JPS61138647A - Algicidal polymer - Google Patents

Abstract

PURPOSE:A polymeric material in the form of nets or sheets that is composed of specific zeolite solid particles holding metal ions which have algicidal actions by ion exchange and an organic polymer, thus preventing barnacles and algae from sticking to or growing on the sheets and nets. CONSTITUTION:Solid particles of zeolite which has more than 150m<2>/g of spe cific surface area, less than 14, preferably less than 11 of SiO2/Al2O3 molar ratio and holds metal ions with algicidal action such as tin, lead or mercury (A-type zeolite or X-type zeolite) are added to an organic polymer and the mixture is molded, then subjected to ion exchange. The content of the zeolite solid particles is 0.01-50wt%, preferably 0.05-40wt%, while the metal content in the metal zeolite is less then 30wt%, preferably 0.01-10wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymer having anti-algae properties, and more specifically to a polymer in the form of a net, sheet, fiber, coating material, etc. that prevents the adhesion of algae, barnacles, etc. related.

Algae such as sea lettuce and barnacles adhere to the surface of objects that are submerged in water, such as fishing nets or ship hulls, which adversely affects the use of nets and the operation of ships. As a method for preventing the adhesion of these plant-based and animal-based deposits, a method is known in which a paint containing O-O is applied to a ship's hull. Scales using organic arsenic, organic mercury, organic lead, or organic tin instead of Ou,0 are also known. In this method, these antifouling agents are eluted little by little from the paint film and act. However, it is necessary to elute them in sufficient amounts to be effective and to maintain the effect for a long time. It was difficult.

The present invention provides a polymer that significantly prevents the adhesion of such deposits and maintains its effect. The polymer of the present invention can prevent not only plant-based deposits such as algae but also animal-based deposits such as fujibo, but for the sake of simplicity, this property will be referred to as "algae-proofing property" below. say.

That is, the present invention comprises zeolite-based solid particles and an organic polymer, wherein the zeolite-based solid particles have a specific surface area of 150 m"/ or more and a S1O!/mroom molar ratio of 14 or less, and It is at least one molecule of zeolite solid particles.

In the present invention, the algae-preventing effect is achieved by zeolite solid particles containing one or more metal ions having an algae-preventing effect in the ion-exchangeable portion of natural or synthetic zeolite made of aluminosilicate. . Preferred examples of metal ions that have an antialgae effect include Ni, Pb,
HPXAt.

Examples include Cu XZn. Bn, Pb, H
f is preferred. Therefore, it is possible to use the above-mentioned algae-proofing metals alone or in combination for the above-mentioned purpose.

Zeolite is generally an aluminosilicate with a three-dimensionally developed skeleton structure, and is generally expressed as XM ynO・A4,0g・78101・z
H! Represented by 0. M represents an ion-exchangeable metal ion, usually a monovalent to divalent metal, and "" corresponds to this valence. On the other hand, X and Y are the coefficient of metal oxide and silica, respectively, and 2 is the crystal water represents the number of

Many types of zeolites are known, differing in their composition ratio, pore diameter, specific surface area, etc.

However, the specific surface area of the zeolite solid particles used in the present invention is 150-/l (based on anhydrous zeolite) or more, and the molar ratio of the zeolite constituents is 14 or less, preferably 11 or less. Must.

Metals with anti-algae action used in the present invention, such as tin,
A solution of water-soluble salts of lead, mercury, copper, silver, and zinc, preferably tin, lead, and mercury, easily undergoes ion exchange with the zeolite defined in the present invention. It is possible to hold the above metal ions alone or in a mixed form in a zeolite stationary phase, but the zeolite particles holding metal ions are
Specific surface area is 150 gl”/1 or more and 8101
/A40g molar ratio must be 14 or less. It has been found that if this is not the case, it will be difficult to obtain an object that achieves an effective algae control effect. This is thought to be due to the lack of the absolute amount of metal ions necessary to exhibit algae-proofing properties over a long period of time. In other words, this is considered to be due to the physicochemical properties of the zeolite, such as the amount of exchange groups, exchange rate, and accessibility.

Therefore, S1o, known as molecular sieve
, /Al, o, a zeolite with a large molar ratio is completely unsuitable for the present invention.

Also 910. /A/, O, in zeolite with a molar ratio of 14 or less, it is possible to uniformly retain metal ions having an antialgae effect, and for this reason, using such zeolite has a sufficient antialgae effect for the first time. was found to be obtained. In addition, zeolite B i OH
/A 1m 01 The acid resistance and alkali resistance of zeolite with a high silica ratio exceeding 14 increase as EliOl increases, but on the other hand, it takes a long time to synthesize it, and from an economical point of view, such a high silica ratio is It is not advisable to use zeolite. The aforementioned S1o, /A/, O1≦
Natural or synthetic zeolite No. 14 can be used satisfactorily in the fields in which the present structure is normally considered in terms of its acid resistance and alkali resistance, and is economically advantageous as it is inexpensive. From this meaning as well, S i OH/A 1
The 101 molar ratio must be 14 or less.

