JP2002336705A - Fiber structure having capacity for preventing fouling of underwater organisms - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber structure suitably used in water not only to prevent the fouling of underwater organisms such as algae, barnacles, parasites but also to reduce the load to the peripheral environment, suppressing the yellowing and deterioration of a binder for bonding a photocatalyst and the fiber structure, suppressed in its yellowing and deteroration and capable of being utilized in a pollution preventing sheet, a fishing net, a breeding net, a mooring rope, a longline rope, a laver net holding rope, or the like. SOLUTION: A sea urchin-shaped composite photocatalyst is added and/or fixed to the fiber structure to prevent not only the fouling of underwater organisms but also the yellowing and deteroration of the binder and the fiber structure caused by the photocatalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber structure having an ability to prevent underwater organisms from adhering to organisms. More specifically, by including and / or fixing a sea urchin-like composite photocatalyst to a fibrous structure used in water, deterioration of the fibrous structure due to the photocatalyst is suppressed, and aquatic organisms such as algae, barnacles, parasites and the like are controlled. The present invention relates to a fiber structure that prevents adhesion to the fiber structure.

[0002]

2. Description of the Related Art When a fiber structure is used in water, various aquatic organisms adhere to the surface thereof. For example, during the construction of underwater large-scale civil engineering works at airports, etc., the anti-pollution sheet used to protect the surrounding sea area from pollution will cause the algae to adhere to the entire surface of the sheet in a few weeks and remove the attached algae. One wash is required. In addition, algae, barnacles, and the like adhere to the aquaculture nets used for marine aquaculture and land-based aquaculture, so that the flow of water in the aquaculture net is hindered, and the water quality in the aquaculture net deteriorates rapidly. Further, barnacles and the like adhere to ropes used near the sea surface in addition to algae. The rope to which the barnacles are attached is not only a cause of injury to the worker, but also damages the winch for winding up the rope. In addition, some parasites of farmed fish breed by laying eggs on farming nets.

[0003] In order to prevent these aquatic organisms from adhering, conventionally,
A method of attaching a toxic substance to a fiber structure has been performed. However, since the fibrous structure is used in water, the adhered toxic substances easily flow out of the fibrous structure, thereby causing a problem in sustaining the effect and polluting the environment. For example, it has been pointed out that organotin compounds, which have been widely used to prevent algae and barnacles from adhering, act as environmental hormones after flowing out into water and cause atypical shellfish. In order to prevent barnacle adhesion, a finely processed fiber structure has been proposed by Hamamatsu Industrial Technology Center of Shizuoka Prefecture (Industrial Technology Information of Shizuoka Prefecture, February 1998).
Moon, # 36), when the rope is wound up, there is a problem that the fine portion falls off and the effect is lost. further,
At present, a large amount of antibiotics is being administered to parasites to prevent the parasites from adhering, and there is a strong demand for measures to prevent aquaculture nets from adhering to aquatic organisms.

[0004] Most of the organisms such as algae and barnacles that adhere to fiber structures used in water float in the sea as fine organisms, then adhere to the fiber structures, and grow on the fiber structures. I will do it. Algae germinate and grow in the spore state after attaching to the fiber structure. Further, barnacles, which are crustaceans, are attached to the fibrous structure as plankton, and then transformed, ending their lives with being attached to the fibrous structure. Therefore, if these spores and plankton can be killed when they adhere to the fibrous structure, adhesion of algae and barnacles can be prevented.

[0005] Algae and barnacles grow where there is sufficient light. The growth of algae requires photosynthetic light, and the growth of barnacles requires the barnacles to be exposed on the sea surface. Therefore, in order to suppress the adhesion of algae and barnacles to the fiber structure, the surface of the fiber structure may be provided with a strong bactericidal power under conditions where there is sufficient light.

[0006] Certain parasites breed by laying eggs on cultivation nets. Therefore, by killing the eggs laid on the culture net, it is possible to suppress parasites on the cultured fish.

[0007] At present, aquaculture is carried out, for economic reasons, mainly in relatively shallow waters into which light enters. Also,
In recent years, aquaculture in pools on land, called onshore aquaculture, has also been actively conducted. In other words, the culture net
It is mainly used where there is sufficient light.
Therefore, the parasites that lay eggs on the culture net can be suppressed by providing the surface of the fibrous structure with a strong bactericidal power under conditions where there is sufficient light.

