Rare earth ferrite-dispersed resin liquid, product, and paint

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, with a specific aqueous resin, 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 an aqueous urethane resin. 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

[0001] The present invention relates to a rare earth ferrite dispersion resin liquid, a product provided with a layer formed from the rare earth ferrite dispersion resin liquid, and a paint containing the rare earth ferrite dispersion resin liquid.

Background Art

[0002] In recent years, ferrite compounds have been proposed as algaecides with low environmental pollution and excellent safety. For example, Patent Document 1 discloses an algaecide additive mainly composed of orthoferrite containing a rare earth element selected from lanthanum (La), praseodymium (Pr), neodymium (Nd), and yttrium (Y), iron, and oxygen, an algaecidal paint using the same, and an algaecide product obtained by applying the paint to the surface of a substrate.

[0003] In Patent Document 1, the algaecide effect is considered in relation to the magnetism of the material, and it is explained that orthoferrite with a rare earth oxide:Fe2O3 = 1:1 (molar ratio), which has a small coercive force and shows a magnetic force close to the intrinsic magnetic field of plants, is most preferable as the algaecide additive.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Generally, rare earth ferrites applied to building materials, ship bottoms, etc. are incorporated into a paint, and a rare earth ferrite-containing layer is formed on the substrate by applying the paint to the surface of the substrate. Therefore, in the paint, it is preferable that the rare earth ferrites are uniformly dispersed.

[0006] The present invention has been made in view of the above background, and an object thereof is to provide a rare earth ferrite-dispersed resin liquid having high dispersibility of rare earth ferrite.

Means for Solving the Problems

[0007] The inventors of the present invention conducted intensive studies to solve the above problems. As a result, they found that a dispersed resin liquid having high dispersibility of rare earth ferrite can be obtained by blending a rare earth ferrite having a specific composition with an aqueous urethane resin, and thus completed the present invention. That is, the present invention is as follows.

[0008] 《Aspect 1》 A rare earth ferrite-dispersed resin liquid containing: a rare earth ferrite represented by the following formula (1); an aqueous urethane resin; Ln 2x Fe 2(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-dispersed 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 an algaecide, a fungicide, and an antibacterial agent. 《Aspect 6》 A product comprising a substrate and a rare earth ferrite-containing layer laminated or impregnated on the 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>> The product according to Aspect 6, selected from the group consisting of a ship, a revetment, building materials, a fishing net, a culture net, a water tank, a pool, a pool course rope, a buoy, and a tile. <<Aspect 8>> The product according to Aspect 6, selected from the group consisting of an outer wall, an inner wall, building materials, an air filter, a packing, and a tank or pipe for storing or passing water. <<Aspect 9>> The product according to Aspect 6, selected from the group consisting of an inner wall, building materials, a joint material, a sealing material, furniture, an air filter, an insole, clothing, sanitary products, medical materials or instruments, a bath mat, a towel, and bedding. <<Aspect 10>> A paint containing the rare earth ferrite-dispersed resin liquid according to any one of Aspects 1 to 4.

Advantages of the Invention

[0009] According to the present invention, a rare earth ferrite-dispersed resin liquid with high dispersibility of rare earth ferrite is provided.

[0010] The treatment liquid such as a coating liquid or an impregnating 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, and the product provided with the rare earth ferrite-containing layer formed from the treatment liquid can uniformly exhibit the effects such as algae prevention, mold prevention, and antibacterial property caused by rare earth ferrite.

Modes for Carrying Out the Invention

[0011] <<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 an aqueous urethane resin: Ln 2x Fe 2(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 greater than or equal to 0.45 and less than 1.00.).

[0012] According to the present invention, there is provided a rare earth ferrite dispersion resin liquid with high dispersibility of rare earth ferrite. Although not limited to theory, this is presumably because in an aqueous urethane resin, that is, an aqueous resin liquid in which a polymer having a urethane bond is dispersed, the urethane groups of the polymer adhere to the particles of rare earth ferrite, etc., promoting the dispersion of the particles of rare earth ferrite.

[0013] The constituent components of the rare earth ferrite dispersion resin liquid of the present invention will be described below.

