JPH09157112A - Resin fiber composite sheet having resistance to organism - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin fiber composite sheet by combining the surface of fibers with a resin containing a specific compound, in prescribed amount, having high decomposition temperature, low water solubility, resistance to organisms and high safety. SOLUTION: This sheet is produced by combining the surface of a fiber sheet with a resin containing at least 4 kinds of chemicals having resistance to organisms selected from nitrile compounds, pyridine compounds, haloalkylthio compounds, organic iodine compounds, thiazole compounds and benzimidazole compounds in an amount of 0.05-30.0wt.% based on the resin weight. The preferred examples of chemicals having resistance to organisms are especially selected from haloisophthalonitrile derivatives, sulfonylhalopyridine derivatives, pyridinethiol-1-oxide derivatives, haloalkylthiosulfamide derivatives, iodosulfonylbenzene derivatives, isothiazolin-3-one derivatives, benzimidazolecarbamic acid derivatives and thiazolebenzimidazole derivatives.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composite fiber sheet which is resistant to the attachment and reproduction of organisms such as mold, algae, marine adherent organisms and bacteria, and is repellent against mites. It is a thing.

[0002]

2. Description of the Related Art Conventionally, various methods have been used for imparting bioresistance to a fiber sheet. For example, a resin containing a thiazobenzimidazole (hereinafter referred to as TBZ) is coated on a fiber cloth so that a part of the tarpaulin has a function. But TB
Under the present circumstances, 50% or more of the bacteria existing in our living environment do not have a resistance function due to the generation of mold and resistant mold which cannot be originally resisted by using Z alone. Therefore, a product having a broader antibacterial spectrum, which is more resistant to mold and the like, has been desired. Needless to say, these products mentioned above have little resistance to algae, marine adherent organisms and mites.

Further, in recent years, quaternary ammonium salts have been used to impart antibacterial properties to textile products. The antibacterial action of such products is due to the cationic (cationic) bactericidal activity of the salt. However, this salt is not sufficiently effective against mold fungi, and its resistance to bacteria is exclusively used. Of course, these products have little resistance to mold, algae, marine adherent organisms and mites.

Further, there is a fine copper powder as an agent for imparting anti-algal properties, but it is necessary to knead a large amount into the resin in order to bring out the effect, and the characteristics of the resin are deteriorated, which is not satisfactory. As described above, there has never been a resin composite fiber sheet that is widely resistant to mold, algae, marine adherent organisms, fungi and mites. The use of such products has awaited the development of such products.

[0005]

DISCLOSURE OF THE INVENTION The present invention was devised in order to solve the problems of "narrow antibacterial spectrum" and "there are few types of resistant organisms" of the prior art. Widely used for molds, algae,
It is an object of the present invention to provide a resin composite fiber sheet having satisfactory resistance and repellent property against marine adherent organisms, bacteria and mites.

[0006]

Means for Solving the Problems The present invention provides the following (A) to (I).
A resin composite fiber sheet comprising a resin containing 0.05 to 30.0% by weight of the resin of at least four kinds of bio-resistant agents consisting of the group (f), which is compounded on the surface of the fiber sheet. (B) nitrile compound (b) pyridine compound (c) haloalkylthio compound (d) organic iodo compound (v) thiazole compound (e) benzimidazole compound

In a preferred embodiment of the present invention, the bioresistant drug is selected from the following groups (A) to (H): (A) haloisophthalonitrile derivative (B) sulfonylhalopyridine derivative (C) pyridinethiol-1 -Oxide derivative (D) Haloalkylthiosulfamide derivative (E) Iodosulfonylbenzene derivative (F) Isothiazolin-3-one derivative (G) Benzimidazolecarbamic acid derivative (H) Thiazolebenzimidazole derivative

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION All the above-mentioned agents (a) to (f) have a high decomposition temperature, a low water solubility, a biological resistance, and a high safety. Here, "biological resistance" refers to a property that shows resistance to the attachment and reproduction of organisms and has a repellent effect on mites. In the present invention, it is possible to broaden the spectrum of antibacterial properties by using a resin containing four or more of the above-mentioned bioresistant agents.
Furthermore, the generation of resistant bacteria can be reduced. From the viewpoint of such effects, it is generally preferable that the number of types of bio-resistant drugs to be mixed is as large as possible, and 4 or more types, more preferably 7
Mix more than one kind. Selection of bio-resistant drugs (a) ~
Two or more kinds may be selected from the above-mentioned similar compounds.

