Films, resin compositions, resin products, fiber materials and fiber products

Abstract

To provide a laminated film, a resin composition, and a textile material having an increased ability to oxidize and degrade harmful substance and excellent antiviral performance.SOLUTION: The present invention discloses: a film containing cerium oxide particles surface-treated with a boron compound on at least one surface layer; a resin composition containing cerium oxide particles surface-treated with a boron compound; and a textile material containing cerium oxide particles surface-treated with a boron compound.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a film having antiviral properties, a resin composition, a resin product, a fiber material, and a fiber product.

Background Art

[0002] Plastic films, including polyester films, have excellent properties such as mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance, and are widely used as base films in many applications such as magnetic recording materials and packaging materials.

[0003] Especially in recent years, with the increasing awareness of safety and hygiene management, antibacterial films that decompose harmful substances and microorganisms have attracted attention. Various particles are used to exhibit antibacterial properties.

[0004] For example, titanium oxide particles have the property of generating reactive oxygen species by photocatalytic characteristics and oxidizing and decomposing organic substances. In addition to being used as an antibacterial agent, they are also expected to be used for decomposing various harmful substances such as low-molecular-weight substances such as acetaldehyde and ammonia, allergens, and viruses.

[0005] Cerium oxide particles (nanoceria) have various characteristics such as oxidation, antioxidant, and antibacterial effects, and are also known to have catalytic activity similar to enzymes such as catalase, oxidase, peroxidase, superoxide dismutase, and phosphatase. In addition, since cerium oxide particles do not require a special light source such as ultraviolet light, they can be expected to be used in different applications from titanium oxide having photocatalytic characteristics. Furthermore, since they are optically transparent when nanoparticulated, there is a possibility of expansion into various optical applications including display applications.

[0006] However, since nanoparticles generally tend to aggregate, a method is used to stabilize and disperse the resulting nanoparticles by including a stabilizing compound in the synthesis process. In the case of cerium oxide nanoparticles, for example, polyacrylic acid can be used as a stabilizer to oxidize cerium(III) ions with hydrogen peroxide to obtain a particle dispersion, or dextran can be used as a stabilizer to neutralize cerium(III) ions with alkali in ammonia water to obtain a particle dispersion.

[0007] Patent Document 1 discloses a technology for a building coating liquid having a photocatalytic layer containing cerium oxide particles, and Patent Document 2 discloses a technology for a laminate using cerium oxide together with an antibacterial compound. Furthermore, Patent Document 3 discloses a technology for an abrasive composition containing colloidal ceria surface-modified with boric acid. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2011-63950 [Patent Document 2] Patent No. 6481619 [Patent Document 3] Japanese Patent Publication No. 2003-183631 [Overview of the project] [Problems that the invention aims to solve]

[0009] However, while Patent Document 1 discloses technology for antifungal and antialgal properties, it does not disclose technology for antiviral properties, and the antifungal and antialgal properties are due to the photocatalytic oxidative power resulting from the interaction between photocatalytic titanium dioxide particles and copper compounds. Furthermore, while Patent Document 2 discloses technology for antibacterial properties, similar to Patent Document 1, it does not describe technology for antiviral properties, and the antibacterial properties are due to inorganic fine particles containing metal ions selected from the group consisting of gold, silver, copper, tin, zinc, and platinum. Moreover, Patent Document 3 does not describe technology for antiviral properties, nor does it describe technology for compounding colloidal ceria surface-modified with boric acid with a film, nor does it describe technology for using it as a resin composition or fiber material.

[0010] The object of the present invention is to provide a film, resin composition, resin product, fiber material, and fiber product that can efficiently inactivate viruses. [Means for solving the problem]

[0011] In view of the above problems, the inventors conducted diligent studies and found that it is possible to produce films, resin compositions, resin products, fiber materials, and fiber products with high oxidation performance, thus completing the present invention.

[0012] This invention consists of the following configuration: [I] A film containing cerium oxide particles (A) surface-treated with a boron compound. [II] The film according to [I], having a laminated structure of two or more layers, wherein at least one surface layer contains the cerium oxide particles (A). [III] The film according to [II], wherein the content of cerium oxide particles (A) in the surface layer is 20% by mass or more and 80% by mass of the total mass of the surface layer. [IV] The film according to any one of [I] to [III], characterized in that the boron compound is a boron compound represented by the following general formula (I).

