JP2023045983A - Rare earth ferrite dispersion resin liquid, product, and coating material - Google Patents

Abstract

To provide a rare earth ferrite dispersion resin liquid having high dispersibility of rare earth ferrite.SOLUTION: A dispersion resin liquid is obtained by blending, in a solvent-based acrylic resin having a reactive group with isocyanate, a rare earth ferrite compound having a specific composition. Specifically, a rare earth ferrite dispersion resin liquid contains a rare earth ferrite compound represented by the following expression (1), and a solvent-based acrylic resin having a reactive group with isocyanate. Expression (1): Ln2xFe2(1-x)O3. In the expression (1), Ln is a rare earth element selected from the group consisting of lanthanum, praseodymium, neodymium and yttrium, and x is a number of 0.45 or more and less than 1.00.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a rare earth ferrite-dispersed resin liquid, a product provided with a layer formed from the rare earth ferrite-dispersed resin liquid, and a paint containing the rare earth ferrite-dispersed resin liquid.

In recent years, ferrite compounds have been proposed as anti-algae agents with low environmental pollution and excellent safety. For example, in Patent Document 1, an anti-algae main component is orthoferrite containing a rare earth element selected from lanthanum (La), praseodymium (Pr), neodymium (Nd), and yttrium (Y), iron, and oxygen. An additive for algae, an anti-algae paint using the same, and an anti-algae product in which the paint is applied to the surface of a substrate are disclosed.

In Patent Document 1, the anti-algae effect is considered in association with the magnetism of the material, and the rare earth oxide: Fe ₂ O ₃ =1:1 (molar ratio ) are described as the most preferred anti-algae additives.

Japanese Patent Application Laid-Open No. 2005-272320

Rare earth ferrite, which is generally applied to building materials, ship bottoms, etc., is mixed with paint, and the paint is applied to the substrate surface to form a rare earth ferrite-containing layer on the substrate. Therefore, it is preferable that the rare earth ferrite is uniformly dispersed in the paint.

The present invention has been made in view of the above background, and an object of the present invention is to provide a rare earth ferrite-dispersed resin liquid having high dispersibility of rare earth ferrite.

The present inventors have made intensive studies to solve the above problems. Then, it was found that a dispersion resin liquid having a high dispersibility of rare earth ferrite can be obtained by mixing rare earth ferrite with a solvent-based acrylic resin having a reactive group with isocyanate to form a dispersion resin liquid. Arrived. That is, the present invention is as follows.

<<Aspect 1>>
A rare earth ferrite represented by the following formula (1);
a solvent-based acrylic resin having a reactive group with isocyanate;
A rare earth ferrite dispersion resin liquid containing:
_{Ln2xFe2 (1-x) O3} (1)
(In formula (1), Ln is a rare earth element selected from the group consisting of lanthanum, praseodymium, neodymium, and yttrium, and x is a number of 0.45 or more and less than 1.00.).
<<Aspect 2>>
The rare earth ferrite dispersion resin liquid according to aspect 1, wherein x in the formula (1) is a number of 0.55 or more and less than 1.00.
<<Aspect 3>>
The rare earth ferrite-dispersed resin liquid according to aspect 1, wherein x in the formula (1) is a number of 0.55 or more and 0.75 or less.
<<Aspect 4>>
The rare earth ferrite-dispersed resin liquid according to aspect 1 or 2, wherein Ln in the formula (1) is lanthanum.
<<Aspect 5>>
The rare earth ferrite-dispersed resin liquid according to any one of aspects 1 to 4, wherein the rare earth ferrite is at least one selected from the group consisting of anti-algae agents, anti-mold agents, and anti-bacterial agents.
<<Aspect 6>>
A product comprising a substrate and a rare earth ferrite-containing layer laminated or impregnated on said substrate,
The rare earth ferrite-containing layer is a layer formed from a treatment liquid containing the rare earth ferrite-dispersed resin liquid according to any one of aspects 1 to 5.
product.
<<Aspect 7>>
7. The product of aspect 6, wherein the product is selected from the group consisting of ships, revetments, building materials, fishing nets, aquaculture nets, aquariums, pools, pool course ropes, buoys, and tiles.
<<Aspect 8>>
7. The product of aspect 6, wherein the product is selected from the group consisting of outer walls, inner walls, building materials, air filters, packing, and tanks or pipes for storing or passing water.
<<Aspect 9>>
7. The product of aspect 6, wherein the product is selected from the group consisting of interior walls, building materials, joint materials, sealants, furniture, air filters, insoles, clothing, sanitary products, medical materials or equipment, bath mats, towels, and bedding.
<<Aspect 10>>
A paint comprising the rare earth ferrite dispersed resin liquid according to any one of aspects 1 to 4.

