JPH09157111A - Molded article having resistance to organisms, its production and finished product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an article having satisfactory resistances to molds, germ, algae and undersea attached algae and a wide spectrum to each analogous organisms and its production method and finished products. SOLUTION: This article having the resistance to organisms is composed of a resin and chemicals having the resistance to organisms comprising at least 4 kinds of compounds selected from nitrile compounds, pyridine compounds, haloalkylthio compounds, organic iodine compounds, thiazole compounds and benzimidazole compounds and the amount of the chemicals is 0.01-30wt.% based on total components of the article.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having bioresistance, a method for producing the same, and a product using the same, more specifically, attachment and reproduction of molds, algae, bacteria, and adherent organisms in the sea. The present invention relates to a molded article having resistance to, and repelling mites, a method for producing the same, and a product using the same.

[0002]

2. Description of the Related Art Conventionally, various molded products having bioresistance have been studied, and for example, molded products containing thiazobenzimidazole (hereinafter referred to as TBZ) are known. This molded product has been widely used for textile products, building materials, wallpaper, wall soil, etc. for 25 to 30 years. But,
TBZ is resistant to certain molds and bacteria, but there are molds and bacteria that originally do not exhibit resistance, and resistant molds and resistant bacteria do not exhibit resistance and TBZ has a narrow spectrum. Therefore,
A product using such a molded product was only about 50% effective against mold and bacteria present in the living environment. Further, such a molded product showed almost no resistance to algae, adhering organisms in the sea, and mites.

In recent years, molded articles containing quaternary ammonium salts have begun to be widely used especially for textile products for clothing. The resistance of this salt is due to the bactericidal activity of cations (cations). Such a molded article had sufficient resistance to bacteria, but did not have resistance to mold, algae, adhering organisms in the sea, and mites.

Furthermore, a fixed net or a mooring rope obtained by immersing a fishing net or rope in a resin mixed with organic tin, drying and hardening the same has resistance to algae and adhering organisms in the sea. It has been known. However, the toxicity of organotin has been a problem in recent years, and these have not been produced.

Furthermore, it is known that a net made of a thread formed by kneading fine copper powder into a solution before polymerization, extruding after polymerization, and having resistance to algae and adhering organisms in the sea. There is. However, such a net is not sufficiently effective unless the content of the copper powder is increased, and the method for obtaining the net containing a high concentration of copper powder has problems in production and products. In addition, such nets had little resistance to mold and mites.

Therefore, a molded article having sufficient resistance to fungi, bacteria, algae, adhering organisms in the sea and mites, and having a broad spectrum for each organism has not yet been developed. Development of such a product is desired in applications requiring the above-mentioned resistance, or in applications where the respective resistances are not satisfied by conventional molded products.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks, and its object is to provide sufficient resistance to mold, bacteria, algae, adhering organisms in the sea and mites. (EN) A molded product having a broad spectrum for each organism, a method for producing the same, and a product using the same.

[0008]

The present invention is a bioresistant molded article containing a resin and a drug having bioresistance, wherein the drug having bioresistance is a nitrile compound,
At least 4 selected from the group consisting of pyridine compounds, haloalkylthio compounds, organic iodine compounds, thiazole compounds and benzimidazole compounds
A bio-resistant molded product, which is a compound of a kind and has a drug content in the range of 0.05 to 30% by weight based on all components constituting the molded product. In a preferred embodiment, the agent is a haloisophthalonitrile derivative,
At least one selected from the group consisting of a pyridinethiol-1-oxide derivative, a sulfonylhalopyridine derivative, a haloalkylthiosulfamide derivative, an iodosulfonylbenzene derivative, an isothiazolin-3-one derivative, a thiazole benzimidazole derivative and a benzimidazolecarbamic acid derivative. There are four compounds. In a preferred embodiment, the molded product is a fiber. The present invention is also a product characterized by using the above-mentioned bio-resistant molded product. Furthermore, the present invention is a method for producing a bioresistant molded article in which a resin and a drug having bioresistance are mixed and then molded, wherein the drug having bioresistance is
It is at least four kinds of compounds selected from the group consisting of nitrile compounds, pyridine compounds, haloalkylthio compounds, organic iodine compounds, thiazole compounds and benzimidazole compounds, and the addition amount of the drug is a molded product. 0.05 to 30 for all components that make up
A method for producing a bio-resistant molded article, characterized in that the content is in the range of wt%.