Examples of the nitrile compound include a haloisophthalonitrile derivative, and examples of the pyridine compound include a pyridinethiol-1-oxide derivative and a sulfonylhalopyridine derivative.
Examples of the haloalkylthio-based compound include a haloalkylthiosulfamide derivative, a tetrachloroethylthiotetrahydrophthalimide derivative, and the like. Examples of the organic iodine compounds include iodosulfonylbenzene derivatives, propargylbutylcarbamic acid derivatives and the like. 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 agents 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, particularly preferably 2,4,5,6-
Tetrachloroisophthalonitrile, 2-pyridinethiol-1-oxide sodium, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, N, N-dimethyl-N'-phenyl-N '-(florodichloro From methylthio) sulfamide, diiodomethyl-p-tolylsulfone, 2- (n-octyl) -4-isothiazolin-3-one, 2- (4-thiazolyl) -1H-benzimidazole, 1H-2-benzimidazole carbamate. At least four compounds selected from the group consisting of: 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 agents, the compound having resistance to mold is 2,4,5,6-tetrachloroisophthalonitrile, and the compound having resistance to bacteria is
A compound that is 2,3,5,6-tetrachloro-4-methylsulfonylpyridine and has resistance to algae is N, N-dimethyl-N′-phenyl- (florodichloromethylthio) sulfamide.

The composition ratio of each bioresistant drug used in the present invention is arbitrary, but the weight ratio of each drug used is at least 1.0% by weight, preferably 3.0% by weight or more. Further, in the present invention, the content ratio of the bio-resistant drug to the resin compounded on the surface of the fiber sheet is 0.05 to 30.0% by weight based on the weight of the resin. Even if the content is lower than this, it may have biological resistance, but it should be effective in the environmental conditions (appropriation for the growth of microorganisms) of the intended use of the product, and it should also maintain its function. Therefore, a content of at least 0.05% by weight is required. The content is preferably 0.15% by weight or more, particularly when considering the case where the environmental condition of the use of the product is very favorable for the growth of organisms or the case where the product is placed in running water. The upper limit of the content may be determined depending on the environmental conditions of the use of the product. Naturally, as the content rate of the drug increases, the bioresistance and the durability of the effect increase, but on the other hand, the characteristics of the product decrease and the cost of the bioresistance drug increases, resulting in poor economic efficiency. For normal use, a content of at most 3.0% by weight is sufficient.

The bioresistant drug used in the present invention preferably has a particle size as small as possible in order to facilitate mixing with the resin. The drug preferably has a particle size of 50 μm or less, and more preferably a 1 μm class drug. Examples of the resin compounded in the fiber sheet of the present invention include urethane-based resins, vinyl chloride-based resins, acrylic-based resins, vinyl acetate-based resins, silicon-based resins, fluorine-based resins, and resins obtained by mixing these resins. To be done.

The fiber sheet used in the present invention includes sheet fibers such as woven fabric, knitted fabric and non-woven fabric, natural fibers such as cotton and hemp, recycled fibers such as rayon, polyester type, polyamide type, polyacrylonitrile type and polyethylene type. Examples thereof include synthetic fibers such as polypropylene-based fibers and fibers obtained by mixing these.

The resin and the fiber sheet are compounded by, for example, a coating method such as a knife coater, a roll coater, a dip coater, or a method of forming a resin film sheet and bonding it with an adhesive. The resin compounded on the surface of the fiber sheet may have a multi-layered structure formed of several kinds of resin layers. In that case, if the bioresistive agent of the present invention is contained in the outermost layer, the effect of bioresistance is obtained with a small addition amount. It is preferable because it becomes large. As a method of adding the bio-resistant agent to the resin, it is possible to add it by sufficiently uniformly dispersing it by a general method such as kneading and stirring, as with the colorant and other modifiers.

Applications of the resin composite fiber sheet of the present invention include tents, gymnastics mats, bags, curing sheets, light-shielding nets, insect nets, truck hoods, wall cloths, waterproof cloths,
Examples include curtains, shower curtains, table cloths, and the like. In the present invention, other additives such as a colorant, a light stabilizer, a filler, a deodorant and the like can also be applied when adding the bioresistance agent.

The invention is illustrated by the following examples.
The present invention is not limited to these.

