH adjustment include:
Hydrochloric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, benzenesulfonic acid, salicylic acid, perchloric acid, and the like can also be used, and these are preferable because they also have a function as a dopant. Further, an organic compound having a sulfonic acid group such as p-toluenesulfonic acid is particularly preferred. In the case of acid dyes and cationic dyes, the dye concentration in the processing solution is
It is preferably about 0.01 to 2% by weight.
To 7 are preferred. The immersion conditions are not particularly limited, and may be the same as ordinary dyeing conditions. However, it is preferable that a predetermined amount of the fibers is accurately and uniformly exhausted. When the treatment is carried out with a direct dye or a disperse dye, the same conditions as those for the acid dye can be employed. Further, the treatment with a sulfonic acid group-containing organic compound other than the dye is not particularly limited as long as the organic compound is exhausted by the fibers. If necessary, an auxiliary agent such as ammonium acetate, ammonium sulfate, or a leveling agent can be added to the treatment liquid. Alcohols such as methanol, ethanol, propanol and butanol may be added to the sulfonic acid group-containing organic compound.Addition of alcohols has the effect of lowering the processing temperature of polyamide, The permeability to textile products is also improved.

A disperse dye is used for dyeing the polyester fiber product. The disperse dye used is insoluble in water, but is finely dispersed in water in the presence of a dispersant, and is a dye showing an affinity for polyester fibers.Most of the dyes are azo dyes and anthraquinone dyes, but yellow dyes There are also some nitrodiphenylamine derivatives. In general, it has a relatively small molecular weight structure and mostly has a substituted amino group. Further, many of them do not contain a water-soluble group and have a nonionic hydrophilic group such as an oxyalkyl group and a cyanoalkyl group in order to improve dispersibility.

As the disperse dye, for example, Amacr
on (AAP), Calcosperse (CCC),
Dianix Fast, Dianix Light
(Mitsubishi), Eastman Polyester (T
E), Esteroquinone (Fran), Fo
ron (S), Genacron (G), Interc
hem Polydye (IC), Kayalon P
olyster (chemical), Latyl (Dup), M
iketon Polyester (Mitsui), Pala
nil (BASF), Resoline (FBy), S
amaron (FH), Sumikaron (Sumitomo),
Terasil (Ciba) and the like.

Dyeing with a disperse dye includes a carrier dyeing method under normal pressure and a dyeing method under high temperature and high pressure. In consideration of the effect on the working environment of the carrier, generally, 12 dyes are used.
It is carried out under a high temperature and a high pressure of 0 to 140 ° C. and ^{2 to} 3.5 kg / cm ² . The dye concentration of the disperse dye is 0.001 to
The dyeing conditions are not particularly limited, and may be the same as ordinary dyeing conditions. However, it is preferable that a predetermined amount of the fibers is accurately and uniformly exhausted.

Further, in the case of an acrylic fiber product, a cationic dye is used.
C. I. 42025 (CI Basic Blue)
1) or C.I. I. 42555 (CI Basic)
Violet 3), such as a triallylmethane dye, C.I.
I. 46005 (CI Basic Orange 1)
Acridine dyes such as 4); I. 50240 (C.I.
I. Basic Red 2) or C.I. I. 1221
Azine dyes such as C.I.0 (CI Basic Blue 16); I. 52015 (CI Basic B)
thiazine dyes such as C.lue 9); I. 48070
(CI Basic Red 12) or C.I. I.
48065 (CI Basic Yellowll)
Methine and polymethine dyes such as C.I. I. 4100
0 (CI Basic Violet 10) and the like, and in addition, Aizen Cathilon
(Hodogaya), Astrazon L (FBy), Bas
acryl (BASF), Calocozine Ac
lylic (CCC), Deorlene (Cib
a), Diacrul Supara (Mitsubishi), Gen
acryl (G), Maxilon (Gy): Nika
lon (Nippon Chemical), Sevron (DuP), Sum
iacryl (Sumitomo) and the like.