[0014] 《Rare Earth Ferrite》 The rare earth ferrite used in the rare earth ferrite dispersion resin liquid of the present invention is a rare earth ferrite compound having a specific composition, and is represented by the following formula (1): Ln 2x Fe 2(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 greater than or equal to 0.45 and less than 1.00.).

[0015] If the rare earth (Ln):Fe ratio in the rare earth ferrite is within the above range, a high anti-mold effect can be obtained.

[0016] The rare earth ferrite may be in any form as long as x in the above formula (1) is a number greater than or equal to 0.45 and less than 1.00. For example, it may form a solid solution with a uniform composition throughout, or may be a mixture of the LnFeO3 phase and the Ln2O3 phase, or a mixture of a solid solution with a uniform composition, the LnFeO3 phase, and the Ln2O3 phase. Further, it may contain phases other than these.

[0017] In formula (1), x may be 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, 0.70 or more, or 0.75 or more, and may also be 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 0.60 or less.

[0018] In the above formula (1), x may be, for example, a number of 0.55 or more and less than 1.00, and further may be a number of 0.55 or more and 0.75 or less. Regarding this, as a result of a detailed study on the composition of the rare earth ferrite and its algae-proof effect, the inventors of the present invention set the Ln:Fe ratio in the rare earth ferrite in a region richer in rare earths than 1:1 (molar ratio), thereby (1) improving the dispersibility of the rare earth ferrite compound in the aqueous urethane resin, and (2) finding that the algae-proof effect is improved and the period during which the effect continues also becomes longer.

[0019] In addition, the rare earth (Ln) in formula (1) may particularly be lanthanum from the viewpoints of excellent mold-proof property, algae-proof property, 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.

[0020] <Content of rare earth ferrite> The content of the rare earth ferrite in the rare earth ferrite-dispersed resin liquid of the present invention may be, 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 with respect to the solid content of the aqueous urethane resin from the viewpoint of sufficiently ensuring the dispersibility of the rare earth ferrite, and 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 from the viewpoint of obtaining good coatability.

[0021] <Method for producing rare earth ferrite> The method for manufacturing the rare earth ferrite used in the present invention is not particularly limited. For example, it may be manufactured by applying an appropriate stress to a mixture containing a rare earth source and an iron source in a predetermined ratio, pulverizing and mixing them, and then firing them.

[0022] The stress applied here may be, for example, frictional force, shear force, shear stress, or impact force. As a method of applying such stress to the mixture of the rare earth source and the iron source, for example, a method of wet pulverization in a ball mill can be mentioned.

[0023] As the rare earth source, for example, oxides of desired rare earth elements may be used, or bastnasite, monazite, xenotime, etc. may be used.

[0024] As the rare earth element, from the viewpoints of the excellent algaecidal property, antifungal property, antibacterial property, and cost of the obtained rare earth ferrite, it is preferable to use lanthanum. Among them, if La2O3 is used, a lanthanum ferrite with high effect and relatively low cost can be manufactured.

[0025] As the iron source, oxides such as FeO, Fe3O4, and Fe2O3; oxyoxides such as FeOOH, ferrihydrite, and schwertmannite; hydroxides such as Fe(OH)2 and Fe(OH)3; etc. may be used.

[0026] Among these, if FeOOH is used as the iron source, since the reactivity is higher compared to Fe2O3 etc., firing at a low temperature becomes possible, and a rare earth ferrite with a smaller particle diameter compared to Fe2O3 etc. can be manufactured.

[0027] When the pulverization and mixing of the mixture of the rare earth source and the iron source are carried out by wet pulverization, as the liquid medium, for example, water, alcohol, etc. may be used. After the mixture of the rare earth source and the iron source is pulverized and mixed, if necessary, the liquid medium may be removed by an appropriate method such as heating and drying, and then firing may be carried out.

[0028] The firing temperature is not particularly limited and can be set as appropriate. For example, it may be carried out at a temperature of 700 °C or higher, 800 °C or higher, 900 °C or higher, or 1,000 °C or higher, and, for example, 1,300 °C or lower, 1,200 °C or lower, 1,100 °C or lower, or 1,000 °C or lower.

[0029] For example, if it is in the range of 800 °C or higher and 1,000 °C or lower, a rare earth ferrite having a more excellent algae-proof effect, mold-proof effect, and antibacterial effect can be obtained.