E i O! used in the present invention! /A/! As the zeolite material having an OH molar ratio of 14 or less, either natural or synthetic zeolite can be used. For example, as a natural zeolite, Tsuji Anal-ci
e: Si, Ot/A/l Os -16 to 5.6
), ChabaZits: 810!
/At@OB=5.2~&O and &4~7.
6), Clinoptilolite (Olinoptilo-1)
1te: 5i02/A/1%= & 5~1 (L
5), Erionite (Irion engineering to: 81
02/A120g=5.8~Z4), Faujaeite: 8101/At
@O@ '-4,2~4.6), mordenite (no
raeni t13: S Lo! /A/1032a
34-111.0), Philli
psite: Sin, /At! OB-λb~a
, a), etc. These typical natural zeolites are suitable for the present invention. On the other hand, a typical synthetic zeolide is 8-type zeolide (shellfish/A120B
= 1.4-2-4), X-type zeolide (slo.

/A/! false=2~3), Y-type zeolide (a1~/A
Examples include hehe-3 to 6), mordenite (810!/A/Fuji 9 to 10), and these synthetic zeolites are suitable as the zeolite material of the present invention. Particularly preferred are synthetic A-type zeolides, X-type zeolides, Y-type zeolides and synthetic or natural mordenites.

The shape of the zeolite is preferably in the form of fine powder particles, and the particle size can be selected appropriately depending on the shape of the polymer and the intended use. For applications such as a few microns to several tens of microns or several hundreds of microns or more, the particle size may be several microns to several tens of microns or several hundred microns or more.On the other hand, when molding into fine denier fibers or thin sheets, the smaller the particle size is, for example, 5 microns or less, especially 2 microns or less. It is desirable that

In the present invention, the shape of the polymer is typically a net, sheet, fiber, covering material, container, etc., but is not limited thereto. The term "coating material" as used herein includes a coating film or a paint for forming a coating film. The polymer itself is a synthetic or semi-synthetic organic polymer, such as polyethylene/, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polyester, polyvinyl alcohol, polycarbonate, polyacetal, Be resin, acrylic resin, Thermoplastic synthetic polymers such as fluororesin, polyurethane elastomer, polyester elastomer, thermosetting synthetic polymers such as phenol resin, area resin, melamine resin, unsaturated polyester resin, epoxy resin, urethane resin, rayon,
Examples include recycled or semi-synthetic polymers such as cupro, acetate and triacetate, typically polyolefins such as polyethylene and polypropylene.

The zeolite particle-containing polymer of the present invention is composed of such zeolite solid particles and an organic polymer, and at least a part of the zeolite solid particles retains metal ions having an anti-algae effect. ing. The proportion of the zeolite solid particles in the whole is 01 to 50% by weight (based on anhydrous zeolite). If it is less than the above lower limit, the algae-preventing effect is unsatisfactory. On the other hand, even if the above-mentioned upper limit is exceeded, the anti-algae effect remains almost unchanged, and the physical properties of the polymer change significantly, which is not preferable. From this point of view, a more preferable content range is [105 to 40% by weight;
A range of 10% by weight is preferred.

Metal ions undergo an ion exchange reaction with zeolite solid particles.
It must be maintained well. If the algae is simply adsorbed or attached without ion exchange, the algae-preventing effect and its sustainability will be insufficient. The present inventors have found that two methods are possible for retaining metal ions.

The first method is to add and mix Kanaoka zeolide, which has an anti-algae effect, to an organic polymer, and the second method is to add and mix zeolite to an organic polymer, mold it, and then mold the polymer molded product. This is a method in which ion exchange treatment is performed to retain metal ions that have an anti-algae effect in zeolite within the polymer.

First, the first method of the present invention will be explained. This method utilizes a metal-zeolide having an anti-algae effect, and the metal-zeolide can be prepared using an ion exchange reaction as described above.

Taking the case of converting various zeolites defined in the present invention to the At-zeolite of the present invention as an example, Mut-zeolite conversion is usually carried out using a solution of a water-soluble silver salt such as silver nitrate. However, it is preferable that the concentration is not excessive. For example, when converting 8-type or
~2 When using MAfN01) During ion exchange, silver ions replace sodium ions in the solid phase, and at the same time, silver oxides etc. are precipitated in the zeolite solid phase. This silver oxide is wasted because it does not contribute to long-term, sustainable algae-proofing properties.

In order to prevent such excess silver from being deposited on the zeolite phase, the concentration of the silver solution is diluted, for example, α3 MAPNO.
It is necessary to keep it below 1. Extremely safe fN
The concentration of o@ is [11M or less.