Next, the present invention will be described in detail. In the present invention, the bioresistance means the property of showing resistance to the attachment and reproduction of mold, bacteria, algae, and marine organisms, and repelling mites. The bio-resistant molded article of the present invention,
It contains a binder and a drug having bioresistance.

Drugs having bioresistance include nitrile compounds, pyridine compounds, haloalkylthio compounds,
At least four kinds of compounds selected from the group consisting of organic iodine compounds, thiazole compounds and benzimidazole compounds, preferably at least six kinds of compounds, particularly preferably at least seven kinds of compounds. When the type of the drug is less than 4, the obtained molded article has a narrow spectrum for organisms and cannot suppress the generation of resistant organisms. 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 drug is preferably a haloisophthalonitrile derivative, a pyridinethiol-1-oxide derivative, a sulfonylhalopyridine derivative, a haloalkylthiosulfamide derivative, an iodosulfonylbenzene derivative, an isothiazolin-3-one derivative, a thiazolebenzimidazole. 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 fungi is 2,4,5,6-tetrachloroisophthalonitrile, and the compound particularly having resistance to bacteria is 2 , 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 the drug in the molded product is such that the total amount is 0.05 to 3 with respect to all the components constituting the molded product.
0% by weight, preferably 0.15 to 6.0% by weight, particularly preferably 0.20 to 3.0% by weight. 10 to 30% by weight is particularly preferable for preventing adhesion of marine organisms. When this content is less than 0.05% by weight, the resistance to the above-mentioned organisms is insufficient and the effect is not sustainable. On the other hand, when it exceeds 30% by weight, the characteristics of the molded product are deteriorated and the cost is greatly affected, resulting in poor economy.

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 in 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 content of each drug and each content are appropriately determined within the above range depending on the usage environment of the product obtained from the molded product.

The drug is contained in a granular form, but the smaller the particle size, the better the dispersibility in the manufacturing process. Therefore, the drug is preferably 50 μm or less, more preferably 10 μm or less, and particularly preferably 2 μm or less.

The resin used in the present invention is not particularly limited as long as it has a molding ability and can be uniformly mixed with a drug, and the effect of the drug does not disappear during the manufacturing process. However, due to the high thermal decomposition temperature of the drug, general-purpose polyethylene-based resins such as polyethylene terephthalate, polyurethane resins, acrylic resins, nylon resins such as nylon 6 and nylon 66, and polypropylene resins are also used. Can be done.

In addition to the resin and the chemical agent, the molded article of the present invention may further contain a colorant, a light resistance improver, a heat stabilizer, a dyeability improver, a flame retardant, etc. depending on the use of the product obtained from the molded article. The modifier may be included. Examples of the colorant include powdered carbon black, pigments such as titanium oxide and disperse dyes, and examples of the light resistance improver include benzotriazole-based, hindered amine-based, benzophenone-based and the like, and heat stabilizers. Examples of the nylon resin include a copper compound, and examples of the dyeability improving agent include a urethane resin such as a polyurethane resin having a tertiary nitrogen atom in a side chain. The content and blending method of these are appropriately selected within a range that does not affect the effects of the drug and the characteristics of the molded product.

The form of the molded article of the present invention is not particularly limited,
For example, fibers, thin films such as films or thick films,
Examples thereof include a plate-shaped product, a rod-shaped product, a tubular product, a foamed product, a product processed by using at least a part thereof, a composite product, a laminated product, and a filling product. Examples of the fibers include multifilament yarns, monofilament yarns, various processed yarns obtained by processing these, twisted yarns, staples, spun yarns, hard cotton, cut fibers and the like. Further, curable adhesives, paints, surface finishing agents and the like which do not have a molding step are also included in the molded product of the present invention.