[0017]

【Example】

Examples 1 to 10 and Comparative Examples 1 to 3 Vinyl chloride resins having the composition shown in Table 1 were prepared. The compounding symbol a is an example in which an isocyanate adhesive is compounded as a base coat for a fabric using polyester multifilament yarn. The combination symbol (b) is an example of a resin for topcoat containing a light resistance improver and a filler. In addition, bio-resistant drugs of drug numbers 1 to 4 having different composition ratios of drug components shown in Table 2 using a particle size distribution of 0.8 to 1.2 μm were prepared. The procedure for mixing the bioresistant agent with the vinyl chloride resin is as follows. O. P. And then mixed with vinyl chloride resin.

[0018]

[Table 1]

[0019]

[Table 2]

As a base cloth for coating vinyl chloride, a woven fabric having a polyester multifilament yarn of 250 denier and warp and weft densities of 53 and 50 (pieces / inch) respectively was prepared. A vinyl chloride resin was prepared by changing the combination of the combination of the vinyl chloride resin, the combination of the bio-resisting drug and the content ratio thereof, and applied to both sides of the prepared base cloth by the hand coating method. The coating amount was set to 250 to 350 g / m ² . After coating, preheating was performed at 150 ° C. for 2 minutes, and then heating was performed at 195 ° C. for 5 minutes to prepare a sample.

Table 3, Table 4, Table 5, and Table 6 show the evaluation results of the respective tests for antifungal, antialgal, antibacterial, and mites repellent. Table 7 shows the undersea test evaluation.

[0022]

[Table 3]

[0023]

[Table 4]

[0024]

[Table 5]

[0025]

[Table 6]

[0026]

[Table 7]

Among the above-mentioned tests, a sample treated with water only for the mildew-proof test was also subjected to the test. For water treatment, 24 samples with a diameter of 4 cm
Immerse in a water storage container having a time bath ratio of 500, and then run 10 g / sec tap water into the container for 24 hours to cause overflow, and then wipe off water droplets on the sample surface with a waste cloth.
The method of air-drying for an hour was adopted. As will be described in detail later, the antifungal test is MIL STD 810D Method5.
Adopting the 08.3 modified method, a culture test was conducted with a mixed fungus of 62 molds. The algae proof test was an in-house test method, and a culture test was conducted using a mixed alga of 25 kinds of algae. For the antibacterial test, the method of the Textile Products Sanitary Processing Council (abbreviation SEK) using Staphylococcus aureus was used.

Tables 8 and 9 show the judgments of the evaluations of the antifungal, antialgal and antibacterial tests.

[0029]

[Table 8]

[0030]

[Table 9]

The superiority of the present invention will be described in more detail by using each test result. First, the formulation of the drug will be described using Example 2, Comparative Example 2, Comparative Example 3, Example 5, and Example 6 in Table 3. Comparative Example 2 using a simple antifungal agent TBZ alone is also effective in Comparative Example 3 in which the content is increased to 5.0% in the test of a mixed bacterium of 62 bacteria as in the present antifungal test. unacceptable. The antifungal property is improved when the types of the medicines to be mixed are sequentially increased, but the effect is recognized in Example 5 in which 4 kinds are mixed. Example 6 containing 5 kinds
It can be seen that a better effect can be obtained in Example 3 in which 8 or 8 kinds are mixed.

Regarding the drug content, as shown in Tables 3, 4, and 6, in Examples 1 to 6, the drug content of 0.05% by weight or more was confirmed to be antifungal, algae-proof and mites-repellent. ,
It can be seen that a better effect is obtained when it exceeds 0.25% by weight. Further, the effect is against various kinds of 62 types of mold and 25 types of algae, and it is understood that the range of effective antibacterial spectrum is wide. As shown in Example 3, even in the case where the drug was used in combination with an adhesion improver, a product having excellent bioresistance could be obtained. Further, as is clear from the antifungal evaluation before and after water treatment in Table 3, Examples 1 to 6 show that the sustainability of the effect is good. Further, as is clear from the antibacterial tests of Example 1 and Example 2 shown in Table 5, it is understood that the antibacterial property is exhibited by the SEK standard. As is clear from the results of the tick repellent tests of Example 1 and Example 4 in which Comparative Example 1 shown in Table 6 was used as a standard sample, it can be seen that both have repellent properties. As shown in Table 7, it can be seen that it is also resistant to marine adherent organisms. As is clear from the above, it can be seen that the biological resistance of the present invention is effective not only for mold fungi but also for a wide range of algae, marine adherent organisms, bacteria and mites.