[0030] The firing time is not particularly limited either and can be set as appropriate. For example, it may be carried out for a time of 1 hour or longer, 2 hours or longer, 3 hours or longer, 4 hours or longer, 6 hours or longer, 8 hours or longer, 12 hours or longer, or 15 hours or longer, and 72 hours or shorter, 48 hours or shorter, 36 hours or shorter, 24 hours or shorter, 18 hours or shorter, or 15 hours or shorter.

[0031] The ambient atmosphere during firing may be an oxidizing atmosphere. For example, firing may be carried out in air.

[0032] After firing, if necessary, by appropriately performing pulverization, classification, etc. in an appropriate method, a rare earth ferrite that can be used in the present invention can be obtained.

[0033] <Uses of rare earth ferrite> Since rare earth ferrite has a low environmental pollution level and excellent safety, it can be used in various applications.

[0034] Rare earth ferrite can be used, for example, in at least one or more uses selected from the group consisting of an algae-proof agent, a mold-proof agent, and an antibacterial agent. In particular, it exhibits excellent performance as an algae-proof agent or a mold-proof agent.

[0035] For example, when used as an algae-proof agent, it is possible to suppress a decrease in the algae-proof effect over time, and when used as a mold-proof agent, it is possible to exhibit a mold-proof effect on its surroundings as well.

[0036] 《Water-based urethane resin》 The water-based urethane resin used in the rare earth ferrite dispersion resin liquid of the present invention is not particularly limited as long as a polymer having a urethane bond is dispersed in water as a medium.

[0037] Therefore, as the water-based urethane resin, an emulsion-type urethane resin or a water-soluble urethane resin to which a hydrophilic group (any of anionic, cationic, and nonionic) or a hydrophilic segment is added may be used.

[0038] Here, the emulsion-type urethane resin may be one obtained by reacting a polyisocyanate and a polyol and forcibly emulsifying them using a surfactant, or one obtained by emulsifying a urethane resin to which a hydrophilic group (any of anionic, cationic, and nonionic) or a hydrophilic segment is added.

[0039] In addition, a chain extender may be used to obtain a urethane resin with a higher molecular weight.

[0040] Examples of the polyol used as a raw material for the urethane resin include polyester polyol, polycarbonate diol, polyether polyol, and the like.

[0041] As the solvent constituting the water-based urethane resin, other solvents may be blended as long as water is used as the main component. Examples of the other solvents include alcohols such as isopropanol, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, esters, and the like.

[0042] As the water-based urethane resin, commercially available products can also be used. Examples of the commercially available products include Boncoat (registered trademark) HY-364 (DIC Corporation), which is an aqueous urethane composite acrylic resin emulsion, and Hydran (registered trademark) series, which is a water-based polyurethane dispersion.

[0043] 《Other components》 The rare earth ferrite-dispersed resin liquid of the present invention may contain optional components in addition to the above-described rare earth ferrite and the aqueous urethane resin. Examples of other components include resins, solvents, additives, etc. other than the components of the aqueous urethane resin.

[0044] <Resin other than the components of the aqueous urethane resin> The resin other than the components of the aqueous urethane resin, which is optionally contained in the rare earth ferrite-dispersed resin liquid of the present invention, is not particularly limited. For example, it may be an acrylic resin, an acrylic-silicone resin, a silicone resin, an aminoalkyd resin, an epoxy resin, a phenol resin, a polyurethane resin, an unsaturated polyester resin, a fluororesin, etc.

[0045] <Solvent> The solvent contained in the rare earth ferrite-dispersed resin liquid of the present invention is not particularly limited, and may be selected from, for example, alcohol, ketone, aliphatic hydrocarbon, aromatic hydrocarbon, ester, etc.

[0046] 《Method for producing rare earth ferrite-dispersed 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 an aqueous urethane resin, a rare earth ferrite, and other optional components at a predetermined ratio.

[0047] 《Product》 Another aspect of the present invention is a product comprising a substrate and a rare earth ferrite-containing layer laminated 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 impregnating liquid containing the rare earth ferrite-dispersed resin liquid of the present invention.

[0048] <Substrate> The substrate in the product of the present invention may be any article to which rare earth ferrite is to be applied. It may be an article made of any material, having any shape, and being any article to which the performance of rare earth ferrite is to be applied.

