JPH01295905A - Alga-proof material - Google Patents

Abstract

PURPOSE:To obtain an underwater structure full of flexibility and excellent in shellfish-attachment-proof property, by using polytetrafluoroethylenic fibers or polyethylenic fibers, for a surface section coming in contact with the water of the underwater structure of a rope, a floating wave dissipation bank, a gate, or the like. CONSTITUTION:A section coming in contact with the water of the underwater structure of a finishing rope, a mooring rope, a surface layer or intermediate layer floating fish gathering place, a floating wave dissipation bank, a fishing net, a marine station or a dam, the gate of an irrigation canal, or the like is composed of alga-proof materials. The alga-proof materials are composed of polytetrafluoroethylenic fibers and/or polyethylene system fibers. As a result, various underwater structures having flexibility and also shellfish-attachment- proof property can be obtained.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to durable anti-algae materials.

[Prior Art] Various attempts have been made to impart algae-proof properties, such as applying chemicals that algae dislike, and using resins and fibers containing the chemicals.

[Problems to be Solved by the Invention] However, all of these anti-algae materials lack durability, and their anti-algae effects are also unsatisfactory.

In view of such conventional algae-preventing materials, the present invention was achieved by investigating that a specific fiber has an excellent algae-preventing effect.

In other words, the present inventors have discovered that polytetrafluoroethylene fibers and ultrafine polyethylene fibers surprisingly have the property of repelling algae, shellfish, corals, etc., and that the thinner the fibers, the more effective they are. This is what we have investigated.

The present invention is characterized in that algae do not easily adhere to it over a long period of time, and since it is made of a textile product, it can be attached freely as the shape changes. All of the fibers of the present invention are characterized by being rich in water repellency and slipperiness, having little water resistance, and having little friction problem.

[Means for Solving the Problems] In order to achieve the above object, the present invention employs the following configuration. That is, (1) an anti-algae material characterized in that at least the surface of the construct is composed of polytetrafluoroethylene fibers and/or polyethylene fibers;

(2) The algae-preventing material according to claim 1, wherein the surface is composed of a raised structure made of polytetrafluoroethylene fibers and/or polyethylene fibers.

(3) The polyethylene fiber has a tensile strength of 25 g
/d or more, and the initial tensile modulus is 530 (11/d or more).

In the present invention, polytetrafluoroethylene (hereinafter referred to as PTF)
(referred to as E type) refers to a homopolymer of tetrafluoroethylene or 60 mol% or more of the total, preferably 90 mol%
The above are copolymers of tetrafluoroethylene.

Monomers that can be copolymerized with such tetrafluoroethylene include fluorinated vinyl compounds such as trifluoroethylene, trifluorochloroethylene, tetrafluoropropylene, and hexafluoropropylene, as well as propylene, ethylene, isobutylene, styrene, acrylonitrile, and the like. Examples include vinyl compounds, but there is no need to limit them to these.

Among such monomers, vinyl fluoride compounds, especially compounds with a high fluorine content, are preferred from the viewpoint of fiber properties.

In the present invention, the PTFE fibers may be m-fibers produced by either melt spinning or wet spinning.

The finer the average fineness, especially the finer the finer, the better the anti-algae effect, but preferably 3 d or less, more preferably 1 d.
It is as follows.

Such PTFE fibers are applied in the form of filaments or short fibers, but when used in the form of short fibers, those with a fiber length of at least 3 cm, preferably 5 cm or more are selected from the viewpoint of entanglement.

In the PTFE fibers of the present invention, preferable fibers have a small-angle X-ray scattering intensity of 80 Cf) or less, preferably 50 cp when measured by small-angle X-ray scattering method at 2θ=1°.
S or less, particularly preferably 40C1)S or less, and by wide-angle X-ray diffraction method (counter method) (110)
It has a surface crystal size of 95 Å or more, preferably a thickness of 100 Å or more, and is characterized by excellent strength and dimensional stability.

There are no restrictions on the fiber properties of such PTFE fibers, but a strength of 1.0 g/d or more is sufficient. Preferably it is 1.5 g/d or more. The lower the elongation, the better, 30
% or less, preferably 20% or less, dry heat shrinkage rate (230″
It is preferable that CX30'>20% or less, more preferably 15% or less.