[0008] As a substance having a bactericidal effect in the presence of light,
Photocatalysts are known, and disinfection and deodorization of clothes have been proposed by utilizing their effects, but their effects on aquatic organisms have not been known.

The antibacterial mechanism by the photocatalyst is to radicalize water adhering to the surface of the photocatalyst by light, and to kill nearby organisms by the radicals. This photocatalytic antibacterial mechanism differs from the antibacterial mechanism of toxic substances,
Light is the energy source of the disinfection and, in theory, lasts forever. In addition, the generated radical immediately reacts with a nearby substance and returns to a harmless substance. Therefore, unlike the antibacterial mechanism of a general toxic substance, the load on the environment is extremely small.

Therefore, the photocatalyst has a high efficiency of radical generation, a long-lasting effect, and a small environmental load.
It exerts its excellent effects without fail. In addition, among the organisms that adhere to the fiber structure used in water, all of the organisms in question grow and adhere to the fiber structure in a region where there is sufficient light for obtaining the photocatalytic effect. Therefore, in order to suppress such biofouling, it is suitable to include a photocatalyst in the fiber structure.

However, when the conventional photocatalyst used conventionally is contained and / or fixed in the fiber structure,
At the time of processing such as fixing the photocatalyst to the fiber structure, there is a problem that the binder and / or the fiber structure that binds the photocatalyst and the fiber structure are decomposed by the photocatalyst and the fiber structure turns yellow. Due to the decomposition action, there is a problem that the decomposition of the fiber structure or the like progresses with time, and the fiber structure is deteriorated.

In order to solve these problems, it has been proposed to fix a mask melon type photocatalyst, in which a part of the surface of the photocatalyst is covered with apatite or the like having no photocatalytic ability, to a fiber structure. Have been. However, the muskmelon-type photocatalyst does not deteriorate the binder and the like, but the photocatalyst is widely covered with apatite and the like, so that the photocatalyst is inferior in ability and cannot have a sufficient effect of suppressing the adhesion of organisms in water.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to solve these problems, to provide a high level of environmental safety, to be able to use any species, and to have a long-lasting ability to prevent biological adhesion. Another object of the present invention is to provide a fiber structure suitable for use in water while suppressing deterioration and the like of the fiber structure.

[0014]

According to the present invention, a sea urchin-like composite photocatalyst having a plurality of needle-like substances having no photocatalytic ability on the surface of a substance having photocatalytic ability is contained in the surface or inside of the fiber structure. And / or a fixed fibrous structure having an ability to prevent underwater biofouling.

In the present invention, the sea urchin-like composite photocatalyst may be fixed to the fibrous structure via a binder.

It is preferable that 0.01 to 30% by weight, based on the weight of the fiber structure, of the sea urchin-like composite photocatalyst is fixed to the fiber structure.
Further, it is preferable that the fibrous structure contains 0.01 to 20% by weight of the sea urchin-like composite photocatalyst based on the weight of the fibrous structure.

In the sea urchin-like composite photocatalyst, the flatness of the needle-like substance having no photocatalytic ability is preferably 2 or more and 40 or less. Further, it is preferable that the sea urchin-like composite photocatalyst has four or more needle-like substances per one catalyst particle.

In the sea urchin-like composite photocatalyst, it is preferable that 10% or more and 90% or less of the surface of the substance having photocatalytic ability is not covered with the needle-like substance having no photocatalytic ability.

It is preferable that the photocatalytic substance in the sea urchin-like composite photocatalyst contains titanium oxide and / or strontium titanate. Further, it is preferable that the substance having photocatalytic ability in the sea urchin-like composite photocatalyst includes a visible light responsive photocatalyst.

It is preferable that the binder contains an acrylate resin and / or a prepolymer of an acrylate resin.

The fibrous structure may be a sheet, a rope,
It is preferably a fish net or a culture net.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have found that most of substances having no photocatalytic properties are used as binders in order to prevent the adhesion of living organisms in water and to prevent deterioration of fiber structures and the like due to photocatalysts. And a structure in which a part thereof comes into contact with the fiber structure, and a part having photocatalytic ability does not come into contact with the binder and the fiber structure. , Found the most favorable.