It was found that when an AjNOn solution of such a concentration was used, the specific surface area of the resulting hp-zeolite was almost the same as that of the zeolite used as the conversion material, and that the algae-preventing effect could be exhibited under optimal conditions for a long period of time.

The above also applies to ion exchange with metal ions outside the silver plate, in the sense that it prevents the metal ions from simply depositing on the zeolite without ion exchange.

When carrying out the ion exchange reaction by a batch method, the zeolite material 1c may be immersed in a salt solution having an appropriate concentration. In order to increase the metal content in the zeolite material, K may be used by increasing the number of patch treatments. On the other hand, when treating a zeolite material using a column method using a salt solution, the desired metal-zeolide can be easily obtained by filling an adsorption tower with the zeolite material and passing the salt solution through it.

The amount of metal in the above metal-zeolide (based on anhydrous zeolite) is not more than 30% by weight, preferably Q
, 01 to 10% by weight, especially 1 to 5% by weight.

Next, the composition of the present invention is obtained by adding and mixing such metal zeolite to the organic polymer in the above-mentioned content.

Metals - Amount of metals with antialgal action against zeolides (
The amount of metal-zeolide (B wt%) relative to the composition are both related to the algae-preventing effect; the more A, the less B is needed; conversely, the less A, the more B. There is a need. In order to effectively demonstrate the anti-algae effect, use AX.
It is desirable to adjust the value of B to 0.01 or more, preferably CL1 or more. General K Xan SP'
b, Hf SAt gives the same effect at about half the amount compared to Ou and Zn. The timing and method of adding and mixing the metal ion-containing zeolite are not particularly limited. For example, a method of adding to raw materials and mixing and then polymerizing, a method of adding and mixing to a reaction intermediate, a method of adding and mixing to the polymer after polymerization, a method of adding and mixing to polymer pellets and molding, a method of adding and mixing to polymer pellets and molding, a method of adding and mixing to a polymer pellet, etc. There are methods such as adding and mixing. In the following, these methods will be simply referred to as ``adding and mixing to an organic polymer''. In short, the most suitable method may be adopted depending on the properties of the polymer used, the characteristics of the process, etc. Usually, a method of adding and mixing just before molding is suitable. However, in some cases it may be preferable to add it to the monomer for better particle dispersion. The metal-zeolide may be dried if necessary before being added to the polymer.

The drying conditions may be appropriately selected from the range of 100 to 500° C. under normal pressure or reduced pressure. Preferred drying conditions are 100-35% under reduced pressure.
It is 0°C.

Next, the second method will be explained. The second method is basically similar to the first method in many respects, although the timing of the ion exchange treatment is different.

First, the zeolite defined above is added to a polymer and mixed without ion exchange treatment. The content range of zeolite is the same as in the first method. The timing and method of addition and mixing are not particularly limited. As in the first method, the additives may be added and mixed at any stage from preparation of raw materials to molding of the polymer. Furthermore, if it is necessary to dry the zeolite, the method described above may be followed. In the second method, the zeolite-containing polymer obtained in this manner is formed into a molded body and then subjected to ion exchange storage. The type and shape of the molded product are not particularly limited; for example, it may be an intermediate molded product such as a pellet, or it may be in the form of a final product. In order to increase the ion exchange efficiency, a molded body with a large specific surface area is suitable. Therefore, a molded body having a small diameter and thickness is preferable, such as a granular body, a film, or a fiber. The method of ion exchange treatment is basically similar to the method of ion exchange treatment of zeolite described above, and the zeolite-containing polymer molded body is treated with a solution of water-soluble salts of metals that have an anti-algae effect. . In this case, the concentration range of the metal salt is
This is the same as described for the method. As a processing method, either a patch method or a continuous method is possible. In order to increase the amount of metal ions retained, the number of patch treatments may be increased or, in the case of a continuous method, the treatment time may be increased.

The second method is that the zeolite confined within the polymer body retains ion exchange ability, and that by appropriate ion exchange treatment, the zeolite can retain metal ions that have an anti-algae effect. It is based on two findings.

The proportion of zeolite in the polymer body that is ion-exchanged depends on the properties of each polymer body. In the case of relatively highly hydrophilic polymers, metal ions permeate into the interior as water permeates, so that the zeolite inside the polymer is also ion-exchanged. However, it was found that even with hydrophobic polymers, zeolite near the surface undergoes ion exchange at a considerable rate. It is thought that the bactericidal power of the particle-containing polymer of the present invention mainly depends on the metal ions near the surface of the molded body, so there is no problem even if only the zeolite near the surface retains the antialgal ions. Algae-proofing property - It is an efficient method from the viewpoint of utilization rate of metal ions. In either case, the ratio of the metal having an antialgal action to the total t (based on anhydrous zeolite) K of the zeolite is the same as described for the first method.