[0013] BR n (OR') 3-n (I) (In formula (I), n is an integer between 0 and 2, R represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group, and R' represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. If there are multiple R or R', they may be the same or different.) [V] The film according to [IV], characterized in that the cerium oxide particles (A) are cerium oxide particles produced by adding an oxidizing agent to a solution containing a boron compound represented by the general formula (I) and cerium(III) ions. [VI] The film according to [IV] or [V], wherein the boron compound represented by the general formula (I) is boric acid, boric acid ester, boronic acid, boronic acid ester, boric acid, boric acid ester, or borate. [VII] A film according to any one of [I] to [VI], wherein at least one layer is a polyester-based layer. [VIII] A resin composition containing cerium oxide particles (A) surface-treated with a boron compound. [IX] The resin composition according to [VIII], characterized in that the boron compound is a boron compound represented by the following general formula (I). BR n (OR') 3-n (I) (In formula (I), n is an integer from 0 to 2, R represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group, and R' represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. If there are multiple R or R', they may be the same or different.)[X] The resin composition according to [IX], characterized in that the cerium oxide particles (A) are cerium oxide particles produced by adding an oxidizing agent to a solution containing a boron compound represented by the general formula (I) and cerium(III) ions. [XI] The resin composition according to [IX] or [X], wherein the boron compound represented by the general formula (I) is boric acid, boric acid ester, boronic acid, boronic acid ester, boric acid, boric acid ester, or borate. A resin product made using the resin composition according to any one of [XII] to [VIII]. The resin product according to [XII], wherein the resin product is selected from the group consisting of an automotive interior material, an electric product housing, a suspension leather, a handrail, a doorknob, and a partition board. A fiber material containing cerium oxide particles (A) surface-treated with a boron compound. The fiber material according to [XIV], wherein the boron compound is a boron compound represented by the following general formula (I). BR n (OR’) 3-n (I) (In formula (I), n is an integer of 0 to 2, R represents any one of an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group, and R’ represents any one of hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. When a plurality of R or R’ exist, they may be the same or different from each other.) The fiber material according to [XV], wherein the cerium oxide particles (A) are cerium oxide particles produced by adding an oxidizing agent to a solution containing the boron compound represented by the general formula (I) and cerium (III) ions. The fiber material according to [XV] or [XVI], wherein the boron compound represented by the general formula (I) is boric acid, a boric acid ester, boronic acid, a boronic acid ester, phosphonic acid, a phosphonic acid ester, or a borate. A fiber product made using the fiber material according to any one of [XIV] to [XVII]. The fiber product according to [XVIII], wherein the fiber product is selected from the group consisting of a mask, a filter, a mat, a chair, a gown, a white coat, a curtain, a sheet, an automotive interior material, and a wipe. [Advantages of the Invention]

[0014] According to the present invention, it is possible to provide a film, a resin composition, and a fiber material that have higher oxidation performance and can efficiently inactivate viruses, compared to conventional films, resin compositions, and fiber materials containing cerium oxide nanoparticles.

Embodiments for Carrying Out the Invention

[0015] The film, resin composition, and fiber material of the present invention are a film, resin composition, and fiber material containing cerium oxide particles surface-treated with a boron compound. The dispersion containing cerium oxide particles used in the present invention may be described as the dispersion liquid of the present invention in this specification.

[0016] The cerium oxide particles surface-treated with the boron compound used in the present invention may be described as the surface-treated cerium oxide particles of the present invention in this specification.

[0017] <Cerium Oxide Particles> The surface-treated cerium oxide particles of the present invention are composed of a mixture of Ce2O3 and CeO2. With the cerium oxide particles (which may be described as the central core in this specification) as the center, the surface has a structure coated with the above boron compound. It is known that cerium oxide may actually include forms such as hydroxides and oxyhydroxides in addition to the above oxide form. The particle size of the central core is preferably 1 nm or more and 100 nm or less. The particle size is measured using a transmission electron microscope to measure two or more lengths among the major axis diameter, minor axis diameter, and fixed-direction diameter, and the average value is calculated as the particle size.

[0018] The ratio of Ce2O3 and CeO2 in the central core can be calculated as the ratio of cerium(III) and cerium(IV). When calculating the ratio, the surface-treated cerium oxide particles of the present invention are dried and calculated by X-ray photoelectron spectroscopy (XPS).

[0019] Here, in the present invention, that the cerium oxide particles are surface-treated means that the ratio of cerium(III) and cerium(IV) calculated by XPS satisfies cerium(III) / cerium(IV) ≤ 1.0.