The sea urchin-like composite photocatalyst is a photocatalyst having a sea urchin-like shape in which a plurality of needle-like projections made of a substance having no photocatalytic ability are provided with a gap on the surface of the substance having photocatalytic ability. It is. The sea urchin-like composite photocatalyst is a substance in which a substance having photocatalytic ability is substantially spherical, and has a needle-like substance having no photocatalytic ability on the surface of the sphere in a substantially radial shape so that the tip of the needle faces outward. is there. Sea urchin-like composite photocatalyst is a part of the surface of a substance having photocatalytic ability, which is not covered with needle-like protrusions, is exposed and the surface is peeping,
Exhibits the effect of photocatalyst and suppresses the adhesion of underwater organisms.

The size of the sea urchin-like composite photocatalyst is not particularly limited. For example, the average secondary particle size, which is an aggregate of fine particles having photocatalytic ability, is 0.1 to 1 μm.
Preferably, the length of the needle-like substance is about half to twice the secondary particle size.

If the flatness of the shape of the needle-shaped projection having no photocatalytic ability is too small, the function of the photocatalyst is not sufficiently exhibited. The oblateness refers to a ratio of a long side to a short side when a vertically long acicular substance having no photocatalytic ability is approximated to a rectangle. On the other hand, if the oblateness is too large, it is difficult to maintain the shape of the acicular substance. Therefore, the flatness is preferably in the range of 2 to 40, and particularly preferably in the range of about 5 to 20.

If the number of needle-like substances having no photocatalytic ability per substance having photocatalytic ability is too small, the effect of suppressing deterioration of the fiber structure or the like due to the photocatalyst becomes low. On the other hand, if the amount is too large, the needle-like substance having no photocatalytic ability covers most of the surface of the substance having photocatalytic ability, and the performance of the photocatalyst decreases. Therefore, the number of needle-like substances having no photocatalytic ability per sea urchin-like composite photocatalyst is
The number is preferably 4 or more and 50 or less, particularly 4 or more and 3 or less.
0 or less is more preferable.

Similarly, in the sea urchin-like composite photocatalyst, if the area having the photocatalytic substance covered with the non-photocatalytic substance is too small, the effect of suppressing the degradation of the fiber structure or the like by the photocatalyst is low. On the other hand, if the covering area is too large, the performance of the photocatalyst decreases. Therefore, in the sea urchin-like composite photocatalyst, it is preferable that 10% or more and 90% or less of the total surface area of the photocatalytic substance is exposed and the surface is peeped, and particularly, 20% or more and 70% or less. More preferred.

The proportion of the substance having photocatalytic ability exposed on the surface of the sea urchin-like composite photocatalyst is a metal component in which a substance having photocatalytic ability is different from a needle-like substance having no photocatalytic ability. In this case, measurement can be performed with, for example, an X-ray microanalyzer (XMA), and when the sample is composed of only the same kind of metal, it can be quantified by electron spectroscopy (ESCA).

The photocatalytic substance in the sea urchin-like composite photocatalyst is not particularly limited as long as it exhibits a remarkable photocatalytic function by light, and known substances can be used. Metal oxides such as tungsten trioxide, zinc oxide, iron sesquioxide, and strontium titanate; metal sulfides such as cadmium sulfide, zinc sulfide, and indium sulfide; metal selenides such as cadmium selenate and zinc selenide; and phosphorus Metal phosphides such as germanium hydride and indium phosphide, and those in which a metal and a metal oxide such as platinum, rhodium, ruthenium, niobium, copper, and iron are supported on these photocatalysts, etc. In particular, titanium oxide, strontium titanate, and the like are preferable in terms of catalytic activity, safety, and price.