According to the present invention, a rare earth ferrite-dispersed resin liquid having high dispersibility of rare earth ferrite is provided.

A treatment liquid such as a coating liquid or an impregnation liquid to which the rare earth ferrite-dispersed resin liquid of the present invention is applied becomes a treatment liquid with high dispersibility of rare earth ferrite. Effects such as anti-algae, anti-mold, and anti-bacterial due to rare earth ferrite can be uniformly exhibited.

《Rare earth ferrite dispersed resin liquid》
The rare earth ferrite dispersed resin liquid of the present invention contains a rare earth ferrite represented by the following formula (1) and a solvent-based acrylic resin having a reactive group with isocyanate.
_{Ln2xFe2 (1-x) O3} (1)
(In formula (1), Ln is a rare earth element selected from the group consisting of lanthanum, praseodymium, neodymium, and yttrium, and x is a number of 0.45 or more and less than 1.00.)

ADVANTAGE OF THE INVENTION According to this invention, the rare-earth-ferrite dispersion|distribution resin liquid with high dispersibility of rare-earth-ferrite is provided. Although not limited to theory, this is because in a solution in which a solvent-based acrylic resin having a reactive group with isocyanate exists, the bias in the charge in the resin caused by the reactive group with isocyanate and the rare earth ferrite This is believed to be due to the fact that an electrostatic interaction occurs between the particles and the charges possessed, thereby promoting the dispersion of the rare earth ferrite particles.

The constituent components of the rare earth ferrite-dispersed resin liquid of the present invention are described below.

《Rare earth ferrite》
The rare earth ferrite used in the rare earth ferrite dispersed resin liquid of the present invention is a rare earth ferrite compound having a specific composition and is represented by the following formula (1):
_{Ln2xFe2 (1-x) O3} (1)
(In formula (1), Ln is a rare earth element selected from the group consisting of lanthanum, praseodymium, neodymium, and yttrium, and x is a number of 0.45 or more and less than 1.00.).

If the rare earth (Ln):Fe ratio in the rare earth ferrite is within the above range, a high antifungal effect can be obtained.

The rare earth ferrite may take any form as long as x in the above formula (1) is a number of 0.45 or more and less than 1.00. For example, a solid solution having a uniform composition as a whole may be formed, or a mixture of LnFeO ₃ phase and Ln ₂ O ₃ phase may be formed, or a uniform composition solid solution, LnFeO ₃ phase, and Ln ₂ O may be formed. It may be a mixture with _three phases. Also, phases other than these may be included.

x in formula (1) is 0.50 or more, 0.55 or more, 0.56 or more, 0.57 or more, 0.58 or more, 0.59 or more, 0.60 or more, 0.65 or more, 0 0.70 or more, or 0.75 or more, 0.95 or less, 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, 0.70 or less, 0.65 or less, Or it may be 0.60 or less.

x in the above formula (1) may be, for example, a number of 0.55 or more and less than 1.00, or a number of 0.55 or more and 0.75 or less. In this regard, as a result of detailed examination of the composition of rare earth ferrite and its anti-algae effect, the present inventors set the Ln:Fe ratio in rare earth ferrite to a region rich in rare earth than 1:1 (molar ratio). It has been found that (1) the dispersibility of the rare earth ferrite compound in the water-based urethane resin is improved, and (2) the anti-algae effect is improved, and the period during which the effect continues is extended. .

The rare earth element (Ln) in the formula (1) may be lanthanum, in particular, from the viewpoint of excellent antifungal properties, antialgae properties, and cost of the obtained rare earth ferrite. Therefore, the rare earth ferrite used in the rare earth ferrite dispersed resin liquid of the present invention may be lanthanum ferrite.