Note that the small-angle X-ray scattering intensity is measured by a small-angle X-ray scattering method (small-angle X-ray diffraction method).

Further, the crystal size of the (1io) plane is measured by wide-angle X-ray diffraction method (counter method).

As a method for producing such PTFE fibers, for example, a mixed solution of viscose and PTFE dispersion is used as a spinning stock solution, which is discharged into a coagulation bath, coagulated, and then washed and refined with water. After immersing in scouring and condensed alkaline water and squeezing, it is dried or directly sent to the firing process, and is heated to a temperature of 300 to 45
It is fired at 0°C and stretched at least 5 to 10 times. Next, this fired fiber is produced by two methods: oxidative aging in a high-temperature atmosphere of 300 to 340°C, or melt-spinning by melting a PTFE copolymer at a temperature higher than the melting point of the copolymer. There is a way.

Any of the above-mentioned spinning methods may be used, but in short, it is sufficient as long as the single fiber fineness can be made small. That is, it is sufficient if ultrafine fibers of 3 d or less, preferably 0.1 to 3 d, can be obtained.

This point is the same for polyethylene II, for example,
Polyethylene fibers having a single yarn denier of 0.1 to 3 d can be obtained by spinning at a high draw ratio. This fiber has a tensile strength of 25 aid or more and an initial tensile modulus of 530a.
/d or more. This fiber also has higher strength (40o/d) and higher modulus (1000a/d).
) can also be manufactured and can be suitably applied to the present invention.

An example of a method for manufacturing such polyethylene fibers will be explained.

Ultra-high strength polyethylene filament is a weight average molecule! 2
It is composed of a polymer of X105 or more.

If the weight average molecular weight is lower than this, the strength and initial elastic modulus will be insufficient. Preferably it is 1X106 or more.

A polymer solution consisting of such a polymer is prepared.

The solvent includes aliphatic hydrocarbons, alicyclic hydrocarbons,
Examples include aromatic hydrocarbons and mixtures thereof. For example, decalin, xylene, tetralin and wax can be applied as long as they are liquid at 100°C or higher.

After heating a polymer solution containing such a solvent and having a polymer concentration of 0.5 to 15% by weight to 120 to 250'C,
This is extruded through a nozzle through an inert gas atmosphere into a spinning bath. It is necessary to pass an inert gas because of the agglutination between single filaments, and usually air or nitrogen is used.

Next, this fibrous solution is mixed with cooling water liquid and halogenated hydrocarbon,
For example, it is permeated by spinning, which is composed of a coagulant such as methylene chloride or carbon tetrachloride. Here, while extracting the solvent, it is cooled to below the gelling point, and only the surface of the fibrous solution is solidified in the lower layer.

It is then passed through an extraction bath to extract the remaining solvent, sent to a drying step, and then sent to a stretching step. The fiber thus obtained has no inter-filament adhesion.

Such fibers are drawn to a magnification of at least 8 times, preferably 12 times or more, selecting temperature conditions as high as possible, and a stretching factor of 0.1 to 3. It becomes an ultrafine fiber of Od.

The PTFE fibers and polyethylene fibers of the present invention are characterized in that the thinner the fibers are, the more excellent they are in water repellency and slipperiness, and the fibers are also excellent in abrasion resistance. Generally speaking, the latter type of fiber is characterized by high strength. These fibers can be used alone or in combination.

Furthermore, it is possible to mix these fibers with other synthetic fibers within a range that does not impede the purpose of the present invention, and in the case of thread-like fibers, it is possible to mix the fibers with other synthetic fibers in the core and sheath, for example, PTF.
E-type fibers may also be arranged.

The present invention skillfully utilizes such water-repellent fibers and effectively utilizes them for algae-proofing purposes.Moreover, the resulting product is highly flexible, has excellent antistatic and anti-pilling properties, and has a rough texture. It has the characteristic that it is easy to obtain a product with a high fiber density, and also has the characteristic that it has excellent stitching properties because it has good needle threadability in combination with electric training properties.

Such fibers are formed into a suitable form and applied as an anti-algae material.