Zeolite content in polymer containing zeolite particles (
3wt%) and 'Jl! for metal-zeolite)K of metal ions retained in zeolite by ion exchange treatment.
: (Awt%) is related to the magnitude of the anti-algae effect as described in the first method; if there is a lot of B, less A is needed; conversely, if there is less B, less A is needed. need to do more. AX
It is desirable to adjust the value of B to 101 or more, preferably 11 or more.

The bonding force between the zeolite defined in the present invention and the algae-proofing metal ion is extremely large, unlike a method in which the zeolite defined in the present invention is held by an adsorbent substance such as activated carbon or alumina simply by physical adsorption. Therefore, the strong anti-algae effect of the polymer containing such metal zeolite and its long-term sustainability should be particularly noted as the characteristic advantages of the present invention. The zeolite limited as in the present invention contains an, Pb, and HP which have an antialgal action.
.

It has the advantage of high reactivity with Af, Ou and Zn.

For example, the ion-exchangeable metal ions (Na'') in Mu-type zeolite, It retains metal ions and has a high ability to retain them.Also, the zeolite defined as in the present invention has the advantage of having a high selective adsorption property for the above-mentioned metal ions.This fact indicates that the zeolite particle-containing polymer of the present invention Even when liquids containing various metal ions are used in seawater for the purpose of preventing algae, the above-mentioned algae-preventing metal ion is stably retained in the zeolite matrix for a long period of time, and the algae-preventing effect is maintained for a long period of time. It means that

In addition, the zeolite defined as in the present invention has a large exchange capacity and has the advantage of being able to hold a large amount of metal ions having an anti-algae effect.

Moreover, the zeolite defined in the present invention hardly deteriorates the physical properties of the polymer, and a wide variety of polymer types can be selected.

Since the zeolite particle-containing polymer of the present invention is mainly composed of a polymer, it can be molded into various shapes and sizes. For example, films, fibers, various containers,
It can be formed into a pipe, a painted film or any other molded body, and can be used in any application requiring an anti-algae effect. Further, by dissolving or dispersing the zeolite particle-containing polymer of the present invention in a liquid to impart fluidity, it can be widely applied to algae-proof paints, coatings, and the like.

Next, embodiments of the present invention will be described, but the present invention is not limited to these embodiments unless the gist thereof is exceeded.

Example Preparation of algae-proofing metal ion-containing zeolite Composition α94N
ano 4!1% ・1.92 EliOl ・x%O
, an average particle size of 1.1 μm, dried at 00°C, moisture content of 1&0%, specific surface area of 664 m”/?, and 2502 pieces of dried fine powder of A-type zeolite were collected, and 11 pieces of f/20M steel sulfate aqueous solution were collected.
added. The resulting mixture was kept under stirring at room temperature for 5 hours. The copper-zeolide obtained by such an ion exchange method was washed with water until sulfate ions were removed after suction and filtration.

Next, the water-washed copper-zeolide was dried at 100 to 105°C and then ground to obtain a finely powdered copper-zeolide conversion product. It contains 173% by weight (based on anhydrous zeolite) copper. By repeating ion exchange, a zeolite containing 2.3% by weight of copper was obtained and used in the following evaluation of algae resistance.

Similarly, using A-type zeolite, tin 1.1 weight,
A zeolite containing 1.20% silver was prepared and used in the experiments described below.

Manufacture of sheet and evaluation of algae-proofing property The A-type zeolite containing each of tin, copper, and silver obtained above was immersed in a polyethylene pellet for 25 days as shown in Table 3, and then pulled out to observe the adhesion of Ulva and Fujibuki. The results are summarized in Table 3.

Zeolite that does not contain anti-algae metals (contains Tsuma υHa)
It is clear that the sheet of the present invention has better anti-algae properties than a control product mixed with zeolite and a blank product without zeolite mixed therein. The effect is particularly remarkable when tin is used.

Claims (1)

[Claims] 1. Consisting of zeolite solid particles and an organic polymer, the zeolite solid particles have a specific surface area of 150 m^2/g or more and a SiO_2/Al_2O_3 molar ratio of 14 or less, and An anti-algae polymer, characterized in that at least one part of the zeolite-based solid particles retains metal ions having an anti-algae effect through ion exchange. 2. The polymer according to claim 1, wherein the zeolite solid particles are composed of A-type zeolite, X-type zeolite, Y-type zeolite, or mordenite. 3. The polymer according to claim 1, wherein the metal ion having a bactericidal effect is one or more metal ions selected from the group consisting of tin, lead, and mercury. 4 Claim 1 in which the content of zeolite solid particles is 0.01 to 50% by weight (based on anhydrous zeolite)
Polymer described in Section. 5. The polymer according to claim 1, which is in the form of a net, sheet, fiber or covering material.