[0049] When the product of the present invention is in a form in which the rare earth ferrite-containing layer is impregnated into the substrate, the substrate may be, for example, a woven or non-woven fabric formed from fibers, or a porous film or the like.

[0050] <Rare earth ferrite-containing layer> 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 impregnating liquid containing the rare earth ferrite dispersion resin liquid of the present invention. The rare earth ferrite-containing layer is laminated or impregnated on the substrate.

[0051] The rare earth ferrite-containing layer formed from the treatment liquid containing the rare earth ferrite dispersion resin liquid of the present invention contains rare earth ferrite and urethane resin as essential components, but the rare earth ferrite-containing layer may contain any other components. The optional components are not particularly limited, and examples thereof include resins, binders, additives, and the like.

[0052] The treatment liquid containing the rare earth ferrite dispersion resin liquid of the present invention for forming the rare earth ferrite-containing layer may be, for example, a mixture obtained by mixing the rare earth ferrite dispersion resin liquid of the present invention with a solution or dispersion liquid containing other resins and additives, or a mixture obtained by adding other resins and additives to the rare earth ferrite dispersion resin liquid of the present invention.

[0053] In the treatment liquid containing the rare earth ferrite dispersion resin liquid of the present invention for forming the rare earth ferrite-containing layer, from the viewpoint of sufficiently expressing the performance of the rare earth ferrite, the content of the 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 or more as a ratio of the rare earth ferrite to the total solid content of the treatment liquid. 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, 40% by mass or less, 30% by mass or less, or 20% by mass or less.

[0054] The method for forming the rare earth ferrite-containing layer is not particularly limited. For example, there are a method of applying a treatment liquid containing a rare earth ferrite-dispersed resin liquid to a substrate and drying it to form a cured product, or a method of immersing the substrate in a treatment liquid containing a rare earth ferrite-dispersed resin liquid, impregnating the substrate with the treatment liquid, and then drying it.

[0055] 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.

[0056] The coating amount of the treatment liquid for forming the rare earth ferrite-containing layer, as the dry mass after solvent removal per unit area, is, for example, 5 g / m 2 or more, 10 g / m 2 or more, 15 g / m 2 or more, 20 g / m 2 or more, or 25 g / m 2 or more, and may be, 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.

[0057] <Other configurations> The product of the present invention only needs to include a substrate and a rare earth ferrite-containing layer laminated or impregnated on the substrate as essential configurations, and may also include other configurations. Examples of other configurations include other layers, and the other layers may be on the outside of the substrate, between the substrate and the rare earth ferrite-containing layer, or on the outside of the rare earth ferrite-containing layer.

[0058] Examples of other layers include a primer layer formed on the substrate. By forming a rare earth ferrite-containing layer on the primer layer, the adhesion can be improved.

[0059] Further, by laminating and coating resin or the like on the outside of the rare earth ferrite-containing layer, it is possible to suppress a decrease in the effect caused by rare earth ferrite due to the dropout or leakage of rare earth ferrite during long-term use.

[0060] Furthermore, by laminating a hue pigment layer or the like on the outside of the rare earth ferrite-containing layer, the degree of freedom of the color design of the product may be increased. Also, other functional layers may be laminated or combined to provide performance different from that of the rare earth ferrite.

[0061] <Use> The use of the product of the present invention is not particularly limited. However, when rare earth ferrite is used as an algaecide, for example, it may be a product selected from the group consisting of outer walls, ships, revetments, building materials, fishing nets, aquaculture nets, water tanks, pools, pool course ropes, buoys, and tiles.

[0062] When rare earth ferrite is used as a fungicide, for example, it may be a product selected from the group consisting of outer walls, inner walls, building materials, air filters, packings, and tanks or pipes for storing or passing water.

[0063] When rare earth ferrite is used as an antibacterial agent, for example, it may be a product selected from the group consisting of inner walls, building materials, joint materials, sealing materials, furniture, air filters, insoles, clothing, sanitary products, medical materials or instruments, bath mats, towels, and bedding.

[0064] 《Paint》 Another aspect of the present invention may be a paint containing the rare earth ferrite-dispersed resin liquid of the present invention.

[0065] In addition to the rare earth ferrite-dispersed resin liquid of the present invention, the paint may contain other components such as resin and solvent.