In addition, in the molded article of the present invention, if the shape is large or thick, it is preferable to manufacture it so that the drug is contained only in the surface or in a portion where organisms are easily generated. Further, the content rate of the drug may be changed for each part of the molded article, and in the production of such a molded article, a method of unevenly distributing these by using resins having different drug content rates during molding, A method of compounding separately molded products using resins having different rates is adopted.

In the production of the molded article of the present invention, a predetermined amount of a drug, a colorant or a modifier as required, is added and mixed in a resin, a melt thereof, or a solution thereof, and the mixture is injected. Molding is performed by using molding methods such as molding, extrusion molding and compression molding. When molding into fibers, the molding method is
For example, a melt spinning method, a dry spinning method, a wet spinning method, or the like is adopted.

For example, in the case of molding into fibers, when the resin and the drug are mixed, the drug is preliminarily contained in the mother resin in a high concentration (3 to 50% by weight) in order to improve the dispersibility of the drug. It is also possible to employ a method in which a masterbatch resin is prepared by the following method, and at the time of melt extrusion and spinning, mixing with a raw material resin containing no drug. The mother resin used for the masterbatch resin may be the same as the raw material resin containing no drug, or may be the same kind of resin having a different degree of polymerization,
It may be a different type of resin that facilitates the production of a masterbatch resin. When molding into a yarn having a large breaking force for industrial materials, the mother resin used in the masterbatch resin is preferably the same as the raw material resin.

The above-mentioned masterbatch resin and the raw material resin are mixed by, for example, preliminarily mixing the masterbatch resin and the raw material resin in a chip state so that the amount of the drug contained in the molded product is within a predetermined range, A method of extruding and spinning while melting and mixing, a method of mixing a predetermined amount of master batch resin chips immediately before extruding while melting the raw material resin chips, and spinning are adopted.

When a modifier such as a colorant is used in combination, for example, a method of adding it during preparation of the masterbatch resin, and when there are a plurality of modifiers, a masterbatch resin is prepared for each modifier. A method of mixing these with a masterbatch resin containing a drug or the like can be adopted. The former method is economical and economical. The latter method is
The ratio of the mother resin used in the masterbatch resin to the raw material resin becomes large, and it is difficult to obtain fibers with good performance especially when there is a difference in characteristics between the masterbatch resin and the raw material resin There may be a problem such as a poor yield in the inside.

As the drawing method after melt spinning, the undrawn yarn obtained by melt spinning is once wound, and then a finished yarn is obtained through a drawing step, or the hot drawing is performed directly without winding the undrawn yarn. The method is adopted. Further, a multi-step drawing method, a steam jet drawing method, which is mainly used for manufacturing yarns for industrial materials, and a composite spinning method of compounding and melting two-component resins are also adopted. In the case of a sheath core type composite yarn, it is preferable in terms of efficacy to contain a drug in the outer peripheral portion of the fiber.

