JPH09273073A - Processing of textile product having biological resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To carry out the control of-molds, bacteria, algae and mites by applying specific chemicals having the biological resistance to a fiber, heat-treating the resultant fiber, fixing a prescribed amount of the chemicals thereto and efficiently processing a textile product. SOLUTION: Four or more kinds of chemicals selected from the group consisting of nitrile-based compounds such as a haloisophthalonitrile derivative, pyridine-based compounds such as a pyridinethiol 1-oxide derivative, haloalkylthio-based compounds such as a haloalkylthiosulfamide derivative, organic iodine-based compounds such as an iodosulfonylbenzene derivative, a thiazole-based compound such as an isothiazolin-3-one derivative and benzimidazole-based compounds such as a benzimidazolecarbamic acid derivative having biological resistance are applied to a fiber in a dyeing step and/or a finishing processing step thereof together with a dye or a finishing agent and the chemicals in an amount of 0.01-5.0wt.% based on the fiber are then fixed to the fiber by heat treatment to process the textile product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a bio-resistant textile product, and more specifically, it is resistant to the attachment and growth of organisms such as molds, algae and bacteria.
Further, the present invention relates to a method for processing a textile product having a mites repellent property.

[0002]

2. Description of the Related Art Conventionally, various fiber products having resistance to mold, algae, bacteria, and mites have been studied, for example, thiazobenzimidazole (hereinafter referred to as TBZ).
Textile products containing are known. This drug is 25
-30 years ago, it has been widely used for textile products, building materials, wallpaper and wall soil applications. However, TBZ is resistant to some molds and bacteria, but there are molds and bacteria that are not originally resistant, and TBZ is not resistant to resistant molds and bacteria.
Narrow antibacterial spectrum. Therefore, a textile product using such a drug has only about 50% effectiveness against mold and bacteria existing in the living environment. Furthermore, such agents showed almost no resistance to algae and mites.

In recent years, antibacterial agents such as quaternary ammonium salts and silver-containing ceramics have been widely used especially in textile products for clothing. These antibacterial agents are mainly kneaded and post-processed on the fiber surface, and have appropriate antibacterial properties, but even though they are resistant to bacteria, they are mostly resistant to mold, algae, and mites. Nothing is resistant.

On the other hand, a fiber material has been developed which is provided with organotin or fine copper powder to the fiber and has resistance to adhering organisms in water or in the sea. Therefore, there are problems in manufacturing technology and cost.

A lot of fibers imparted with mites resistance (mainly repellent) are also on the market, and the chemicals thereof are processed products of diethyltoluamide (DEET) (microencapsulation), amide type and thiocyanate type. , Mainly carboxylic acid esters and bornyl alcohol derivatives.
Considering safety to the human body, these drugs mainly show the repellent effect of mites and show a repelling rate above a certain level, but almost no one showing resistance to fungi, bacteria and algae is found. is the current situation.

As described above, a fiber product having sufficient resistance to fungi, bacteria, algae, and mites and having a broad spectrum for each organism has not yet been developed, and a plurality of fiber products have not yet been developed. The development of such products is desired for applications that require resistance or for applications where each resistance is not satisfied by conventional products.

On the other hand, as a means for imparting these functional processing chemicals to fibers, there are roughly classified a method of kneading at the raw material stage and a post-processing treatment using a resin in combination. In the kneading method,
Restricted by heat resistance, discoloration, cotton making, yarn-forming property, lot size, etc., and problems such as durability, appearance and texture change remain in the post-processing, making it more economical and efficient. A method is desired.

[0008]

The present invention was devised to solve the above-mentioned drawbacks of the prior art, and its purpose is to provide sufficient resistance to mold, bacteria, algae, and mites. An object of the present invention is to provide an economical and efficient method for processing a textile product which has a biological resistance having a broad spectrum with respect to each organism.

[0009]

In order to achieve such an object, the present inventor has a fiber which is resistant to the attachment and growth of organisms such as mold, algae and bacteria, and which is repellent to mites. As a result of intensive studies on economical and efficient processing methods for products, the present invention has been completed.

That is, in the present invention, the following chemical agent (I) having bioresistance is added to the fiber in the dyeing step and / or finishing processing step together with the dye and the finishing agent, and the following chemical agent (I) is applied to the fiber by heat treatment. It is a method for processing a textile product having a biological resistance of 0.01 to 5.0% by weight. Drug (I): At least four compounds selected from the group consisting of nitrile compounds, pyridine compounds, haloalkylthio compounds, organic iodo compounds, thiazole compounds and benzimidazole compounds.