[0066] The resin optionally contained in the coating is not particularly limited and may be, for example, an acrylic resin, an acrylic-silicone resin, a silicone resin, an amino alkyd resin, an epoxy resin, a phenol resin, a polyurethane resin, an unsaturated polyester resin, a fluororesin, or the like.

[0067] The solvent contained in the coating is not particularly limited and may be selected from, for example, water, alcohol, ketone, aliphatic hydrocarbon, aromatic hydrocarbon, ester, etc.

[0068] In the coating, from the viewpoint of sufficiently exhibiting the performance of the rare earth ferrite, the content of the rare earth ferrite, as the ratio of the rare earth ferrite to the total solid content of the coating, may be, 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, and 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, 40% by mass or less, 30% by mass or less, or 20% by mass or less.

[0069] The method for producing the coating is not particularly limited. For example, it may be prepared by mixing a commercially available synthetic resin coating and the rare earth ferrite dispersion resin liquid of the present invention at a predetermined ratio.

[0070] <Use> The coating of the present invention can be used for forming the rare earth ferrite-containing layer in the product of the present invention described above. Further, for example, it may be used as a joint material (a filler for gaps between tiles, concrete, bricks, etc.), a sealing material, a caulking material, an adhesive, or the like.

Example

[0071] 《Example 1》 <Production of lanthanum ferrite> In a ball mill using 10 mmΦ alumina balls as the grinding medium, 0.25 mol part of La2O3, 0.5 mol part of FeOOH, and water were charged and ground and mixed for 5 hours. The obtained ground product was dried at 300 °C for 15 hours and then disintegrated with a rotary grinder. The obtained disintegrated product was fired at 1,000 °C for 15 hours and then ground with a hammer mill to obtain lanthanum ferrite (formula LaFeO3) with La:Fe = 50:50 (molar ratio).

[0072] <Preparation of Lanthanum Ferrite Dispersion Resin Liquid> To an aqueous urethane composite acrylic resin emulsion (trade name: Boncoat (registered trademark) HY-364, manufactured by DIC Corporation), the lanthanum ferrite prepared above was added at a composition such that the solid content concentration was 30%. Further, 20 g of 3 mmφ zirconia beads were added and stirred with a paint shaker for 30 minutes to obtain a lanthanum ferrite dispersion resin liquid.

[0073] <Dispersibility Evaluation> The prepared lanthanum ferrite dispersion resin liquid was allowed to stand for 4 days, and the dispersion state of the lanthanum ferrite after 4 days was visually evaluated according to the following evaluation criteria. The results are shown in Table 1. ◎: There was no sedimentation of lanthanum ferrite and it was uniformly dispersed. 〇: Sedimentation of lanthanum ferrite had started, but there was no boundary between the precipitate and the dispersion resin liquid. △: Lanthanum ferrite had sedimented, there was a boundary between the precipitate and the dispersion resin liquid, and it was separated into two layers.

[0074] <<Example 2>> A lanthanum ferrite dispersion resin liquid was prepared in the same manner as in Example 1 except that the resin for constituting the dispersion resin liquid was changed to the products shown in Table 1. The obtained lanthanum ferrite dispersion resin liquid was evaluated for dispersibility in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0075] <<Examples 3 to 4, Comparative Examples 1 to 2>> Lanthanum ferrite was synthesized in the same manner as in Example 1, except that the composition ratio shown in Table 1 was used. Using the obtained lanthanum ferrite and the products shown in Table 1 as the resin, a lanthanum ferrite-dispersed resin liquid was prepared in the same manner as in Example 1. The obtained lanthanum ferrite-dispersed resin liquid was evaluated for dispersibility in the same manner as in Example 1. The evaluation results are shown in Table 1.

[0076]

Table 1

[0077] From the above Examples and Comparative Examples, when rare earth ferrite is dispersed in an aqueous urethane resin, that is, an aqueous resin liquid in which a polymer having a urethane bond is dispersed, regarding the molar ratio of rare earth (La) to iron (Fe), when the rare earth is less than iron (La:Fe (molar ratio) = 40:60), compared to when the rare earth is equivalent to iron (La:Fe (molar ratio) = 50:50), especially when the rare earth is more than iron (La:Fe (molar ratio) = 60:40), it is understood that the dispersion of rare earth ferrite is promoted.