For example, filaments, short fibers, tows, threads, ropes, webs, knitted fabrics, non-woven fabrics, paper, as well as raised (raised) and flocked products made of these fibers, etc. It can be applied in the form of textile products.

It is important that such fiber products be placed on at least the surface of the base material forming the algae-proofing material. It is also placed in areas that come into contact with water, where algae are likely to grow.

The most effective embodiment of the present invention is that the surface is made up of raised fluff consisting of these fibers. It suffices if the density of the piloerection is such that it fluctuates due to currents and waves. Of course, the finer the fineness of the fibers constituting the nap, the more effective it is.

In the present invention, such an anti-algae material is used on at least the surface of the portion of the underwater construct that comes into contact with water.

Here, an underwater structure is one that is immersed in water, floating on the water surface or in water, or subject to water resistance.
This refers to structures that are damaged by the growth of sphagnum moss and algae. There are no restrictions on the type of material constituting such a structure, such as metal, other inorganic materials, synthetic resin, etc.

Such structures include, for example, ropes for parts, mooring ropes, surface or mid-layer floating reefs, floating breakwaters, fishing nets, marine stations (offshore stations), underwater stations, ships (ship bottom, ship side, whole), marine beacons. This includes, but is not limited to, ship parts such as dams, water gates, and screws for irrigation canals, ship supplies, underwater (undersea) cables, and undersea (undersea) walkways (vehicle traffic).

In general, the anti-algae material of the present invention is effective even when applied to structures in the civil engineering and architectural fields, such as bridge girders, piers, foundation work members of buildings, walls and structural members of kitchens and bathrooms. be.

There are no restrictions on the method of joining the algae-proofing material to such a construct, and the method may be selected as appropriate depending on requirements such as the scale of the construct and the condition of the joined portion. - Methods such as sewing, gluing, bolt donuts, etc. can be applied to the inside of the membrane, and methods using adhesives are particularly easy.

Examples of such adhesives include acrylic resins, epoxy resins, urethane resins, unsaturated polyester resins, vinyl alcohol resins, and modified products thereof;
Examples include adhesives made of synthetic rubber resins.

Particularly preferred are acrylic resins and vinyl alcohol resins such as copolymers of cyanoethylated ethylene and vinyl alcohol.

In addition, in order to further increase the adhesive strength, the surface of the algae-proofing material to be adhered can be subjected to plasma treatment.

The plasma treatment conditions are 20 tOrr or less and are achieved by exposing the fiber to glow discharge in the presence of Ar, N2, He, NH3, air, etc.

The anti-algae material of the present invention is placed inside a cylindrical structure,
For example, the effect can be exerted when water or a substance containing water is made to flow.

Here, the term cylindrical includes tubular and groove shapes.

Suitable examples of such cylindrical structures include structures used for transportation, transportation, transfer, drainage, etc., such as various water pipes, sewage pipes (including irrigation canal pipes), irrigation canals and sewage grooves, and various drainage ditches. can be given to

Next, the present invention will be explained in more detail using Examples.

[Example] The tensile strength and initial elastic modulus in Examples were measured according to the following measurement method.

Using multifilament yarn as a sample, JIS-L-
It was measured according to the test method specified in 1017. That is, the multifilament yarn was wound into a skein and placed in an atmosphere adjusted to 20'C165%Rl-1.
After leaving it for 4 hours, a sample was taken from the skein and tested using a Pachinshiron UTM-4L tensile tester (manufactured by Toyo Baldwin) with a sample length of 25 cm and a tensile speed of 3QC.
m/min. The initial elastic modulus was measured from the load-elongation curve obtained here according to the definition of JIS-L-10'17.

Example 1 PTFE resin dispersed in ion-exchanged water using alkylaryl polyether alcohol as a dispersant
% dispersion and viscose (8.9% cellulose, 5.4% caustic soda, 29% carbon disulfide/cellulose amount, remaining ion-exchanged water >100 parts) were loaded into a vacuum mixer at 8°C. and vacuum level 10 Tor
The mixture was mixed and degassed at r for 21 hours to prepare a spinning stock solution.