The kind of the substance having photocatalytic ability in the sea urchin-like composite photocatalyst may be contained singly or two or more kinds may be contained in the fiber structure. Further, as long as the effects of the present invention can be obtained, an ordinary photocatalyst other than the sea urchin-like composite photocatalyst may be used in combination. Further, the substance having photocatalytic ability in the sea urchin-like composite photocatalyst and / or the ordinary photocatalyst used in combination is not limited to an ultraviolet light responsive photocatalyst, and a visible light responsive photocatalyst may be used. For example, if a visible light responsive photocatalyst is used in combination with an ultraviolet light responsive photocatalyst in a fibrous structure and the like, the deeper the water depth, the more ultraviolet light attenuates, and the effect of the ultraviolet light responsive photocatalyst decreases. Since the visible light responsive photocatalyst exerts its effect up to a depth of water deeper than the ultraviolet light that the visible light can reach, the fiber structure has the ability to prevent underwater organisms from adhering to a deeper depth than when the ultraviolet light responsive photocatalyst alone is fixed. Is obtained.

As the acicular substance having no photocatalytic ability in the sea urchin-like composite photocatalyst, an acicular substance can be formed on the surface of the substance having the photocatalytic ability, and an organic substance, Both inorganic substances can be used. In particular, from the viewpoint of stability and the like, inorganic substances are preferable, and inorganic oxides, metal oxides, and composite metal oxides are more preferable. Examples of the acicular substance having no photocatalytic ability include apatite.

The sea urchin-like composite photocatalyst is bonded to the fiber structure,
For the binder to be fixed by adhesion and lamination,
There is no particular limitation, for example, any resin can be used, such as an acrylate resin, a urethane resin, a polyester resin, a silicone resin, a melamine resin, a polypropylene resin, or a fluororesin, or any of its prepolymers. In terms of fixing stability and texture,
Acrylic ester resins and prepolymers thereof are particularly preferred.

The acrylate resin as the binder resin is not particularly limited as long as it is a polymer resin containing an acrylate ester and / or a methacrylate ester as a main constituent monomer unit. Among them, a methacrylate ester resin is particularly preferable. . Specific examples of the monomer constituting the acrylate resin, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, methacrylic acid Non-functional monomer types represented by cyclohexyl, benzyl methacrylate, and the like; and
Methacrylic acid, 2-hydroxypropyl methacrylate,
Monofunctional monomer types represented by dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc .; and ethylene dimethacrylate and diethylene glycol dimethacrylate. And polyfunctional monomer types represented by triethylene glycol dimethacrylate, allyl methacrylate, diethylene glycol dimethacrylate phthalate, and the like. Copolymerizing these non-functional monomers with mono-functional or multi-functional monomers,
It is more preferable because a polymer having excellent adhesiveness and reactivity can be obtained.

When used in a field where washing durability is required, it is preferable to use a melamine resin as the binder resin in order to enhance the durability.

In the present invention, means for containing and / or fixing the sea urchin-like composite photocatalyst to the fiber structure can be roughly classified into two methods. One is a method in which a polymer composition containing a sea urchin-like composite photocatalyst is spun, and a fiber structure is produced from the obtained fibers, so that the sea urchin-like composite photocatalyst is contained in the fiber structure. The other is to use sea urchin-like composite photocatalyst with yarn, cotton, fabric,
This is a method in which the sea urchin-like composite photocatalyst is fixed to a fiber structure by being fixed to a fiber which is a solid material such as a knit.

In the present invention, the specific means for containing and / or fixing the sea urchin-like composite photocatalyst to the fiber structure is not particularly limited. For example, the fiber structure is prepared by using a fiber spun with a polymer containing a photocatalyst. Method for producing body, method for blending photocatalyst after melting polymer, method for producing fiber structure using fiber spun by incorporating into polymer, fiber structure after fixing photocatalyst to fiber not containing photocatalyst , A method of manufacturing a fiber structure using a fiber containing no photocatalyst, and then fixing the photocatalyst, a method of manufacturing a fiber structure after further fixing the photocatalyst to the fiber containing the photocatalyst, and a fiber containing the photocatalyst A method for producing a fiber structure using the method, further fixing the photocatalyst, producing a fiber structure after fixing the photocatalyst to the fiber containing the photocatalyst. This method for fixing the photocatalyst and the like in the al.