<Rare earth ferrite content>
From the viewpoint of sufficiently ensuring the dispersibility of the rare earth ferrite, the content of the rare earth ferrite in the rare earth ferrite dispersion resin liquid of the present invention is, for example, 1% with respect to the solid content of the solvent-based acrylic resin having a reactive group with isocyanate. % by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more, From the viewpoint of obtaining good coatability, it may be, for example, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, or 40% by mass or less.

<Method for producing rare earth ferrite>
The method for producing the rare earth ferrite used in the present invention is not particularly limited. , may be produced by firing.

The stress applied here may be, for example, friction force, shear force, shear stress, or impact force. A method of applying such a stress to the mixture of the rare earth source and the iron source includes, for example, wet grinding in a ball mill.

As the rare earth source, for example, oxides of desired rare earth elements may be used, and bastnaesite, monazite, xenotime, etc. may also be used.

As the rare earth element, lanthanum is preferably used from the viewpoints of excellent anti-algae, anti-mold, and antibacterial properties of the obtained rare earth ferrite and cost. Among them, La ₂ O ₃ is highly effective, and lanthanum ferrite can be produced at a relatively low cost.

Iron sources include oxides such as FeO, _Fe3O4 and _Fe2O3 ; oxyoxides _such as FeOOH, _ferrihydrite and schwermannrite; water such as Fe(OH) ₂ and Fe(OH) ₃ . oxide; and the like may be used.

Among these, if FeOOH is used as the iron source, it is more reactive than Fe ₂ O ₃ and the like, so it can be fired at a low temperature, and the grain size is smaller than Fe ₂ O ₃ and the like. Small rare earth ferrites can be produced.

When the mixture of the rare earth source and the iron source is pulverized and mixed by wet pulverization, for example, water, alcohol, or the like may be used as the liquid medium. After pulverizing and mixing the mixture of the rare earth source and the iron source, if necessary, the liquid medium may be removed by an appropriate method such as drying by heating, and then firing may be performed.

The firing temperature is not particularly limited and can be set as appropriate. For example, the temperature.

For example, if the temperature is in the range of 800° C. or higher and 1000° C. or lower, it is possible to obtain rare earth ferrite having even better anti-algae, anti-mold and anti-bacterial effects.

The firing time is also not particularly limited, and can be set as appropriate. For example, 1 hour or more, 2 hours or more, 3 hours or more, 4 hours or more, 6 hours or more, 8 hours or more, 12 hours or more, or 15 hours or more, and 72 hours or less, 48 hours or less, 36 hours or less, 24 hours hours or less, 18 hours or less, or 15 hours or less.

The ambient atmosphere during firing may be an oxidizing atmosphere, for example firing in air.

After sintering, the rare earth ferrite that can be used in the present invention can be obtained by pulverizing, classifying, etc. by an appropriate method, if necessary.

<Uses of rare earth ferrite>
Rare-earth ferrite can be used in various applications because of its low degree of environmental pollution and excellent safety.

Rare earth ferrite can be used, for example, for at least one or more applications selected from the group consisting of anti-algae agents, anti-fungal agents, and anti-bacterial agents, and in particular, exhibits excellent performance as an anti-alg agent or anti-fungal agent. show.

For example, when used as an anti-algae agent, it is possible to suppress the deterioration of the anti-algae effect over time, and when used as an anti-fungal agent, the anti-mold effect can also be expressed in the surrounding area. can be done.

<<Solvent-based acrylic resin having a reactive group with isocyanate>>
The solvent-based acrylic resin having an isocyanate-reactive group used in the rare earth ferrite dispersion resin liquid of the present invention is not particularly limited, and the acrylic resin having an isocyanate-reactive group dissolves or disperses the resin. Anything that is dissolved or dispersed in a solvent may be used.

Therefore, the solvent-based acrylic resin having a reactive group with isocyanate may be dissolved in a solvent or dispersed in a solvent as an emulsion or solid.

The reactive group of the acrylic resin with isocyanate is not particularly limited, but examples thereof include a hydroxyl group and an amino group. Among these, a hydroxyl group is preferred.

When the solvent-based acrylic resin having a reactive group with isocyanate has a hydroxyl group, the hydroxyl value is preferably high. A solvent-based acrylic resin having a high hydroxyl value is more easily adhered to particles of rare earth ferrite, so that the dispersibility of particles of rare earth ferrite can be enhanced.