In a preferred embodiment of the present invention, the above drug (I) is haloisophthalonitrile derivative, pyridinethiol-1-oxide derivative, sulfonylhalopyridine derivative, haloalkylthiosulfamide derivative, iodosulfonylbenzene derivative, Isothiazoline-3-
It is at least four compounds selected from the group consisting of on-derivatives, thiazolebenzimidazole derivatives and benzimidazolecarbamic acid derivatives.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The agents having bioresistance used in the present invention include nitrile compounds, pyridine compounds,
At least four compounds selected from the group consisting of haloalkylthio compounds, organic iodine compounds, thiazole compounds and benzimidazole compounds,
It is preferably at least 6 compounds, particularly preferably at least 7 compounds. When the type of the drug is less than 4, the obtained fiber product has a narrow resistance spectrum to organisms, and the generation of resistant organisms cannot be suppressed. All of these compounds have high decomposition temperatures, low solubility in water, and high safety.

Examples of the nitrile compound include a haloisophthalonitrile derivative and the like, and examples of the pyridine compound include a pyridinethiol-1-oxide derivative and a sulfonylhalopyridine derivative. Examples of haloalkylthio compounds include haloalkylthiosulfamide derivatives and tetrachloroethylthiotetrahydrophthalimide derivatives. Examples of the organic iodine compounds include iodosulfonylbenzene derivatives and propargylbutylcarbamic acid derivatives. Examples of thiazole compounds include isothiazolin-3-one derivatives and thiazole benzimidazole derivatives. Examples of the benzimidazole compound include benzimidazolecarbamic acid derivatives.

The above-mentioned drugs are preferably haloisophthalonitrile derivatives, pyridinethiol-1-oxide derivatives, sulfonylhalopyridine derivatives, haloalkylthiosulfamide derivatives, iodosulfonylbenzene derivatives, isothiazolin-3-one derivatives, thiazolebenzimidazoles. At least 4 selected from the group consisting of derivatives and benzimidazolecarbamic acid derivatives
Compounds, more preferably at least 6 compounds,
Particularly preferred are at least 7 compounds, and more preferred are 2,4,5,6-tetrachloroisophthalonitrile, 2-pyridinethiol-1-oxide sodium, 2,3,5,6-tetrachloro- 4-Methylsulfonylpyridine, N, N-dimethyl-N'-phenyl-
N'-dichlorofluoromethylthiosulfamide, diiodomethyl-p-tolylsulfone, 2- (n-octyl) -4-isothiazolin-3-one, 2- (4-thiazolyl) -1H-benzimidazole, 1H-2- At least 4 compounds selected from the group consisting of methyl benzimidazole carbamate, particularly preferably at least 6 compounds, most preferably at least 7 compounds. In addition, two or more compounds may be selected from the similar compounds as long as they have sufficient resistance to the above organisms, the spectrum is not narrowed, and the generation of resistant organisms can be suppressed.

Among the above-mentioned agents, the compound having resistance to mold is 2,4,5,6-tetrachloroisophthalonitrile, and the compound having resistance to bacteria is 2 in particular. , 3,5,6-Tetrachloro-4-methylsulfonylpyridine, which is particularly resistant to algae, is N, N-dimethyl-N'-phenyl-N'-dichlorofluoromethylthiosulfamide. Therefore, it is considered that there is a combined action of these compounds on mites.

The content of each drug with respect to all the drugs is preferably 1.0% by weight to 90% by weight, more preferably 3.0% by weight to 70% by weight, based on the total amount of the agents. If this content is less than 1.0% by weight, the effects of each drug will be insufficient, and conversely, if it exceeds 90% by weight, the contents of other drugs will be low and their effects will be insufficient. Not preferable. The total applied amount and each content of the drug are appropriately determined within the above range depending on the usage environment of the obtained product and the like.

The amount of the drug applied to the textile product is 0.05.
-5% by weight is preferable, but when imparted by the kneading method, the medicinal effect is diluted with the fiber polymer, so 0.5-5%
A high rate of kneading by weight% is required, which greatly affects the cost and is inferior in economic efficiency. Further, depending on the fiber to be kneaded, there is a risk of shining, discoloration, etc. when the polymer is dissolved (melted). This tendency is greater in fibers having a higher spinning temperature, such as polyester and nylon. It is necessary to fix the drug to the fiber surface as much as possible, and there is a post-processing method that uses it together with a resin binder such as an acrylic, vinyl acetate, or urethane resin, but to improve the texture, appearance, and processability in textileization. There was an influence, and a more economical and efficient processing method was desired. In consideration of such a request, the present inventor has found an economical processing method for fixing the drug to the fiber surface by utilizing the heating process in the dyeing process of the fiber and / or the subsequent finishing process of the drug. Completed the invention. Since the majority of the fibers pass through the dyeing and finishing processes, these heat treatments are effectively utilized.