Dyeing with a cationic dye is carried out by adjusting the pH of the treatment solution to an acidic side with acetic acid or the like. This pH
Examples of the acid used for the adjustment include hydrochloric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, salicylic acid, perchloric acid, and the like. The dye concentration in the treatment solution of the cationic dye is 0.001 to 0. 0.2% by weight is preferred, and the pH of the treatment liquid is preferably 3-7. The staining conditions are
The dyeing conditions are not particularly limited, and may be the same as ordinary dyeing conditions. However, it is preferable that a predetermined amount of the fibers is accurately and uniformly exhausted. In addition, a heat dissociation type cationic dye can also be used as another cationic dye. Examples of the thermal dissociation type cationic dye include Kayacryl ED [manufactured by Nippon Kayaku Co., Ltd.] and AIZEN CATHILON DP [manufactured by Hodogaya Chemical Co., Ltd.].

Next, as a method for treating the conductivity of a short flat fiber product according to the present invention, for example, various short flat fiber products can be treated with a monomer capable of forming an electronic conjugated polymer and an oxidized product. A method of immersing the fiber product in a treatment liquid containing a polymerization agent (hereinafter sometimes referred to as a “conductivity treatment liquid”) to complex the electronic conjugated polymer with the fiber product may be used. After dyeing as described above, a method of conducting treatment may be used. Monomers capable of forming this electron conjugated polymer are those having a conjugated double bond in the molecular structure,
A substance that undergoes polymerization by oxidation. A typical example is a 5-membered heterocyclic compound,
Preferred examples of the membered cyclic compound used in the present invention include pyrrole, thiophene, furan, indole and derivatives thereof such as N-methylpyrrole,
Examples include, but are not limited to, methylpyrrole, 3-methylthiophene, 3-methylfuran, and 3-methylindole.

[0021] These monomers are polymerized by contact with an oxidizing polymerizing agent, preferably in the presence of a dopant. As the dopant, any commonly used acceptor dopant can be used. As the acceptor dopant, halogens such as chlorine, bromine and iodine; Lewis acids such as phosphorus pentafluoride; protonic acids such as hydrogen chloride and sulfuric acid; transition metal chlorides such as ferric chloride; silver perchlorate And transition metal compounds such as silver boron fluoride.

Examples of the oxidizing polymerization agent include permanganic acid or permanganic acids (salts); chromic acids such as chromium trioxide; nitrates such as silver nitrate; halogens such as chlorine, bromine and iodine; Hydrogen, oxides such as benzoyl peroxide; peroxodisulfuric acid, peroxodisulfuric acid and other peroxoic acids; peroxoacid salts; hypochlorous acid, potassium hypochlorite, and potassium hypochlorite; Oxyacid salts; ferric chloride, cupric chloride,
Transition metal chlorides such as stannic chloride and potassium chloride; and metal oxides such as silver oxide. Among these oxidative polymerization agents, halogens, peroxo acids (salts)
Classes, transition metal chlorides, and the like have an action as a dopant, so when they are used as an oxidative polymerization agent, it is not necessary to use another dopant in combination, but when used together, the conductivity is further improved. May be possible. In addition, as the oxidative polymerization agent, for example, cupric perchlorate, ferric perchlorate and the like can be used, and these can be used alone or in combination. The amount of the oxidizing polymerization agent to be used with respect to the monomer capable of forming the electron conjugated polymer is preferably 2 to 3 times, particularly preferably about 2 times.

The various fiber products are immersed in a conductive solution, and a monomer capable of forming an electron conjugated polymer is contacted with an oxidizing polymer in the conductive solution. Examples of a method of treating a textile with a conductive treatment liquid include, for example, a method of immersing the fiber product in a conductive treatment liquid containing a monomer, an oxidizing polymerization agent, and optionally a dopant before the monomer is substantially polymerized. A treatment solution containing an oxidative polymerization agent and, if necessary, a dopant, and a method of sequentially immersing the fiber product in a treatment solution containing a monomer. After immersion, a method of adding a monomer to the treatment liquid may be used.