The molded product thus obtained is used for applications utilizing bioresistance, for example, textile products, daily necessities, sports / leisure products, construction and civil engineering materials, agricultural and forestry materials, industrial materials, public facilities and transportation. It is processed into various products such as related materials and used for various purposes. The application of the product utilizing the characteristics of biological resistance as used herein is an application in a place where organisms are generated while the product is in use or during transportation and storage, which attaches to and parasitizes and propagates on the product. Textile products include, for example, woven and knitted fabrics, non-woven fabrics, spunbonds, felts, synthetic paper intermediate products, and further processed clothes (outer clothes, work clothes, underwear, socks, hats, etc.) and clothing. Knitting, industrial sewn products, strings, tapes, ropes, ribbons, etc. Examples of daily necessities include bathroom items, kitchen items, laundry clothes, cleaning items, rugs, interior items, curtains, towels, bedding, beds, rain gear, garbage baskets, vases, garden tools, flowerpots, cleaning tools, brushes, Cushion, nobori,
There are flags and handles. As a sports leisure item,
For example, sports equipment, sports clothing, protectors, gloves, shoe materials, bags, grip taping materials, pool products,
Park supplies, beach equipment, light shields, tents, ropes, boat yacht supplies, etc. Examples of building civil engineering materials include tents, curing sheets, curing meshes, pollution-preventing membrane materials, canvas, roofing materials, artificial grass, building interior materials, interior material reinforcing fibers, paint reinforcing fibers, and wall soil reinforcing fibers. Materials for agriculture, forestry and fisheries include, for example, fishing nets, aquaculture equipment, mooring ropes, fenders, sea anchors, floating bodies, water tanks, tubs, agricultural hoses, agricultural films, greenhouse equipment, cold gauze, hydroponics materials, insect repellent nets. Etc. Examples of industrial materials include water pipes, hoses, conveyor belts, land nets, land ropes, filters, felts, various containers, packaging materials, drainage intake gutters, water treatment materials, food processing materials, home appliances, and personal computer products. There are buttons, operating tools, water evaporation materials, etc.
Examples of public institutions and transportation-related materials include automobile interior materials, door handles, hanging leather, vending machine operation buttons, escalator handles, guide ropes, road signs, advertising sign materials, and interior material for hospitals and nursing homes. , Interior materials, etc. The processed product is also used for the purpose of imparting bioresistance to nearby objects. For example, there are application examples in which products are arranged to prevent the invasion of bacteria and fungi, and application examples in which mesh products are arranged to reduce the invasion of flying bacteria.

The bio-resistant molded article of the present invention and the product using the same have resistance to fungi, bacteria, algae, adhering organisms in the sea and mites. Examples of molds include Nigrospora oryzae, Cladosporium regine, Cladosporium Herbalem, Cladosporium Cladosporioidas, Cladosporium safaero sperma, Trichoderma koningi, Trichoderma.
T-1, Trico del Maviridi, Forma Glomerata, Former Terescias, Pluraria Pullulance, Gliocladium Vilens, Geotricum Lactus, Geotricum Candidum, Pestalothia Adasta, Pestalothia Negrekta, Milotesium Felucaria, Alternaria tenor, Altera Teruna Buratella 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 oxysporum, Rhizopus niglycans, Rhizopus stronifel, Penicillium citrinum, Penicillium ikupansa, Penicillium funiculozam, Penicillium liracinum, Penicillium nitricans, Penicillium frequentus cilantus, Penicillium nitricans, Penicillium frequentus, Penicillium nitricans, Penicillium frequentus, Penicillium nitricans Trichophyton mentagrophytes, Monilia fructigana, Ketomium globosaum, Epicoccum perplacense, Acremonium charticola, Waremia sevier, Candida albicans, Streptofetesillium reticalem, Saccharomyces cerevisiae, Botrytis cinerea, etc.
Examples of algae include Prolococcus species,
Anabaena Species, Cladophora Gromorata, Anacystini Nidarans, Anquistro Demas Angustus, Chlamydi Monas Reinhardy, Nost Caress Species, Urotricase
Species, Trento Polia Odalata, Trento Poliaole, Anathisti Montana, Anasithisi Samari, Chlorococcanma Species, Cytnima Hofmane, Carothrix Parletina, Schizosurix calcicicola, Chlorella esculani, Chlorella vulgaris, Tribonniemas, Tribonny
Examples include Schizothurix Rubera, Ossellatoria Rootie, Home Medium Species, Sirindro Capsa Species, and Navicara Species. Examples of the bacteria include Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Bacillus subtilis, Bacillus subtilis, Swine fever,
Examples thereof include S. typhi, Mycobacterium tuberculosis, S. typhimurium, Klebsiella pneumoniae and the like. Examples of adhering organisms in the sea include, for example, Fujitsubo,
Examples include mussels such as crows and oysters, and seaweeds such as agaric agar. Examples of mites include Dermatophagoides farinae and Dermatophagoides farinae.