The method of heat-fixing the agent of the present invention at the same time as dyeing or by heat treatment thereafter is less economical than the kneading method, the amount of application is about 0.05 to 1.0%, and at the same time economical. Since the heat treatment temperature lower than the melting temperature of kneading is used, there is an advantage that the stability of the drug is improved.
In addition, since the one to which the chemical is applied in the process from the spinning to the dyeing process is easily removed by the heat treatment of the dyeing,
Although the method of utilizing heat in the dyeing step and / or the finishing step after dyeing of the present invention is inferior to the kneading type fiber, it does not drop off during washing or dry cleaning and has sufficient durability.

The processing method of the present invention includes all natural fibers such as cotton, wool, hemp and silk, chemical fibers such as rayon, polynosic and acetate, synthetic fibers such as polyester, acrylic, nylon, polypropylene, modacrylic and polyurethane. Applicable to fiber. Further, the processing form can be applied to a dyeing finishing process suitable for the form, such as a staple form, a filament form, a knitted form, a woven form, and a non-woven fabric form.

Since the processing method of the present invention utilizes the heat of dyeing and finishing, the smaller the particle size of the chemical agent used in the present invention is, the more uniform the adhesion and the improvement of durability are, and the particle size is 10 μm. Hereafter, fine powder of 1 μm or less is preferable.

The fiber products thus obtained are processed into various fiber products such as bio-resistant clothes, daily necessities, sports / leisure products, construction civil engineering materials, agricultural / forestry / fishery materials, industrial materials, and the like. Is effectively used in a place where organisms are generated during use or storage, and these attach to and parasitize products and propagate.

The textile product obtained by the method of the present invention is broad-spectrum resistant to fungi, bacteria, algae and mites present in living spaces. Examples of the molds to which the fiber product obtained by the method of the present invention has resistance include, for example, Grospora oryzae, Cladosporium regine, Cladosporium herbalem, Cladosporium cladsporioidas, Cladosporium safaerosperma, Trichoderma koningi. , Trichoderma T-
1, Tricoderma Viridi, Forma Glomerata, Former Terescias, Pluraria Pullulance, Gliocladium Vilens, Geotricum Lactus, Geotricum Candidum, Vestalothia Adasta, Vestalothia Negrecta, Milotesium Felucaria, Alterna Tenerus, Alterna Teruna Burassa Lunatha, Aspergillus niger, Aspergillus flavus, Aspergillus felsicor, Aspergillus oryzae, Aspergillus terreus, Aspergillus fumigatus, Aureobasidium pullulans, Fusarium moniforme, Fusarium semitectum, Fusarium plaliferatum, Fusarium
Roseum, Fusarium solani, Fusarium oxysvolum, Rhizopus niglycans, Rhizopus stronifel, Penicillium citrinum, Penicillium ikupansa, Penicillium funiculozam, Penicillium relicanthrum, Penicillium citricium frictus, Penicillium licoricea, Penicillium pericythium citricum Grofites, Monilia Fructicana, Ketomium globotham,
Examples include Ebicoccum perplacensis, Acremonium chalticola, Waremia sevi, Candida albicans, Streptofetecilium reticalem, Saccharomyces cerevisiae and Botrytis cinerea.

Examples of algae include Prorococcus species, Anavena species, Cladophora gromorata, Anacystin nidarans, Anxtrodemas Angustus, Chlamydimonas.
Reinharty, Nostokales species, Urotricase species, Trent Paulia Odalata, Trent Paulia Ole, Anasity Montana, Anasity Samari, Chlorococcanma spices, Cytnima Hofmany, Carothrica les Relais Calescora, Schizosuricus karismora, Chlores cholera, Schizosuricus cloisola Examples include Free Sea, Schizo Thrix Rubera, Ossellatoria Rootie, Home Medium Species, Sirindro Capsa Species, and Navicara Species.

Examples of the bacterium include Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Bacillus subtilis, modified bacterium, Swine fever bacterium, Salmonella typhi, Mycobacterium tuberculosis, Salmonella typhimurium, Klebsiella pneumoniae and the like. Examples of the mites include Dermatophagoides farinae and Dermatophagoides farinae.