The processing method for fixing the sea urchin-like composite photocatalyst to the fiber structure is not particularly limited, but may be any method such as a dipping method, a pad drying method, a spray method, a coating method, and a laminating method. It can be appropriately selected depending on the form of the fibrous structure, the resin, and the type of the solution. The immersion method is a method in which the fiber structure is immersed in a processing liquid containing a sea urchin-like composite photocatalyst and a binder resin, and then dried to fix the functional agent containing the sea urchin-like composite photocatalyst to the fiber structure. The pad dry method is one type of dipping method, and is a method of dipping a fiber structure in a pad. The spray method is a method of spraying a working liquid onto a fiber structure. The coating method is a method of applying a high-viscosity working liquid to the surface of a fiber structure. The lamination method is a method of laminating a film containing a functional agent containing a sea urchin-like composite photocatalyst to a fiber structure.

For example, in a padding treatment in which a treatment liquid is contained in a fibrous structure, which is a dipping method or a pad drying method, first, these sea urchin-like composite photocatalysts and a binder resin or a prepolymer thereof are treated with heptane, acetone, methyl ethyl ketone, Dissolve in organic solvents such as methyl isobutyl ketone, ethyl acetate, butyl acetate, mineral terpene, isopropyl alcohol, or disperse them in water without using organic solvents, or in water, Disperse the sea urchin-like composite photocatalyst, and use a suitable emulsifier such as high-grade alcohol.
Sulfates, alkylbenzenesulfonates,
A working fluid is prepared by emulsifying a binder resin or a prepolymer thereof with a higher alcohol polyoxyalkylene adduct, a higher fatty acid polyoxyalkylene adduct, a higher fatty acid sorbitan ester, or the like. Next, after immersing the fiber structure in this processing liquid, the fiber structure is dried,
A sea urchin-like composite photocatalyst is bonded to the surface of the fiber structure via a binder.

The process of fixing the sea urchin-like composite photocatalyst to the fiber with the binder resin can be performed at any stage such as raw cotton, yarn, woven / knitted material, dyed product, and final product.

By fixing the sea urchin-like composite photocatalyst to the solid fiber after spinning or the like, if the amount of the sea urchin-like composite photocatalyst to be adhered to the fiber structure is too small, the photocatalyst cannot function sufficiently. On the other hand, if the amount is too large, the fiber structure is hardened by the photocatalyst. Therefore, the content is preferably in the range of 0.01% by weight to 30% by weight based on the fiber structure. More preferably, 0.1 wt% to 20 wt%,
More preferably, it is 0.2 to 10% by weight.

By including a sea urchin-like composite photocatalyst in the polymer before spinning, if the amount of the sea urchin-like composite photocatalyst to be contained in the fiber structure is too small, the photocatalyst cannot function sufficiently, while on the other hand, it is too large. And yarn breakage occurs frequently during spinning, so that the weight of the fiber structure is 0.01 to 20% by weight.
Preferably it is in the range of weight%. More preferably,
0.1 wt% to 20 wt%, more preferably 0.2 wt%
% By weight.

When a normal photocatalyst is used in combination with the sea urchin-like composite photocatalyst and fixed to the fiber structure, it can be contained or fixed to the fiber structure in the same manner as the sea urchin-like composite photocatalyst.

The fibrous structure used in the present invention is not particularly limited, and it is a general term for all fibers made of fibers such as woven fabric, nonwoven fabric, knitted fabric, lace, braid, felt, thread, cotton, etc. For example, a sheet-like structure such as a pollution prevention sheet during underwater civil engineering work, a rope used for holding a mooring line or a longline and a glue net, and a net-like structure such as a fish net or a culture net can be used. Sheet-like structures include woven fabrics, knitted fabrics,
Nonwoven fabrics and the like are also included. As the aquaculture net, a land-based aquaculture net or a sea-culture aquaculture net is preferable because it can be used in a place with light and can sufficiently exhibit the function of the photocatalyst.

The material of the fiber structure of the present invention is not particularly limited, but is preferably a synthetic fiber from the viewpoint of handling during underwater work. In particular, polyester fibers such as polyethylene terephthalate, polypropylene terephthalate, and polyethylene naphthalate, polyolefin fibers such as polyethylene and polypropylene, polyamide fibers such as nylon 6, nylon 66, and aramid fibers, and fluorine fibers are preferable.