Examples 11 to 15 and Comparative Examples 11 to 13 As the acrylic resin coated base fabric, woven fabrics having warp and weft density of 43 and 32 (pieces / inch) using polyester spun yarn 10th count twin yarn were prepared. Particle size distribution of 0.
The bioresistant drugs of drug numbers 1 to 4 having different composition ratios of the drug components shown in Table 2 using 8 to 1.2 μm were added at the drug content rates of Table 10. The base fabric was coated with 120 g / m ² of each of the resins of Examples 11 to 15 and Comparative Examples 11 to 13 to prepare a resin composite fiber sheet.

[0034]

[Table 10]

Table 11, Table 12, Table 13, and Table 14 show the evaluation results of the respective tests for antifungal, antialgal, antibacterial, and mites repellent.

[0036]

[Table 11]

[0037]

[Table 12]

[0038]

[Table 13]

[0039]

[Table 14]

Among the above-mentioned tests, a sample treated with water only for the mildew-proof test was also subjected to the test. For the water treatment, the same method as described above was adopted. The same methods as described above were used for the mildew-proof test, algae-proof test, and antibacterial test. The evaluation of each of the antifungal, antialgal, and antibacterial tests was also determined by the same method.

The superiority of the present invention will be described in more detail by using each test result. First, the formulation of the drug will be described with reference to Example 12, Comparative Example 12, Comparative Example 13, Example 14, and Example 15 in Table 11. Comparative Example 12 using a simple antifungal agent TBZ alone is effective even in Comparative Example 13 in which the content is increased up to 5.0%, in the test of a mixed bacterium of 62 kinds of fungi as in the present antifungal test. It is not allowed. On the other hand, when the types of the medicines to be mixed are sequentially increased, the antifungal property is improved, but the effect is recognized in Example 14 in which 4 kinds are mixed. It can be seen that better effects can be obtained in Example 15 in which 5 types are blended and Example 12 in which 8 types are blended.

Regarding the drug content, Tables 11 and 12 show
As shown in Table 14, in Examples 11 to 15, the antifungal, antialgal, and tick repellent effects were observed at a drug content of 0.05% by weight, and a better effect was obtained at a content of 0.20% by weight. You can see that The effect is also 62 types of mold, 25 algae.
It can be seen that there is a wide range of effective antibacterial spectra for various kinds of species. Furthermore, as is clear from the antifungal evaluation before and after water treatment in Table 11, Examples 11 to 15 show that the sustainability of the effect is good. Further, as is clear from the antibacterial tests of Example 11 and Example 12 shown in Table 13, it is found that they have antibacterial properties. Comparative Example 1 shown in Table 14
As is clear from the results of the tick repellent tests of Examples 11 and 12 in which No. 1 was used as the standard sample, it is clear that both have repellent properties. As is clear from the above, it can be seen that the one according to the present invention has bioresistance not only to mold fungi but also to a wide range of algae, bacteria and mites.

The details of the antifungal, antialgal, antibacterial, mites repellent test and undersea test are shown below.

Antifungal test (1) Test method MIL STD 810D Method 508-3 modified method (2) Inoculation Direct inoculation of a mixed spore suspension of test bacteria by a wet method. (3) Culture area No antibiotics such as chloramphenicol were added. Potato dextrose agar (PDA). (4) Incubator and culture conditions Temperature: 30 ° C ± 5 ° C Humidity: 95% ± 5% RH. Wind speed: 60 cm / sec. (5) Culture period 28 days. (6) Test Bacteria Use pure culture culture of stock culture and test subculture culture for 6 days at ± 4 ℃.・ Nigrospora oryzae ・ Kladsporium resine ・ Kladsporium Herbalem ・ Kladsporium Cladosporioidas ・ Kladsporium Safaero sperma ・ Trichoderma coninghi ・ Trichoderma T-1 ・ Trichoderma viridi forma glomerata ・ Formerestias ・ Pluraria purrrance ・ Guri Ocladium Vilens-Geotricum Lactus-Geotricham Candidum-Pestalothia Adasta-Pestalocia Negreta-Milotesium Felucaria-Alternaria Tenors-Alternaria Plasicola-Alternaria Alternatha-Aspergillus-Fergus-Aspergillus-Fergus-Asfergill-Asfergill-Fergus-Aspergillus・ Aspergillus fumigatus ・ Aureobasidium pullulans ・ Fusarium moniliforme ・ Fusarium semitectam ・ Fusarium plaliferatam ・ Fusarium roseum ・ Fusalium solani ・ Fusarium oxysporum ・ Rhizopus cypriscinicum Nitricans ・ Rhizopus stroniferum cispenis cypenicillium penicillium Liracinum-Penicillium niglycans-Penicillium frequentus-Penicillium citreability-Mukoll racemasus-Eurotium tonafilum-Trichofton mentaglophytes-Moniria fructigana-Ketomium globosum-Epicoccum perprasense-Acremonium charlotilla- Mia cevi, Candita albicans, Streptofeteschillium reticarem, Saccharomyces cerevisia, Bacillus subtilis, Bacillus megaterium, Staphylococcus aure, Pseudomonas aeruginosa, Pseudomonas fullrescens, Salmonella taifimariam, Escherichia cineris, botrytis, botrytis.