The hydroxyl value is not particularly limited. , 170 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, or 110 or less.

The solvent constituting the solvent-based acrylic resin having a reactive group with isocyanate is not particularly limited, and may be a known solvent.

For example, alcohols such as ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol and diacetone alcohol, ethers such as methyl ether, ethyl ether and propyl ether, esters such as ethyl acetate, butyl acetate and isobutyl acetate, acetone, Ketones such as methyl ethyl ketone, diethyl ketone, cyclohexanone, ethyl isobutyl ketone, and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, xylene, and benzene, aliphatic hydrocarbons such as normal hexane, heptane, and cyclohexane, and propylene glycol monomethyl ether. Various organic solvents such as acetate, glycol ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, and mineral spirits can be used. The solvent may be used alone or in combination of two or more.

As the solvent-based acrylic resin having a reactive group with isocyanate, a commercially available product can be used, and examples of commercially available products include Acrydic (registered trademark) series (DIC Corporation), which are isocyanate-curable acrylic resins. be done.

《Other Ingredients》
The rare earth ferrite-dispersed resin liquid of the present invention may contain optional components in addition to the rare earth ferrite and the solvent-based acrylic resin having a reactive group with isocyanate. Other components include, for example, resins other than solvent-based acrylic resin components having groups reactive with isocyanate, solvents, additives, and the like.

<Resin other than the component of the solvent-based acrylic resin having a reactive group with isocyanate>
The resin, which is optionally contained in the rare earth ferrite-dispersed resin liquid of the present invention, other than the component of the solvent-based acrylic resin having a reactive group with isocyanate, is not particularly limited. For example, acrylic resins, acrylic silicon resins, silicon resins, aminoalkyd resins, epoxy resins, phenolic resins, polyurethane resins, unsaturated polyester resins, fluorine resins, etc., which do not have reactive groups with isocyanate may be used.

<Solvent>
The solvent contained in the rare earth ferrite dispersion resin liquid of the present invention is not particularly limited. There may be.

<<Method for producing rare earth ferrite dispersion resin liquid>>
The method for producing the earth-ferrite-dispersed resin liquid of the present invention is not particularly limited. For example, it may be prepared by mixing a solvent-based acrylic resin having a reactive group with isocyanate, a rare earth ferrite, and other optional components in a predetermined ratio.

"product"
Yet another aspect of the present invention is an article comprising a substrate and a rare earth ferrite-containing layer laminated to or impregnated on the substrate. The rare earth ferrite-containing layer is a layer formed from a treatment liquid such as a coating liquid or an impregnation liquid containing the rare earth ferrite dispersed resin liquid of the present invention.

<Substrate>
The substrate in the product of the invention can be any article to which one wishes to apply the rare earth ferrite. It can be any article made of any material, having any shape, and any article to which the performance of rare earth ferrite is desired.

In the case where the substrate is impregnated with the rare earth ferrite-containing layer, the substrate may be, for example, a woven fabric or non-woven fabric formed from fibers, or a porous film or the like.

<Layer containing rare earth ferrite>
The rare earth ferrite-containing layer in the product of the present invention is not particularly limited as long as it is a layer formed from a treatment liquid such as a coating liquid or an impregnation liquid containing the rare earth ferrite dispersed resin liquid of the present invention. The rare earth ferrite-containing layer is laminated or impregnated on the substrate.

The rare earth ferrite-containing layer formed from the treatment liquid containing the rare earth ferrite dispersed resin liquid of the present invention contains rare earth ferrite and an acrylic resin having a reactive group with isocyanate as essential components. Any component other than these may be contained. Examples of optional components include, but are not limited to, resins, binders, additives, and the like.

The treatment liquid containing the rare earth ferrite-dispersed resin solution of the present invention for forming the rare earth ferrite-containing layer is, for example, a solution or dispersion containing the rare earth ferrite-dispersed resin solution of the present invention and other resins and additives. A mixed mixture may be used, or a mixture obtained by adding other resins, additives, and the like to the rare earth ferrite-dispersed resin liquid of the present invention may be used.