[0078] 《Reference Examples and Reference Comparative Examples》 In the following Reference Examples and Reference Comparative Examples, it is shown that by setting the Ln:Fe ratio in rare earth ferrite in a rare earth-rich region more than 1:1 (molar ratio), the algae prevention effect is improved and the period during which the effect continues is also prolonged.

[0079] 《Reference Example 1》 (1) Synthesis of lanthanum ferrite 0.3 mol part of La2O3, 0.4 mol part of FeOOH, and water were charged into a ball mill using 10 mmΦ alumina balls as the grinding media, and ground and mixed for 5 hours. The obtained ground product was dried at 300 °C for 15 hours and then crushed with a rotary crusher. The obtained crushed product was calcined at 1,000 °C for 15 hours and then ground with a hammer mill to obtain lanthanum ferrite with La:Fe = 60:40 (molar ratio) (composition formula La 1.2 Fe 0.8 O3).

[0080] (2) Preparation of Algae-Resistant 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 prepare an algae-resistant coating liquid. The composition of this algae-resistant coating liquid was adjusted such that the blending amount of lanthanum ferrite was 10% by mass with respect to 90 parts by mass of the resin contained in the synthetic resin paint.

[0081] (3) Manufacture of Algae-Resistant Product As the base material, a polyethylene terephthalate (PET) film (thickness 50 μm) was used. The above-mentioned algae-resistant coating liquid was applied onto one side thereof using a wire bar #32, and then dried at 60 °C for 2 days (48 hours) to produce an algae-resistant product having an algae-resistant layer on one side of the PET film. The coating amount of the algae-resistant layer was 36.8 g / m 2 .

[0082] (4) Evaluation of Algae-Resistant Product An evaluation sample obtained by cutting the obtained algae-resistant product into a 5 cm × 5 cm square was suspended in a rectangular water tank with a bottom area of 25 cm × 20 cm by a string. Seawater collected from the sea was poured into this water tank to a water depth of 10 cm, and the evaluation sample was completely submerged in the seawater. The water tank in this state was left standing in an environment exposed to outdoor sunlight, and every time a predetermined period elapsed, the adhesion state of algae on the coated surface was visually examined and evaluated according to the following criteria. The evaluation results are shown in Table 2. When no algae adhesion was observed on the coated surface: "-" When the adhesion area of algae was 10% or less of the area of the coated surface: "+" When the adhesion area of algae was more than 10% and 50% or less of the area of the coated surface: "++" When the adhesion area of algae exceeded 50% of the area of the coated surface: "+++"

[0083] 《Reference Example 2》 The preparation amounts of La2O3 and FeOOH were changed to 0.4 mol parts and 0.2 mol parts, respectively, and in the same manner as in Reference Example 1, lanthanum ferrite with La:Fe = 80:20 (molar ratio) (composition formula La 1.6 Fe 0.4 O3) was synthesized, and using this, an anti-algal coating liquid was prepared to produce an anti-algal product. Regarding the obtained anti-algal product, evaluation was carried out in the same manner as in Reference Example 1. The evaluation results are shown in Table 2.

[0084] 《Reference Comparative Example 1》 An evaluation sample was prepared by cutting a PET film in a state where no anti-algal coating liquid was applied into a 5 cm × 5 cm square, and the evaluation of the anti-algal product was carried out in the same manner as in Reference Example 1. The evaluation results are shown in Table 2.

[0085] 《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 blended in the coating liquid. The evaluation results are shown in Table 2.

[0086] 《Reference Comparative Examples 3 to 5》 Lanthanum ferrites with different La:Fe ratios were synthesized in the same manner as in Reference Example 1, except that the preparation amounts of La2O3 and FeOOH were changed as shown in Table 2, and using this, an anti-algal coating liquid was prepared to produce an anti-algal product. Regarding the obtained anti-algal product, evaluation was carried out in the same manner as in Reference Example 1. The evaluation results are shown in Table 2.

[0087]

Table 2

[0088] From the results in Table 2, it was confirmed that anti-algal properties were exhibited in Reference Comparative Examples 3 to 5 and Reference Example 1 using lanthanum ferrite, as compared with Reference Comparative Examples 1 and 2 that did not use lanthanum ferrite. However, in the anti-algal products using lanthanum ferrite with a La:Fe ratio of 50:50 (molar ratio) or a lower La ratio than this, the anti-algal properties could not be maintained for a long period (Reference Comparative Examples 3 to 5).