Algal control test (1) Seeding Direct inoculation of 25 algae mixed dispersion by wet method. (2) culture locations _{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 deionized water 1000ml pH 5.8 (3) Culture conditions Temperature 25 ° C to 30 ° C Humidity 90% RH. ~ 100% RH. (4) Culture status During the culture in the egg incubator, the upper pig of the petri dish is taken and irradiated with 1500 Lux (60 W positive fluorescent lamp) for 4 hours or more per day. (5) Test algae Prorococcus species Anabena species Cladophora gromorata Anacysti nidarans Anxtrodemas Angustus Chlamydimonas Reinharty Nostokales spices Urotrica sesame spices Trentoporia Odalata trento cypressa russia cypressa anthracis anthracis aurina sana spicy aurina spicy sponges Chlorella Emma Soni Chlorella Bvlgares Tribonima Spices Schizo Thrix Fleece Schizo Thrix Rubera Osselatria Rootie Homeium Species Syrindoro Capsa Species Navicarras Pieces

Antibacterial Test The difference between the bacterial increase and decrease values according to the bacterial count measurement method of the Textile Products Sanitary Processing Council (abbreviation SEK) using Staphylococcus aureus was adopted.
The difference in the bacterial increase / decrease value is indicated by the difference between the number of bacteria (logarithm) after culturing the standard white cloth (without antibacterial treatment) for 18 hours and the number of bacteria after culturing for 18 hours (logarithm). SEK says that it has an antibacterial effect at 1.6 or higher. In addition, SEK says that the deodorizing effect is 1.6 or more. Mite repellency test The Osaka Prefectural Institute of Public Health using the Dermatophagoides farinae method was used.

Subsea test A square sample having a side of 30 cm was immersed in the sea to evaluate the resistance to organisms adhering to the sea. Immersion period: August 9 to October 4, 1995, 56 days Immersion place: Off the coast of Iwakuni

[0048]

From the above results, it was confirmed that the resin composite fiber sheet of the present invention has excellent bioresistance against a wide range of organisms such as mold, algae, marine adherent organisms, bacteria and mites. .

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location A01N 43/40 101 A01N 43/40 101E 101L 43/52 43/52 43/80 102 43/80 102 47/18 101 47/18 101C B32B 27/12 B32B 27/12 27/18 27/18 F (72) Inventor Yuichi Komoku 2-2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd. (72) Inventor Ryoji Morimoto 2-1-1 Katata, Otsu-shi, Shiga Toyobo Co., Ltd. Research Institute (72) Inventor Hideo Kawasaki 2-8 Dojimahama, Kita-ku, Osaka Toyobo Co., Ltd. (72) Inventor Junichiro Nakae 2-7-1 Chuo 2-103, Ota-ku, Tokyo

Claims (2)

[Claims] 1. A resin containing 0.05 to 30.0 wt% of a bioresistive agent selected from the group consisting of the following (a) to (f) on the fiber sheet surface: Resin composite fiber sheet characterized by: (a) nitrile compound (b) pyridine compound (c) haloalkylthio compound (d) organic iodo compound (v) thiazole compound (e) benzimidazole compound 2. The resin composite fiber sheet according to claim 1, wherein the bioresistant agent is selected from the following groups (A) to (H): (A) haloisophthalonitrile derivative (B) sulfonylhalopyridine derivative (C) ) Pyridine thiol-1-oxide derivative (D) Haloalkylthiosulfamide derivative (E) Iodosulfonylbenzene derivative (F) Isothiazolin-3-one derivative (G) Benzimidazolecarbamic acid derivative (H) Thiazolebenzimidazole derivative