In the treatment liquid containing the rare earth ferrite-dispersed resin solution of the present invention for forming the rare earth ferrite-containing layer, the content of the rare earth ferrite is, from the viewpoint of sufficiently expressing the performance of the rare earth ferrite, relative to the total solid content of the treatment liquid. The ratio of rare earth ferrite is, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass. It may be at least 80% by mass, from the viewpoint of obtaining good coating properties, for example, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, Alternatively, it may be 20% by mass or less.

The method of forming the rare earth ferrite-containing layer is not particularly limited. For example, a method of coating a substrate with a treatment liquid containing a rare earth ferrite dispersed resin solution and drying to obtain a cured product, or a method of forming a rare earth ferrite dispersed resin. A method of immersing a substrate in a treatment liquid containing a resin liquid, impregnating the substrate with the treatment liquid, and then drying the substrate may be used.

The thickness of the rare earth ferrite-containing layer is not particularly limited, and may be, for example, about 1 μm or more and 1 mm or less.

The coating amount of the treatment liquid for forming the rare earth ferrite-containing layer is, for example, 5 g/m ² or more, 10 g/m ² or more, 15 g/m ² or more, 20 g as a dry mass after removing the solvent per unit area. /m ² or more, or 25 g/m ² or more, for example, 200 g/m ² or less, 150 g/m ² or less, 120 g/m ² or less, 100 g/m ² or less, 80 g/m ² or less, or 70 g /m ² or less.

<Other configurations>
The product of the present invention may contain, as essential constituents, the substrate and the rare earth ferrite-containing layer laminated or impregnated on the substrate, and may contain other constituents. Other configurations include, for example, other layers, and the other layers may be outside the substrate, between the substrate and the rare earth ferrite-containing layer, or outside the rare earth ferrite-containing layer.

Other layers include, for example, a primer layer formed on the substrate. Adhesion can be improved by forming the rare earth ferrite-containing layer on the primer layer.

In addition, by coating the outer side of the rare earth ferrite-containing layer with a resin or the like, it is possible to suppress the deterioration of the effect caused by the rare earth ferrite due to dropout or leakage of the rare earth ferrite due to long-term use.

Furthermore, by laminating a hue pigment layer or the like on the outside of the rare earth ferrite-containing layer, the degree of freedom in color design of the product may be increased, and other functional layers may be laminated or combined. , it may be provided with a performance different from that of the rare earth ferrite.

<Application>
The use of the product of the present invention is not particularly limited, but when rare earth ferrite is used as an anti-algae agent, it can be It may be a product selected from the group consisting of course ropes, buoys and tiles.

When rare earth ferrite is used as an antifungal agent, it may be, for example, a product selected from the group consisting of outer walls, inner walls, building materials, air filters, packing, and tanks or pipes for water storage or water flow.

When rare earth ferrite is used as an antibacterial agent, for example, inner walls, building materials, joint materials, sealing materials, furniture, air filters, insoles, clothing, sanitary goods, medical materials or equipment, bath mats, towels, and bedding It may be a product selected from the group.

"paint"
Another present invention may be a paint containing the rare earth ferrite-dispersed resin liquid of the present invention.

The paint may contain other components such as a resin and a solvent in addition to the rare earth ferrite-dispersed resin liquid of the present invention.

The resin optionally contained in the paint is not particularly limited, and examples thereof include acrylic resins, acrylic silicone resins, silicone resins, aminoalkyd resins, epoxy resins, phenolic resins, polyurethane resins, unsaturated polyester resins, fluorine resins, and the like. can be

Solvents contained in the paint are not particularly limited, and may be selected from, for example, water, alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and the like.

In the paint, the content of the rare earth ferrite is, from the viewpoint of sufficiently expressing the performance of the rare earth ferrite, the ratio of the rare earth ferrite to the total solid content of the paint, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more. , 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more, from the viewpoint of obtaining good coating properties, for example, 80% by mass 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less.

The manufacturing method of the paint is not particularly limited. For example, it may be prepared by mixing a commercially available synthetic resin paint and the rare earth ferrite-dispersed resin liquid of the present invention in a predetermined ratio.

<Application>
The paint of the present invention can be used to form the rare earth ferrite-containing layer in the product of the present invention described above. In addition, for example, it may be used as a joint material (a filler for gaps in tiles, concrete, bricks, etc.), a sealing material, a caulking material, an adhesive, and the like.