[0027]

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 obtained molded product was subjected to a fungicidal test, an algae control test, an antibacterial test and a tick repellent test, and the test method was as follows.

1) Breaking strength of yarn It was measured according to JIS L1013 7.5.1. 2) Elongation at break of yarn It was measured according to JIS L1013 7.5.1.

3) 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 made 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 were the molds shown below. Nigrospora Orize, Cladosporium Regine, Cladosporium Herbalem, Cladosporium Cladosporioidas, Cladosporium Safaero sperma, Trichoderma koningi, Trichoderma T-
1, Tricoderma Viridi, Forma Glomerata, Former Terescias, Pluraria Pullulance, Gliocladium Vilens, Geotricum Lactus, Geotricum Candidum, Pestalothia Adasta, Pestalothia Negrekta, Milotesium Fercaria, Alternaria Tenas, Alter La Teruna, La Teruna Altera Burat Niger, Aspergillus flavus, Aspergillus felsicor, Aspergillus oryzae, Aspergillus terreus, Aspergillus fumigatus, Aureobasidium pullulans, Fusarium moniliforme, Fusarium semitectum, Fusarium plaliferatum, Fusarium rozaium, Fusarium solaurium , Rhizopus niglycans, Rhizopus stronifel, Penicillium citrinum, Penicillium ikupansa, Penicillium funiculosum, Penicillium liracinum, Penicillium niglycans, Penicillium frequentus, Penicillium citreoability, mucor latrichomium trichomes, eurocinus, eurocinus, euroticus Ketomium globotham,
Epicoccum purpurascens, Acremonium charticola, Waremia sevi, Candita albicans, Streptofetecilium reticarem, Saccharomyces cerevisiae, Bacillus subtilis, Bacillus megaterium, Staphylococcus aures, Pseudomonas, Pseudomonas, Pseudomonas
Coli, Botrytis cinerea, Proteus vulgaris. These molds were stock culture pure cultures or subcultures within 30 days stored at 6 ° C ± 4 ° C, respectively.

4) Algae control test The following 25 kinds of 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
(0 W positive fluorescent lamp). The evaluation was performed 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 were the following algae. Prolococcus species, Anavena species, Cladophora gromorata, Anasity
Nidarans, Anquistrodemas Angustus, Chlamydi Monas Reinharty, Nostcareth Species, Urotricase Species, Trent Paulia Odalata, Trent Paulia Ole, Anasisty Montana, Anasisty Samari,
Chlorococcanma species, Cytonima hoffmanné, Carothrix parletina, Schizosurix calcicola, Chlorella ezomani, Chlorella burglares, Tribonniemas species, Schizosthurix fleecy, Schizothurispeise, Homediathus spice, Homedis spice
Navi Cara Species.

5) Antibacterial test The difference in bacterial increase / decrease value by the bacterial count measurement method of the Textile Product Sanitary 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,
If it is 1.6 or more, it has an antibacterial effect and a deodorant effect.
If it is less than 6, the antibacterial effect and the deodorant effect are not provided.

6) Mite repellency test The mites were tested according to the Osaka Prefectural Institute of Public Health using Dermatophagoides farinae.

7) Underwater test A sample of 30 cm on each side was immersed in the sea, and the resistance to marine adherent organisms was compared with the area where the drug-free sample surface was covered with the marine adherent organisms in the following five stages. evaluated. 4 ... about the same. 3 ... 25% less. 2 ... 50% less. 1 ... 75% less. 0: No adhesion at all.