[0025]

EXAMPLES Next, the present invention will be explained with reference to examples and comparative examples, but the present invention is not limited to these.
The antifungal test, antialgal test, antibacterial test, and tick repellent test were carried out on the textile products obtained in Examples and Comparative Examples, and the test methods and evaluation methods are as follows.

Antifungal test The MIL STD 810D Method 508.3 modified method was adopted, and 62 kinds of mixed fungi shown below were used.
Direct inoculation from a mixed spore suspension by the wet method, using potato dextrose agar medium (without addition of antibiotics such as PDA and chloramphenicol) at a temperature of 30 ° C ± 5 ° C and a humidity of 9
The cells were cultured for 28 days under the conditions of 5% ± 5% RH and a wind speed of 60 cm / sec. The evaluation was performed according to the following 5 grades. 0: No mold growth is observed. 1 ... Slight growth of mold. 2 ... There is some mold growth. 3 ... There is considerable mold growth. 4 ... Mold growth is severe.

The molds used in the mildew proof test were the following molds: Nigrospora olize, Cladosporium regine, Cladosporium herbalem, Cladosporium Cladosporioidas, Cladosporium safaerosperma, Trichoderma koningi, Trichoderma T-1, Trichoderma Viridi, Forga Glomerata, Former Terescias, Pluraria pullulans, Gliocladium vilens, Geotricum lactus, Geotricum candidam, Pestalothia Adasta, Pestalothia Negreta, Milotesium ferucaria, Alternaria altera terunas, Alterna Lunaria Alternata, Aspergillus niger, Aspergillus flavus, Aspergillus felsicor, ass Pergillus oryzae, Aspergillus terreus, Aspergillus fumigatus, Aureobasidium pullulans, Fusarium moniliforme, Fusarium semitectum, Fusarium praliferatum, Fusarium roseum, Fusarium solani, Nitricran cyprisnis, Nigerus nitricans, Rhizopus nigricanus, Rhizorium nitricran, Rhizopus nigricans Funiculozam, Penicillium lyracinum, Penicillium niglycans, Penicillium frequentus, Penicillium citreability, Mucor racemasus, Eurotium tonafilum, Trichoften mentaglophytes, Monilia fructigana, Ketomium globosum,
Epicoccum perplacense, Acremonium charticola, Waremia sevier, Candita albicans, Streptofetecilium reticalem, Saccharomyces cerevisiae, Bacillus subtilis, Bacillus megaterium, Staphylococcus aureus, Pseudomonas, Pseudomonas, Pseudomonas
Cori, Potritis cinerea, Proteus vulgaris. These molds were stock culture pure cultures or subcultures within 30 days stored at 6 ° C ± 4 ° C, respectively.

Algae control test The following 25 types of mixed algae were used. Direct inoculation from the mixed algae dispersion by the wet method, using the following medium at a temperature of 2
The cells were cultured in an egg incubator for 28 days under the conditions of 5 ° C to 30 ° C and humidity of 90% RH to 100% RH. During culturing, the pigs on the Petri dish should be removed for at least 4 hours a day to obtain 1500 Lux (6
Irradiation with a 0 W positive fluorescent lamp was performed and evaluated every 7 days according to the following 5 grades. 0 ... No growth of algae is observed. 1 ... Slight growth of algae. 2 ... There is some algae growth. 3 ... There is considerable growth of algae. 4 ... The growth of algae is intense.

The medium used consisted of the following components: _{KNO 3 1.25g MgSO 4 · 7H 2} O 1.25g NaCl 1.25g FeSO 4 · H 2 O 0.05g CaCl 2 0.1g K 3 HPO 4 0.35g Agar 15g of pure water 1000 ml, pH 5.8

The algae used in the algae control test were the following algae: Prorococcus species, Anavena species, Cladophora gromorata, Anacysti nidarans, Anchistro de Mas Angustus, Chlamydimonas reinharti, Nost carless species, Urotricace species, Trent. Paulia Odalata, Torrent Paulia Ole, Anasti Simontana, Anasthisi Samari, Chloro Kockanma Species, Cytnima Hofmane, Carothrix Parretina, Schizosurix Calcicola, Chlorella Ezomani, Chlorella Brugarles, Tribonima Species,
Schizothurix Free Sea, Schizothurix Rupera, Ossellatoria Rootie, Home Medium Species, Cylindro Capsa Species, Navicara Species.