<<Example 1>>
<Production of lanthanum ferrite>
0.25 mol of La ₂ O ₃ , 0.5 mol of FeOOH, and water were placed in a ball mill using 10 mmΦ alumina spheres as grinding media, and pulverized and mixed for 5 hours. The resulting pulverized material was dried at 300° C. for 15 hours and then pulverized with a rotary pulverizer. The obtained pulverized product was fired at 1,000° C. for 15 hours and then pulverized with a hammer mill to obtain lanthanum ferrite (formula LaFeO ₃ ) of La:Fe=50:50 (molar ratio).

<Preparation of Lanthanum Ferrite Dispersed Resin Liquid>
The lanthanum ferrite prepared above was added to an isocyanate-curable acrylic resin (trade name: Acrydic (registered trademark) A-801-P, DIC Corporation) in a composition having a solid concentration of 30%. Further, 20 g of 3 mmφ zirconia beads were added and stirred for 30 minutes with a paint shaker to obtain a lanthanum ferrite dispersed resin liquid.

<Dispersibility evaluation>
The produced lanthanum ferrite-dispersed resin liquid was allowed to stand for 4 days, and the lanthanum ferrite dispersed state after 4 days was visually evaluated according to the following evaluation criteria. Table 1 shows the results.
A: There was no sedimentation of lanthanum ferrite and it was uniformly dispersed. A: Sedimentation of lanthanum ferrite started, but there was no boundary between the sediment and the dispersed resin liquid.
Δ: Lanthanum ferrite was sedimented, and there was a boundary between the sediment and the dispersed resin liquid, which separated into two layers.
x: A large amount of lanthanum ferrite precipitated, the upper layer of the dispersed resin liquid became transparent, and separated into three layers of the precipitate, the dispersed resin liquid, and the supernatant liquid.

<<Example 2, Comparative Example 4>>
A lanthanum ferrite dispersed resin liquid was prepared in the same manner as in Example 1, except that the acrylic resin for constituting the dispersed resin liquid was changed to the product shown in Table 1. Dispersibility evaluation was performed in the same manner as in Example 1 for the obtained lanthanum ferrite dispersed resin liquid. Table 1 shows the evaluation results.

<<Examples 3-4, Comparative Examples 1-3, Comparative Example 5>>
Lanthanum ferrite was synthesized in the same manner as in Example 1, except that the composition ratio shown in Table 1 was used. A lanthanum ferrite-dispersed resin liquid was prepared in the same manner as in Example 1 using the obtained lanthanum ferrite and the products shown in Table 1 as acrylic resins. Dispersibility evaluation was performed in the same manner as in Example 1 for the obtained lanthanum ferrite dispersed resin liquid. Table 1 shows the evaluation results.

From the above examples and comparative examples, (1) the rare earth ferrite is dispersed in a solvent-based resin liquid in which a solvent-based acrylic resin having a reactive group with isocyanate, that is, an acrylic resin having a reactive group with isocyanate is dispersed. and (2) the molar ratio of rare earth (La) to iron (Fe) when the rare earth is less than iron (La:Fe (molar ratio ) = 40:60), when rare earth is equivalent to iron (La:Fe (molar ratio) = 50:50), or when rare earth is more than iron (La:Fe (molar ratio) = 60:40 ) promotes dispersion of the rare earth ferrite.

<<Reference Examples and Reference Comparative Examples>>
In the following reference examples and reference comparative examples, by setting the Ln:Fe ratio in the rare earth ferrite to a region richer in rare earth than 1:1 (molar ratio), the anti-algae effect is improved and the effect indicates that the duration of

<<Reference Example 1>>
(1) Synthesis of lanthanum ferrite In a ball mill using 10 mmΦ alumina spheres as grinding media, 0.3 mol parts of La ₂ O ₃ , 0.4 mol parts of FeOOH, and water were charged, and pulverized and mixed for 5 hours. . The resulting pulverized material was dried at 300° C. for 15 hours and then pulverized with a rotary pulverizer. The obtained pulverized product was fired at 1,000° C. for 15 hours and then pulverized with a hammer mill to obtain lanthanum ferrite of La:Fe=60:40 (molar ratio) (composition formula La _1.2 Fe _{0 .8} O ₃ ).