Example 1 A predetermined amount of a drug having a particle size distribution of 0.8 to 1.2 μm shown in Table 1 was mixed with a polyethylene terephthalate resin to prepare a masterbatch resin having a drug content of 5% by weight in advance. Prior to melt spinning of the masterbatch resin, a predetermined amount of a polyethylene terephthalate resin containing no drug was mixed and melt-spun, and a multifilament yarn having a fineness of 100 denier composed of 24 yarns having a drug content of 0.05% by weight. Got Melt spinning conditions are: discharge rate 46 g / min, melting temperature 28
It was 5 ° C. and the winding speed was 1300 m / min. The intrinsic viscosity measured using a mixed solution of the used polyethylene terephthalate resin of phenol / tetrachloroethane (60/40) was 0.61 g / dl. This multifilament yarn is drawn by a drawing machine at a draw ratio of 95 to 100 denier and a breaking elongation of 30 to 35%, and drawn at a drawing temperature of 85 ° C and a winding speed of 600 m / min. I got a thread. The characteristics of the obtained yarn are shown in Table 2.

Example 2 In the same manner as in Example 1, the drug content was 5% by weight and the coloring agent (A2R-ATN manufactured by Hoechst Japan Co., Ltd.) was used in advance.
A masterbatch resin having a content rate of 30% was prepared. Using this masterbatch resin, a multifilament yarn with a fineness of 100 denier composed of 24 yarns having a drug content of 0.15% by weight and a coloring agent content of 0.9% by weight was obtained in the same manner as in Example 1. It was A drawn yarn was obtained from this multifilament yarn in the same manner as in Example 1.

Examples 3 to 6 and Comparative Examples 1 to 2 Table 1 was prepared in the same manner as in Example 1 using the agents shown in Table 1.
A multifilament yarn having a fineness of 100 denier composed of 24 with the drug content shown in (4) was obtained. A drawn yarn was obtained from this multifilament yarn in the same manner as in Example 1.

[0039]

[Table 1]

[0040]

[Table 2]

The mold resistance test was conducted on the drawn yarns obtained in Examples 3, 5, 6 and Comparative Example 2. Table 3 shows the results. Further, the drawn yarns obtained in Examples 1 to 4 and Comparative Example 1 were used in a tubular knitting machine to produce 10 wales / cm,
A knitted fabric of 12 courses / cm was prepared and treated with water.
The water treatment was carried out by immersing the knitted fabric in a water storage container having a bath ratio of 500 for 24 hours, successively flowing 10 g / sec of tap water into this container for overflowing, and then air-drying for 3 hours. The water-treated knitted fabric was subjected to a fungicide test, an algae test, an antibacterial test, and a tick repellent test. The results are shown in Tables 4-7.

[0042]

[Table 3]

[0043]

[Table 4]

[0044]

[Table 5]

[0045]

[Table 6]

[0046]

[Table 7]

Examples 7 to 12 and Comparative Examples 3 to 4 The agents shown in Table 1 and nylon 6 having a relative viscosity RV = 2.5.
Using a resin, the mixture is mixed so that the drug content in the mixture becomes the value shown in Table 1, melt-mixed at 255 ° C., extruded, water-cooled and cut to a chip having a diameter of 2 to 5 mm and a length of 4 to 7 mm. A resin having a shape of a circle was prepared. 240 ℃ with this chip,
By the heat press method under the pressure of 50 kg / cm ² ,
A film having a thickness of 0.3 to 0.5 mm was prepared. The relative viscosity of nylon 6 is 2 ml of nylon 6 in 20 ml of sulfuric acid.
A viscosity of 00 mg melted was measured.

With respect to the films obtained in Examples 7 to 9 and Comparative Examples 3 to 4, antifungal tests were conducted on the films before and after water treatment. Table 8 shows the results. Water treatment was performed by the following method. A sample having a diameter of 4 cm was immersed in a water storage container having a bath ratio of 500 for 24 hours, and then continuously stored in the container for 10 hours at 10 g /
Seconds water flowed down and overflowed. After that, water drops on the surface of the sample were lightly wiped with a waste cloth and air-dried for 3 hours.

Further, the films obtained in Examples 9 to 12 and Comparative Example 3 were tested in the sea. Table 9 shows the results.