The fibrous structure may be dyed before and after the photocatalyst is contained and / or fixed according to the purpose, or when the photocatalyst is contained and / or fixed, a colorant such as a pigment may be used in combination. May be dyed.

[0046]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples.
In the underwater biofouling test, the fabric to be tested is attached to a plate with a weight attached thereto, and the upper end of the fabric is attached at a position 50 cm below the water surface to a floating pier at a coastline port, and the lower end of the fabric is placed 50 cm below the water surface.
cm, and the state of adherence of organisms over time was examined.

Example 1 (Preparation of working fluid) 50 g of an acrylic binder (Vinetex A6410, manufactured by Daiwa Chemical Industry Co., Ltd.) was added to 850 g of water.
Then, at an average oblateness of 5 and having an average of 10 needle-like apatites having no photocatalytic ability per photocatalyst,
An aqueous dispersion of a sea urchin-like composite photocatalyst (F4-
100 g of APS (solid content: 40%) was added to prepare a working fluid containing 4% by weight of a photocatalyst.

The morphology of the sea urchin-like composite photocatalyst was determined by scanning electron microscope (SEM) photograph and XMA analysis. The oblateness of the needle-like substance was determined by approximating the needle-like substance into a rectangle in an SEM photograph, obtaining the ratio of the long side to the short side, and averaging. The average number of the needle-like substances was obtained by doubling the average of the number of needle-like substances per composite photocatalyst observed in the SEM photograph since one side of the composite photocatalyst was observed in the SEM photograph. In the surface area of the photocatalytic substance, the ratio of the area occupied by the substance exhibiting photocatalytic ability on the surface is determined by performing quantitative analysis (area analysis) of Ti (titanium) by XMA, and The relative value with 100% was calculated as the area ratio of the surface of the substance exhibiting photocatalytic ability to the surface.

(Processing of photocatalyst into fibrous structure) 1670 dTe having a true twist of 120 turns per meter
x, using a polyester multifilament having 250 filaments, a weave density of 23 × 23 and a basis weight of 33
A plain fabric of 3 g / m ² was produced. This plain woven fabric has a width of 10c.
m, cut into 8m long tape, immersed in the above-mentioned working fluid, squeezed out excess working fluid with mangle, dried with hot air dryer at 130 ° C for 5 minutes, Curing at 180 ° C. for 1 minute using a pin setter
e). The adhesion of the processing agent to the cured fabric was 3% by weight, and the adhesion of the photocatalyst was 1.5% by weight.

(State of Fabric by Processing) No yellowing of the fabric due to the fixing of the sea urchin-like composite photocatalyst to the fiber structure was observed.

(Results of Underwater Organism Adhesion Test) When an underwater organism adhesion test was performed using the cloth to which the sea urchin-like composite photocatalyst was fixed, no adhesion of underwater organisms was observed for 16 weeks, and a favorable result was obtained. Obtained. Table 1 shows the results.

Comparative Example 1 The same treatment as in Example 1 was performed except that the photocatalyst was not fixed. Since the photocatalyst is not fixed to the fiber structure, the yellowing of the fabric is
I couldn't see it. As a result of the underwater organism adhesion test, 2
Algae began to adhere to a shallow part from around a week, and after eight weeks, the algae were covered to the deep part of the tape-like cloth. Barnacles were also found to adhere to the part up to a depth of 50 cm. Table 1 shows the results.

[Comparative Example 2] In Example 1, the sea urchin-like composite photocatalyst aqueous dispersion was not used, and instead, a normal photocatalyst aqueous dispersion whose surface was not covered (STS-21, manufactured by Ishihara Techno Co., Ltd.) 100 g of titanium oxide concentration 40%)
Except having used, it carried out similarly to Example 1. As a result of fixing the photocatalyst to the fibrous structure, the fabric turned to yellow mainly during curing. The results of the underwater biofouling test were good. Table 1 shows the results.

[Comparative Example 3] An aqueous dispersion of a muskmelon-type photocatalyst (manufactured by Showa Denko; photocatalyst which is not covered with a substance having no photocatalytic ability but appears on the surface of the photocatalyst instead of the sea urchin-like composite photocatalyst) The active part is located on the surface of the photocatalyst.
%. ) Was carried out in the same manner as in Example 1 except that (1) was used.
As a result of fixing the photocatalyst to the fiber structure, the yellowing of the fabric is
I couldn't see it. As a result of the underwater organism test, from the fourth week,
Although less than the unprocessed one of Comparative Example 1, adhesion of algae started. Table 1 shows the results.