(2) Preparation of anti-algae coating liquid The obtained lanthanum ferrite was blended into a commercially available synthetic resin paint (for concrete ponds, containing vinyl chloride resin), and shaken and mixed with a paint shaker to obtain An anti-algae coating solution was prepared. The composition of this anti-algae coating liquid was adjusted so that the compounding amount of lanthanum ferrite was 10% by mass with respect to 90 parts by mass of the resin contained in the synthetic resin paint.

(3) Production of anti-algae product As a base material, a film made of polyethylene terephthalate (PET) (thickness: 50 μm) is used, and on one side thereof, the above-mentioned anti-algae coating solution is applied using a wire bar #32. After drying at 60° C. for 2 days (48 hours), an anti-algae product having an anti-algae layer on one side of the PET film was produced. The coating amount of the anti-algae layer was 36.8 g/m ² .

(4) Evaluation of algae-proof product The evaluation sample obtained by cutting the obtained algae-proof product into a square of 5 cm x 5 cm was hung with a string in a rectangular parallelepiped water tank with a bottom area of 25 cm x 20 cm. Seawater collected from the sea was poured into this water tank to a depth of 10 cm, and the evaluation sample was completely submerged in the seawater. The water tank in this state was allowed to stand outdoors in an environment exposed to sunlight, and the state of algae adherence to the coated surface was visually examined after each predetermined period of time, and evaluated according to the following criteria. Table 2 shows the evaluation results.
When no algae adhered to the coated surface: "-"
When the algae adhesion area is 10% or less of the area of the coated surface: "+"
When the algae adhesion area is more than 10% and 50% or less of the area of the coated surface: "++"
When the algae adhesion area exceeds 50% of the area of the coated surface: "+++"

<<Reference Example 2>>
La:Fe=80:20 (molar ratio) in the same manner as in Reference Example 1, except that the amounts of La ₂ O ₃ and FeOOH were changed to 0.4 mol parts and 0.2 mol parts, respectively. Lanthanum ferrite (compositional formula: La _1.6 Fe _0.4 O ₃ ) was synthesized and used to prepare an anti-algae coating liquid to produce an anti-algae product. The obtained anti-algae product was evaluated in the same manner as in Reference Example 1. Table 2 shows the evaluation results.

<<Reference Comparative Example 1>>
An anti-algae product was evaluated in the same manner as in Reference Example 1, except that a PET film not coated with an anti-algae coating solution was cut into a 5 cm x 5 cm square and used as an evaluation sample. rice field. Table 2 shows the evaluation results.

<<Reference Comparative Example 2>>
An evaluation sample was prepared and evaluated in the same manner as in Reference Example 1, except that lanthanum ferrite was not added to the coating liquid. Table 2 shows the evaluation results.

<<Reference Comparative Examples 3 to 5>>
Lanthanum ferrite with different La:Fe ratios was synthesized in the same manner as in Reference Example 1, except that the amounts of La ₂ O ₃ and FeOOH were changed as shown in Table 2, and used for algae control. An anti-algae product was produced by preparing a non-toxic coating solution. The obtained anti-algae product was evaluated in the same manner as in Reference Example 1. Table 2 shows the evaluation results.

From the results in Table 2, it can be seen that, compared to Reference Comparative Examples 1 and 2, in which lanthanum ferrite was not used, in Reference Comparative Examples 3 to 5 and Reference Example 1, in which lanthanum ferrite was used, anti-algae properties were expressed. confirmed. However, anti-algae products using lanthanum ferrite with a La:Fe ratio of 50:50 (molar ratio) or a lower La ratio could not maintain anti-algae properties for a long period of time (Reference Comparative Example 3-5).

On the other hand, in the anti-algae products of Reference Example 1 with a La:Fe ratio of 60:40 (molar ratio) and Reference Example 2 with a La:Fe ratio of 80:20 (molar ratio), the coated surface It was confirmed that no algae was observed on the surface, showing an excellent anti-algae effect.