According to the method, the processing time can be shortened. In addition, since the oxidative polymerization agent has a lower permeability to the fiber product than the monomer, a method of separately performing the treatment with the monomer-containing treatment liquid and the immersion treatment with the oxidative polymerization agent-containing treatment liquid as in the methods of (1) to (4) is adopted. However, it is preferable to first perform the immersion treatment with the treatment solution containing the oxidizing polymer agent, and in this case, the impregnation amount of the oxidizing polymer agent into the fiber product increases, so that the composite of the electronic conjugated polymer and the fiber product is formed. Are promoted, and more durable conductivity is obtained.

When the monomer capable of forming the electron conjugated polymer and the oxidative polymerization agent are liquid, they can be used as they are as the electroconductive treatment solution.
When the monomer and the oxidative polymerization agent are used as they are, especially in the method of immersing the fiber product in the conductive processing solution in which the monomer and the oxidative polymerization agent are mixed, the generation of the polymer in the conductive processing solution is fast, and the fiber product It is preferable that the monomer and the oxidative polymerization agent are diluted with an appropriate solvent before use, since the formation of a complex between the polymer and the polymer may be hindered and sufficient conductivity may not be obtained.

As the solvent, water or a commonly used organic solvent can be used. Examples of the organic solvent include methanol, ethanol, n-propanol, i-propanol, t-butyl alcohol, i-butyl alcohol and the like. Aliphatic alcohols; aliphatic ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as methylene chloride and chloroform; esters such as ethyl acetate and butyl acetate; toluene; Aromatic hydrocarbons; aliphatic hydrocarbons such as hexane; nitrogen-containing compounds such as acetonitrile and benzonitrile; and mixtures thereof. Among these solvents, depending on the monomer, dopant, oxidative polymerization agent and fiber Select and use as appropriate The concentration of the monomer and the concentration of the oxidizing polymerization agent in the conductive treatment liquid vary depending on the material of the fiber and the desired degree of conductivity, but the concentration of the monomer is 5 × 10 ⁻³ to 1 × 10 ^−3.
The concentration is preferably about the molar concentration, and the concentration of the oxidative polymerization agent is preferably about 1 × 10 ⁻³ to about 1 molar.
The monomer concentration is 0.01 to 5% by weight per fiber.
The degree is preferred. The dopant concentration is 1 × 10
^The concentration is preferably about ⁻⁴ to 1 × 10 ⁻² mol.

The temperature of the treatment liquid when immersing the short flat fiber product in the treatment liquid for conductivity is preferably -20 to 30 ° C., more preferably -20 to 5 in order to further improve the given conductivity.
° C, more preferably 0 to 20 ° C, particularly preferably 0 to 20 ° C.
5 ° C.

As a specific apparatus used for these dyeing and conductivity treatments, a rotary dyeing machine is most suitable. A partition wall is provided on the inner body, and a textile product to be processed is treated in a processing solution. It is also preferable to increase the stirring effect. Further, it is particularly preferable that the inner body not only rotates in one direction but also automatically reverses at regular time intervals. It is also effective to provide two to four protrusions on the inner surface of the inner body to assist in stirring and rotating the object to be processed in the inner body, and it is more effective to provide the same together with the partition wall. The filling amount of the processing liquid when the inner body is filled with the fiber product to be treated and dyed and made conductive is not particularly limited, and is appropriately determined depending on the amount of the processed material, the dyeing speed, the conductivity speed, and the like. For the supply of the processing liquid component, the entire set amount may be charged in advance. It is more effective to add them continuously or intermittently as appropriate.

In the case of post-addition, the addition method is as follows.
It may be added to the space between the outer shells from above, or may be supplied from below using a separately provided material-added layer using gravity by gravity, or may be forcibly supplied by a pump. When conducting, it is preferable to continuously or intermittently add an oxidizing polymerization agent in order to realize uniform formation of a polymer film on the fiber surface of an electron conjugated polymer such as polypyrrole.