Antibacterial Test The difference between the bacterial increase and decrease values according to the bacterial count measurement method of the Textile Products Hygiene Processing Council (abbreviation SEK) using Staphylococcus aureus was adopted. The difference in the bacterial increase / decrease value was indicated by the difference between the number of bacteria (logarithm) of the standard white cloth (without antibacterial treatment) after 18 hours of culture and the number of bacteria of the test material after 18 hours of culture (logarithm). In SEK,
An antibacterial and deodorant effect is given when it is 1.6 or more, and an antibacterial and deodorant effect is not given when it is less than 1.6. Tick repellent test The test was carried out by the Osaka Prefectural Institute of Public Health using Dermatophagoides farinae.

Example I Acrylic staples (K
82d × 51 mm) was dyed with a cationic dye by a conventional method using an Overmeier dyeing machine. The dyeing heat treatment was carried out by heating the mixture to 70 ° C. for 20 minutes until it boiled, and in the boiling state for 45 minutes. At the same time as the dyeing treatment, the agents shown in Table 1 were added and treated (Examples 1 to 6, Comparative Example 1) ~
3).

[0033]

[Table 1]

Using this acrylic staple as a spun yarn of cotton count No. 20, a circular knit fabric was prepared by a knitting machine. This cloth is subjected to home washing in accordance with JIS-L-0217 103 method 10 times, including unwashed products, to prevent mold, algae,
Antibacterial and tick repellent tests were evaluated.

The results are shown in Table 2.

[Table 2] As can be seen from the results in Table 2, the fabrics of Examples 1 to 6 of the present invention were able to obtain good results in each evaluation.

Example II Polyethylene terephthalate filament manufactured by Toyobo Co., Ltd. 150 denier / 48 filament was used, and the diameter was 65.
A flat woven fabric of books / inch and weft of 50 pieces / inch was created. This woven fabric is sewn from 60 ° C to 130 ° C using a jet dyeing machine.
The temperature was raised for 1 minute, and a conventional disperse dye dyeing was carried out at 130 ° C. for 25 minutes. At the same time as dyeing, the agents listed in Table 1 were added,
It was heat-fixed to the fiber surface (Examples 1'-6 ', Comparative Examples 1'-3'). The same evaluation as in Example I was performed on this processed fabric.

The results are shown in Table 3.

[Table 3] As can be seen from the results of Table 3, Examples 1'to 6'of the present invention.
The fabric of No. 1 could obtain good results in each evaluation.

EXAMPLE III A circular knit knit was made by an 18G circular knitting machine using a cotton comber yarn of cotton count No. 30, and after opening, scouring, bleaching by a conventional method,
A reactive dye dyeing was performed to create a knit fabric. A soft finishing agent (Sansoflon FD-304) manufactured by Nika Kagaku Co., Ltd. together with the agents shown in Table 1 was pad-treated so that the fiber content was 1% owf, and dried at 120 ° C for 20 minutes using a pin tenter. It was treated (Examples 1 ″ to 6 ″, Comparative Examples 1 ″ to 3 ″). The same evaluation as in Example I was performed on this processed fabric.

The results are shown in Table 4.

[Table 4] As can be seen from the results in Table 4, Examples 1 "to 6" of the present invention
The fabric of No. 1 could obtain good results in each evaluation.

[0040]

As described in detail above, according to the processing method of the present invention, it is possible to economically and efficiently provide a fiber product having broad resistance to mold, bacteria, algae and mites.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location D06M 13/322 D06M 13/34

Claims (2)

[Claims] 1. The following chemical agent (I) having bioresistance is added to the fiber in the dyeing step and / or finishing step together with a dye and a finishing agent, and the following chemical agent (I) is added to the fiber by a heat treatment. 01-5.0% by weight A method for processing a textile product having bio-resistance to be fixed. Drug (I): At least four compounds selected from the group consisting of nitrile compounds, pyridine compounds, haloalkylthio compounds, organic iodo compounds, thiazole compounds, and benzimidazole compounds. 2. The drug (I) is haloisophthalonitrile derivative, pyridinethiol-1-oxide derivative, sulfonylhalopyridine derivative, haloalkylthiosulfamide derivative, iodosulfonylbenzene derivative, isothiazolin-3-one derivative, thiazole. The method for processing a textile product having bioresistance according to claim 1, which is at least four kinds of compounds selected from the group consisting of benzimidazole derivatives and benzimidazolecarbamic acid derivatives.