[0050]

[Table 8]

[0051]

[Table 9]

In Table 3, Comparative Example 2 in which only 2- (4-thiazolyl) -1H-benzimidazole (TBZ) was used as the drug had an antifungal effect even when the drug content was 0.25% by weight. Although not observed, the antifungal effect was observed in Example 5 using 4 kinds of agents, and Example 6 using 5 kinds of agents and Example 3 using 8 kinds of agents
In addition, a better antifungal effect was recognized.

In Tables 4, 5, and 7, the content of at least 4 or more chemical agents is set to 0.05% by weight or more, and as shown in Examples 1 to 4, good and long-lasting fungicides are exhibited. It can be seen that the effects, the algae-preventing effect, and the mites-repelling effect are recognized, and that the effects are further improved and the spectrum is broadened when the drug content is 0.15% by weight or more. Further, as shown in Table 2, from Example 2 in which a drug and a colorant were used in combination, the characteristics of the yarn were maintained even when the colorant was contained, and even when the yarn was melted at a high temperature of 285 ° C. It can be seen that the bio-resistance of is good. Further, even in the process of processing the drawn yarn from the multifilament yarns obtained in Examples 1 to 4, there was no yarn breakage and the workability was good. Further, in Table 6, it can be seen that Example 3 shows a good antibacterial effect.

In Table 8, Examples 7 to 9 even after water treatment
The fungicidal effect of No. 1 is almost unchanged, but Comparative Example 4 using only TBZ as the drug is inferior in the antifungal effect before water treatment even if the drug content is as high as 5.0% by weight, and The effect after water treatment was even worse and unsustainable. Further, in Table 9, resistance to the adhering organisms in the sea of Examples 9 to 12 was recognized.

Example 13 Polytetramethylene glycol 3 having a molecular weight of 1500 and 10 parts by weight of methylenebis (4-phenylisocyanate) 3
0 part by weight was reacted at 80 ° C. for 60 minutes to obtain a prepolymer. This was dissolved in 90 parts by weight of dimethylformamide and allowed to react with 1.4 parts by weight of 1,2-propylenediamine dissolved in 30 parts by weight of dimethylformamide while maintaining the temperature at 0 ° C. to obtain a polymer solution. A total of 0.021 parts by weight (0.05% by weight based on all components constituting the molded product) of the chemicals shown in Table 10 was added to and mixed with the obtained polymer solution at a predetermined ratio. This mixture (viscosity 120 at 20 ° C.
0 poise) was spun into a stream of air heated to 250 ° C. through a spinneret having 30 holes. After the formed yarn was converged by mechanical false twisting when the solvent content became 1%, an oil agent was applied and wound at 200 m / min to obtain a yarn.
The drug used here had a particle size distribution of 0.8 to 1 μm.

Example 14 To the polymer solution of Example 13, 0.063 parts by weight of the agents shown in Table 10 were added in a predetermined ratio (0.15% by weight based on all components constituting the molded product). Further, 0.21 part by weight of a coloring agent (A2R-ATN manufactured by Hoechst Japan Ltd.) (0.5% by weight based on all components constituting the molded body).
A yarn was obtained in the same manner as in Example 13 except that was added.

Examples 15 to 18 and Comparative Examples 5 to 7 In the polymer solution of Example 13, each drug shown in Table 10 was used in a predetermined ratio, and the total drug content was based on all the components constituting the molded product. The yarn was obtained in the same manner as in Example 13 except that the proportions shown in Table 10 were added.

[0058]

[Table 10]

In Examples 13 to 18 and Comparative Examples 5 to 7, the processability during spinning was good. Example 15,
The mold resistance test was performed on the yarns obtained in Examples 17 and 18 and Comparative Example 6. Table 11 shows the results.

The yarns obtained in Examples 13 to 18 and Comparative Examples 5 to 7 were used in a tubular knitting machine to produce 10 wales / cm, 1
A knitted fabric of 2 courses / cm was prepared and treated with water. The water treatment was carried out by immersing the knitted fabric in a water storage container having a bath ratio of 500 for 24 hours, successively flowing 10 g / sec of tap water into this container for overflowing, and then air-drying for 3 hours. The water-treated knitted fabric was subjected to a fungicide test, an algae test, an antibacterial test, and a tick repellent test. The results are shown in Tables 12 to 15.