[0030] As described above, the onset Ming, can be widely applied to the processing of short tabular textiles that combine staining and conductive treatment. In addition, the electrical conductivity treatment can be applied to electrical conductivity by copper sulfide coating.

[0031]

According to the method of the present invention for producing a short flat plate-like fiber product, a plurality of short flat plate-like fiber products are superimposed.
This fiber product was ligated with filamentous material or string-like material, for beauty conductive treatment After that staining Oyo, a uniform circulation of the dyeing liquid and conductive agent, uneven dyeing, conductive unevenness without, yet shape-retaining sex, it is possible to provide a uniform dyeing and conductive-treated short flat plate-like fiber product having excellent workability, taking
In other words, a glove having uniform dyeability and conductivity can be obtained.

[0032]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but it goes without saying that the present invention is not limited to these examples. Example 1 As shown in FIG. 1, a thickness of 0.5 knitted from 6 nylon wooly processed yarn (high elongation type) and polyurethane fiber.
10 gloves 10 (textile products) are laid on top of each other, and the 20th polyester sewing thread 20 is pierced at intervals of 1 cm with a sewing needle for tatami so that the length becomes 7 cm on each of the wrist and the base of the middle finger. Tied the department.

Next, this was purified with a rotary dye (not shown) to make Kayakaran Red [manufactured by Nippon Kayaku Co., Ltd.] 1.0% o.
Using wf as a dye, dyeing was carried out at 20 to 95 ° C., 12 revolutions / minute, automatically inverted every 5 minutes, at a bath ratio of 12: 1. After thoroughly washing with water, washing twice with pure water of 0.5 μs / cm, pyrrole monomer 1% owf, oxidizing polymerization agent (ferric chloride) (monomer / oxidizing polymerization agent molar ratio, 1 / 2.5) At 5 ° C., and the reaction was continued for 120 minutes while maintaining the temperature at 5 ° C. after the addition was completed. The resulting product had been uniformly dyed and made conductive. In addition, there was almost no wrinkles or deformation, and the appearance was extremely good.

Comparative Example 1 The gloves 10 were dyed and made conductive in the same manner as in Example 1 except that the gloves 10 were separated without being overlapped, but this was finished in a uniform state, but was slightly entangled. In addition, the product was significantly twisted and wrinkled, and a good appearance as a product could not be obtained in a dry state as it was.

[0035]

According to the method of the present invention for producing a short flat fiber product, a plurality of such short flat fiber products are superimposed, connected by a thread or a string, and then dyed. to and conductive treatment, according to the present invention,
A uniform circulation of the dyeing liquid and conductive agent, uneven dyeing, conductive unevenness without addition shape retention, uniform dyeability and which is excellent stain and guide <br/> imparting process workability conductive It is possible to provide a short flat fiber product having a property .

[Brief description of the drawings]

FIG. 1 is a perspective view of a short, flat fiber product having uniform dyeability and conductivity that has been dyed and made conductive according to one embodiment of the present invention.

[Explanation of symbols]

10 Gloves ( short flat textile products) 20 Polyester sewing thread (filament or string)

Claims (3)

(57) [Claims] 1. A state in which 5 to 100 short flat fiber products are overlapped and connected by a thread or string having a length of 1 to 3 times the total thickness of the fiber products. After the positions 5, immersed in the processing solution, the short flat plate-like
By circulating the textile treatment liquid, dyeing and conductive treatment
A method for producing a short, flat fiber product having uniform dyeability and conductivity . 2. The method according to claim 1, wherein the conductive treatment is performed after dyeing.
A method for producing a short flat fiber product having uniform dyeability and conductivity as described above. 3. A state in which 5 to 100 gloves are stacked.
With a thread or string that is 1-3 times longer than the total thickness of the glove
After connecting more than one to five places , the processing solution
Immersed in the glove and circulate the processing solution,
Dyeing and conductivity treatment for uniform dyeing and conductivity
Gloves with electrical properties.