This spinning stock solution was introduced into a spinneret having 240 holes of 0.12 mmφ at a rate of 43 g/min, and was fed at a speed of 23 m/min to
It was discharged into a coagulation bath controlled at °C. Coagulation bath is sulfuric acid 7
%, and an aqueous solution prepared by dissolving 20% of sodium sulfate in ion-exchanged water was used.

This coagulated fiber is introduced into an ion exchange water tank at 80°C, and the
After being thoroughly washed slowly at a speed of 9 m/min and squeezed with a mangle, the caustic soda concentration is 0.05 mol/min.
The fibers were immersed in an ion-exchange aqueous solution containing 0.32% of caustic soda based on the weight of the fibers.

This alkali-containing fiber was then brought into contact with a roll heated to 380°C and fired.

This fired fiber was then stretched 7 times while being brought into contact with a heated roll at 350°C.

The fibers were left in a relaxed state in an air atmosphere heated to 320° C. for 72 hours.

The obtained PTFE fiber is white and curly, and has a single yarn fineness of 1.7d.
, strength 1.3 Md, elongation 16.1%, dry heat shrinkage rate (
230'CX 30 minutes) 12.3% Teatc.

The small-angle X-ray scattering intensity at 2θ=1° of this fiber was determined by small-angle X-ray scattering to be 38CF)S, and the crystal size of the (110) plane by wide-angle X-ray diffraction was 107.

The plain woven fabric made of the above PTFE fiber was wrapped around a 10 cm square concrete pillar to cover it.

Next, the plain woven fabric was raised with a needle cloth to form a raised fabric, which was then wrapped around the column.

These pillars were immersed in 1 meter of sea water on a rocky shore in the summer and left for three months, but almost no seaweed or shellfish were attached to them. In addition,
The latter pillar had no traces of adhesion and remained unchanged even after 6 months.

In contrast, the concrete pillars had a large amount of algae and shellfish growing and clinging to them after two months.

Example 2 Linear high-density polyethylene with a weight average molecular weight of 3.0 x 106 was dissolved in decalin at a temperature of 160°C to make a 3.0% by weight solution, and the solution was injected with air through a nozzle with a pore diameter of 0.5 mm and a number of holes of 15. The mixture was extruded into a bath, passed through the air bath by a distance of 3 mm, and then cooled and solidified in a two-layer spinning bath consisting of water in the upper layer and methylene chloride in the lower layer. The temperature of the spinning bath was 10°C, the thickness of the upper layer (water) was 2Q mm, and the distance the yarn traveled in the lower layer (methylene chloride) was 800 mm (
Of this, the part where the single yarn separates and runs is 300 mm)
And so. The total discharge amount from the nozzle is 10CC7 minutes,
The coagulated yarn was pulled off at a rate of 7.5 m/min.

The yarn was then passed through a discharge bath made of methylene chloride at 10°C to extract decalin remaining in the yarn.
It was dried and rolled up using a heating roll. This dried yarn is heated on a hot plate with a surface temperature of 140°C and a length of 120cm.
The yarn feeding speed was 20 cmZ and the yarn was drawn 15 times. As a result, fineness: 1.39d strength: 40.1 o/d elongation:
A fiber having properties of 5.44% initial elastic modulus: 1090 g/d was obtained.

The above polyethylene filament yarn was wrapped tightly around a 1Qcm square concrete column to cover it so that no voids were formed.

This pillar was immersed in 1 meter of sea water on a rocky shore in the summer and left for three months, but almost no seaweed or shellfish adhered to it.

In contrast, the concrete pillars had a large amount of algae and shellfish growing and clinging to them after two months.

[Effects of the Invention] The present invention provides an algae-preventing material that has excellent not only algae-proofing properties but also excellent shellfish adhesion prevention properties and is highly flexible, and can be used in various algae-prevention constructions. It can be used extremely effectively as an anti-algae cylindrical structure, and its range of applications is wide.

Claims (3)

[Claims] (1) An anti-algae material characterized in that at least the surface of the construct is composed of polytetrafluoroethylene fibers and/or polyethylene fibers. (2) The algae-preventing material according to claim (1), wherein the surface is composed of a raised structure made of polytetrafluoroethylene fibers and/or polyethylene fibers. (3) The polyethylene fiber has a tensile strength of 25 g/d
Claim (
1) The anti-algae material described.