[0061]

[Table 11]

[0062]

[Table 12]

[0063]

[Table 13]

[0064]

[Table 14]

[0065]

[Table 15]

In the antifungal test of Table 11, the yarns of Example 17 containing 4 kinds of chemicals have antifungal effect, and the yarns of Examples 15 and 18 having more kinds of chemicals have better antifungal properties. It was found to have an effect and a broad spectrum. On the other hand, the yarn of Comparative Example 6 containing only TBZ had no antifungal effect.

In the fungicidal test of Table 12, Example 13
It was found that the knitted fabrics of ˜16 had a fungicidal effect and had a broad spectrum. Further, it was found that the antifungal effect was obtained when the drug content was 0.05% by weight or more. On the other hand, no antifungal effect was observed for the knitted fabrics of Comparative Example 7 containing only TBZ and Comparative Example 5 containing no drug.

In the algal control test of Table 13, Examples 13 to
It was found that the 16 knitted fabrics had an algae control effect and had a wide spectrum. It was also found that the drug content of 0.05% by weight or more has an antialgal effect. On the other hand, the knitted fabric of Comparative Example 5 containing no drug was not observed to have an antialgal effect.

In the antibacterial test shown in Table 14, the knitted fabric of Example 15 was evaluated as having antibacterial properties by SEK standard. Table 1
In the mite repellency test of 5, the knitted fabrics of Examples 13 and 16 both showed mite repellency.

[0070]

As is clear from the above description, according to the present invention, there is no problem in processability and resistance to fungi, bacteria, algae, adhering organisms in the sea and mites. It is possible to provide a molded product having a wide spectrum and sufficient resistance, and a product using the molded product.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 43/40 101 A01N 43/40 101L 101E 43/78 43/78 F Z 47/18 101 47 / 18 101C (72) Inventor Hideo Kawasaki 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd. Main office (72) Hideo Takeuchi 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd. (72) Inventor Hideo Sekiya 2-8-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd. Main office (72) Inventor Kiyohide Hayashi 2-1-1 Katata, Otsu, Shiga Toyobo Co., Ltd. 72) Inventor Junichiro Nakae 2-7-1 Chuo 2-chome, Ota-ku, Tokyo

Claims (5)

[Claims] 1. A bioresistant molded article containing a resin and a drug having bioresistance, wherein the drug having bioresistance is a nitrile compound, a pyridine compound, a haloalkylthio compound, or an organic iodine. Of at least four compounds selected from the group consisting of a series compound, a thiazole compound and a benzimidazole compound, and the content of the drug is 0.05 to 30% by weight based on all components constituting the molded product. A bio-resistant molded product characterized by being within the range. 2. The drug is a haloisophthalonitrile derivative, a pyridinethiol-1-oxide derivative, a sulfonylhalopyridine derivative, a haloalkylthiosulfamide derivative, an iodosulfonylbenzene derivative, an isothiazolin-3-one derivative, a thiazolebenzimidazole derivative. The bio-resistant molded article according to claim 1, which is at least four kinds of compounds selected from the group consisting of and a benzimidazolecarbamic acid derivative. 3. The bioresistant molded article according to claim 1, wherein the molded article is a fiber. 4. A bio-resistant product, comprising the bio-resistant molded product according to any one of claims 1 to 3. 5. A method for producing a bioresistant molded article, which comprises molding a resin and a drug having bioresistance and then molding the compound, wherein the drug having bioresistance is a nitrile compound, a pyridine compound, or a halo compound. It is at least four kinds of compounds selected from the group consisting of alkylthio compounds, organic iodo compounds, thiazole compounds and benzimidazole compounds, and the addition amount of the drug is 0 with respect to all components constituting the molded product. A method for producing a bioresistant molded article, characterized in that the amount is in the range of 0.05 to 30% by weight.