<<Reference Examples 3 to 5, and Reference Comparative Examples 6 to 12>>
Lanthanum ferrites with different La:Fe ratios were synthesized in the same manner as in Reference Example 1, except that the amounts of La ₂ O ₃ and FeOOH were changed as shown in Table 3. Using the obtained lanthanum ferrite, an algae-proof coating solution was prepared in the same manner as in Reference Example 1, except that the amounts of lanthanum ferrite and resin were changed as shown in Table 3. This was used to make an anti-algae product. The obtained anti-algae product was evaluated in the same manner as in Reference Example 1. The evaluation results are shown in Table 3 together with the results of Reference Examples 1 and 2 and Reference Comparative Examples 1-5.

According to Table 3, the anti-algae product of Reference Comparative Example 6, in which the La:Fe ratio is 42:58 (molar ratio), has the same anti-algae effect as in Reference Comparative Examples 1 and 2 in which lanthanum ferrite is not used. It turned out not to occur. In addition, the anti-algae products of Reference Comparative Examples 3, 7, and 8, in which the La:Fe ratio was 46:54 (molar ratio), showed some anti-algae effect, but the effect was low.

On the other hand, the anti-algae products of Reference Comparative Examples 5, 11, and 12, in which the La:Fe ratio was 50:50 (molar ratio), exhibited a certain anti-algae effect. However, at this La:Fe ratio, even if the amount of lanthanum ferrite was increased, the anti-algae product did not maintain its anti-algae property for an extended period of time.

On the other hand, the anti-algae products of Reference Examples 1, 3, and 4 with a La:Fe ratio of 60:40 (molar ratio) exhibited an excellent anti-algae effect. Even in the case of Reference Example 2, in which the amount of lanthanum ferrite in the coating solution is 2% by mass, an excellent anti-algae effect can be exhibited as compared with Reference Comparative Examples 1 and 2, in which lanthanum ferrite is not used. confirmed. In addition, by comparing Reference Examples 1 and 4 with Reference Example 3, it was found that increasing the amount of lanthanum ferrite added prolongs the period of time that the anti-algae product maintains its anti-algae property.

Similarly, it was confirmed that the anti-algae products of Reference Examples 2 and 5, in which the La:Fe ratio was 80:20 (molar ratio), exhibited an excellent anti-algae effect.

From the above results, it can be concluded that an anti-algae agent composed of a predetermined lanthanum ferrite exhibits an excellent anti-algae effect even when used in a small amount, and that the period during which the anti-algae effect is maintained can be extended by increasing the compounding amount of lanthanum ferrite. was confirmed.

Claims (10)

A rare earth ferrite represented by the following formula (1);
a solvent-based acrylic resin having a reactive group with isocyanate;
A rare earth ferrite dispersion resin liquid containing:
_{Ln2xFe2 (1-x) O3} (1)
(In formula (1), Ln is a rare earth element selected from the group consisting of lanthanum, praseodymium, neodymium, and yttrium, and x is a number of 0.45 or more and less than 1.00.). 2. The rare earth ferrite dispersion resin liquid according to claim 1, wherein x in the formula (1) is a number of 0.55 or more and less than 1.00. 2. The rare earth ferrite dispersed resin liquid according to claim 1, wherein x in the formula (1) is a number of 0.55 or more and 0.75 or less. 3. The rare earth ferrite dispersed resin liquid according to claim 1, wherein Ln in the formula (1) is lanthanum. The rare earth ferrite-dispersed resin liquid according to any one of claims 1 to 4, wherein the rare earth ferrite is at least one selected from the group consisting of anti-algae agents, anti-mold agents, and anti-bacterial agents. A product comprising a substrate and a rare earth ferrite-containing layer laminated or impregnated on said substrate,
The rare earth ferrite-containing layer is a layer formed from a treatment liquid containing the rare earth ferrite dispersed resin liquid according to any one of claims 1 to 5.
product. 7. The product of claim 6 selected from the group consisting of ships, revetments, building materials, fishing nets, aquaculture nets, aquariums, pools, pool course ropes, buoys, and tiles. 7. The product of claim 6, selected from the group consisting of outer walls, inner walls, building materials, air filters, packing, and tanks or pipes for water storage or water flow. 7. The product of claim 6, selected from the group consisting of interior walls, building materials, joint materials, sealants, furniture, air filters, insoles, clothing, hygiene products, medical materials or instruments, bath mats, towels, and bedding. . A paint comprising the rare earth ferrite dispersed resin liquid according to any one of claims 1 to 4.