[0089] On the other hand, in the algae-proof 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), no algae growth was observed on the coated surface even after 8 weeks, and it was confirmed that they exhibited excellent algae-proof effects.

[0090] 《Reference Examples 3 to 5, and Reference Comparative Examples 6 to 12》 Except that the charged amounts of La2O3 and FeOOH were changed as described in Table 3 respectively, lanthanum ferrite with different La:Fe ratios was synthesized in the same manner as in Reference Example 1. Using the obtained lanthanum ferrite, except that the compounding amounts of the lanthanum ferrite and the resin were changed as described in Table 3 respectively, an algae-proof coating liquid was prepared in the same manner as in Reference Example 1, and an algae-proof product was produced using this. The obtained algae-proof products were 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 to 5.

[0091]

Table 3

[0092] According to Table 3, it was found that the algae-proof product of Reference Comparative Example 6 with a La:Fe ratio of 42:58 (molar ratio) did not exhibit an algae-proof effect, similar to Reference Comparative Examples 1 and 2 that did not use lanthanum ferrite. Also, in the algae-proof products of Reference Comparative Examples 3, 7, and 8 with a La:Fe ratio of 46:54 (molar ratio), a slight algae-proof effect was exhibited, but the effect was low.

[0093] On the other hand, the algae-proof products of Reference Comparative Examples 5, 11, and 12 with a La:Fe ratio of 50:50 (molar ratio) exhibited a certain algae-proof effect. However, at this La:Fe ratio, even if the compounding amount of lanthanum ferrite was increased, the maintenance period of the algae-proof property of the algae-proof product was not extended.

[0094] In contrast, excellent algicidal effects were exhibited by the algicidal products of Reference Examples 1, 3, and 4 with a La:Fe ratio of 60:40 (molar ratio). Even in the case of Reference Example 2 where the content of lanthanum ferrite in the coating liquid was 2% by mass, it was confirmed that an excellent algicidal effect was exhibited compared to Reference Comparative Examples 1 and 2 where no lanthanum ferrite was used. Also, from the comparison between Reference Examples 1 and 4 and Reference Example 3, it was found that increasing the content of lanthanum ferrite extended the period during which the algicidal property of the algicidal product was maintained.

[0095] Similarly, it was confirmed that excellent algicidal effects were exhibited by the algicidal products of Reference Examples 2 and 5 with a La:Fe ratio of 80:20 (molar ratio).

[0096] From the above results, it was confirmed that an algicide composed of a predetermined lanthanum ferrite exhibited an excellent algicidal effect with a small amount of use, and by increasing the content of lanthanum ferrite, the period during which the algicidal effect was maintained could be extended.

Claims

1. A rare earth ferrite represented by the following formula (1), An aqueous urethane resin, A rare earth ferrite dispersion resin liquid containing: Ln ２ｘ Fe ２（１－ｘ） O ３ (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 0.50 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.

3. 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 0.75 or less.

4. The rare earth ferrite dispersion resin liquid according to Claim 1 or 2, wherein Ln in the formula (1) is lanthanum.

5. The rare earth ferrite dispersion 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 an algaecide, a fungicide, and an antibacterial agent.

6. A product comprising a substrate and a rare earth ferrite-containing layer laminated or impregnated on the substrate, wherein the rare earth ferrite-containing layer is a layer formed from a treatment liquid containing the rare earth ferrite dispersion resin liquid according to any one of Claims 1 to 5. Product.

7. The product according to Claim 6, selected from the group consisting of a ship, a revetment, building materials, a fishing net, a fish farming net, an aquarium, a pool, a pool course rope, a buoy, and a tile.

8. The product according to Claim 6, selected from the group consisting of an outer wall, an inner wall, building materials, an air filter, a packing, and a tank or pipe for storing or passing water.

9. The product according to Claim 6, selected from the group consisting of an inner wall, building materials, a joint material, a sealing material, furniture, an air filter, an insole, clothing, sanitary products, medical materials or instruments, a bath mat, a towel, and bedding.

10. A paint containing the rare earth ferrite dispersion resin liquid according to any one of Claims 1 to 4.

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