[0055]

[Table 1]

[0056]

According to the present invention, the use of a fibrous structure in water provides a high level of safety to the environment, regardless of species, by including a sea urchin-like composite photocatalyst in the fibrous structure.
It is possible to provide a fibrous structure which has excellent sustainability and an ability to prevent biological adhesion, suppresses deterioration of the fibrous structure, and is suitable for use in water.

In particular, since the photocatalyst used in the present invention is a sea urchin-like composite photocatalyst, the binder and the fiber structure in contact with or around the photocatalyst are prevented from being decomposed by the photocatalyst, and Yellowing and deterioration can be suppressed.

Since the fibrous structure used in the present invention can be used in water, it can be used as a pollution control sheet, a fish net, an aquaculture net, a mooring rope, a longline rope, a glue net holding rope, and the like. Can be.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01K 91/18 B01J 33/00 C 4L031 B01J 33/00 35/06 J 35/06 E02B 15/00 B D06M 11/46 A01K 79/00 A // E02B 15/00 D06M 11/12 F-term (reference) 2B104 CC34 CC35 CG03 CG17 2B105 AA04 AA08 AG01 AG12 AG15 HA01 2B106 AA08 AA21 ED01 HA13 HA14 HA16 2D025 AA02 4G004 AA03 BA08A BB06A BC12A BC50A CD10 DA05 EA03X EA03Y EA04Y EA30 EB14X EB14Y EC30 EE01 FA03 FC08 4L031 AA18 AB32 BA09 BA33 DA19

Claims (14)

[Claims] 1. A sea urchin-like composite photocatalyst having a plurality of needle-like substances having no photocatalytic ability on the surface of a substance having photocatalytic ability,
A fibrous structure having the ability to prevent underwater biofouling, which is contained and / or fixed on the surface or inside of the fibrous structure. 2. The fiber structure according to claim 1, wherein the sea urchin-like composite photocatalyst is fixed to the fiber structure via a binder. 3. The fiber structure according to claim 1, wherein the weight of the fiber structure is not less than 0.01% by weight and not more than 30% by weight.
The sea urchin-like composite photocatalyst is fixed.
3. The fibrous structure having the ability to prevent underwater organisms from adhering according to 1.). 4. The method according to claim 1, wherein the fiber structure has a weight of 0.01% to 20% by weight based on the weight of the fiber structure.
The fibrous structure according to claim 1, wherein the sea urchin-like composite photocatalyst is contained. 5. The underwater biofouling according to any one of claims 1 to 4, wherein the flattening rate of the needle-like substance having no photocatalytic ability in the sea urchin-like composite photocatalyst is 2 or more and 40 or less. A fibrous structure having a protective ability. 6. The catalyst particles of the sea urchin-like composite photocatalyst
The fiber structure according to any one of claims 1 to 5, wherein the fiber structure has four or more needle-like substances per piece. 7. The urchin-like composite photocatalyst according to claim 1, wherein 10% or more and 90% or less of the surface of the substance having photocatalytic ability is not covered with the needle-like substance having no photocatalytic ability.
The fibrous structure according to any one of Items 1 to 6, which has an ability to prevent underwater organisms from adhering to organisms. 8. The fiber according to claim 1, wherein the photocatalytic substance in the sea urchin-like composite photocatalyst contains titanium oxide and / or strontium titanate. Structure. 9. The fiber structure according to claim 1, wherein the photocatalytic substance in the sea urchin-like composite photocatalyst contains a visible light responsive photocatalyst. 10. The fiber structure according to claim 2, wherein the binder contains an acrylate resin and / or a prepolymer of the acrylate resin. 11. The fiber structure according to claim 1, wherein the fiber structure has a sheet shape. 12. The fibrous structure according to claim 1, wherein the fibrous structure is a rope. 13. The fiber structure according to claim 1, wherein the fiber structure is a fish net. 14. The fiber structure according to claim 1, wherein the fiber structure is an aquaculture net.