[0020] The surface-treated cerium oxide particles of the present invention are obtained by step a: a step of obtaining a solution containing a boron compound and cerium(III) ions, and The cerium oxide particles can be produced by a method for producing cerium oxide particles, which includes step b: adding an oxidizing agent to the mixed solution obtained in step a to form cerium oxide nanoparticles. The method for producing surface cerium oxide particles of the present invention will be described below step by step.

[0021] Step a is the step of obtaining a solution containing a boron compound and cerium(III) ions. To obtain a solution containing a boron compound and cerium(III) ions, a solution of the boron compound and a solution containing cerium(III) ions may be prepared separately and mixed, or, if the solvent of the boron compound solution is water or a solvent compatible with water, a cerium(III) salt may be added to the boron compound solution and mixed.

[0022] In the synthesis of cerium oxide particles, one of the raw materials is a water-soluble cerium salt, and the synthesis is carried out in water or a water-compatible solvent. Boron compounds have moderate hydrophilicity and possess properties that allow for stable dispersion of nanoparticles by forming complexes with the hydroxyl groups of metal oxides. Therefore, in this embodiment, a boron compound having the structure shown in general formula (I) is used as a stabilizer.

[0023] BR n (OR') 3-n (I) In formula (I), n is an integer between 0 and 2, R represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group, and R' represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. Multiple Rs or R's may be the same or different.

[0024] More preferred embodiments of the boron compounds used in the present invention include boric acid (in general formula (I), n=0, R=H, R'=H), boric acid ester (in general formula (I), n=0, R=H, R'=alkyl, etc.), boronic acid (in general formula (I), n=1, R=alkyl, etc., R'=H), boronic acid ester (in general formula (I), n=1, R=alkyl, etc., R'=alkyl, etc.), boric acid (in general formula (I), n=2, R=alkyl, etc., R'=H), boric acid ester (in general formula (I), n=2, R=alkyl, etc., R'=alkyl, etc.), and borates. In the present invention, borates refer to a general term including salts of boric acid, or salts of metaboric acid and polyboric acid obtained by dehydration condensation of boric acid. These borates exist in equilibrium with boric acid and tetrahydroxyboric acid in aqueous solution, thus adopting the structure of boric acid shown in molecular formula (I) in solution. Any counterion can be used for boric acid in borates, including lithium ions, sodium ions, potassium ions, and ammonium ions.

[0025] Examples of such boron compounds include boric acid; boric acid esters such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, and triisobutyl borate; and boronic acids such as methylboronic acid, ethylboronic acid, propylboronic acid, isopropylboronic acid, butylboronic acid, isobutylboronic acid, and phenylboronic acid. Examples of borates include lithium salts, sodium salts, potassium salts, and ammonium salts of boric acid, metaboric acid, diboric acid, metaboric acid, tetraboric acid, pentaboric acid, hexaboric acid, and octaboric acid.

[0026] A solution of a boron compound can be prepared by dissolving the boron compound in any solvent. Water or a water-compatible solvent is preferred. Specific examples of water-compatible solvents include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, tetrahydrofuran, acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), glycerol, ethylene glycol, and oligoethylene glycol. If the boron compound contains substituents with three or fewer carbon atoms, it is preferable that the boron compound dissolves in water. If it contains substituents with four or more carbon atoms, it is preferable that the boron compound dissolves in a 50% aqueous solution of ethylene glycol. If the boron compound is difficult to dissolve in the solvent, it may be dissolved by heating or sonication.

[0027] A solution containing cerium(III) ions can be prepared by dissolving a cerium(III) salt in any solvent. For example, cerium(III) nitrate hexahydrate can be used as the cerium(III) salt.

[0028] The amount of boron compound may be in the range of 0.1 to 1000 molar equivalents relative to cerium(III) ions, preferably 1 to 200 molar equivalents, more preferably 5 to 200 molar equivalents, and most preferably 10 to 100 molar equivalents.

[0029] The amount of cerium(III) salt can be mixed with the boron compound solution so that the concentration of the mixed solution is in the range of 0.01% to 10% by mass. It is preferable to mix the mixed solution for at least 5 minutes until the solution is homogeneous.

[0030] In step a, the solution containing the boron compound and cerium(III) ions preferably contains substantially no trivalent or higher carboxylic acids, such as the compounds listed below. If present, the amount is preferably 0.1 equivalent or less, and more preferably 0.01 equivalent or less, relative to the cerium(III) ions. Specifically, trivalent or higher carboxylic acids include nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), ethylenediamine disuccinic acid (EDDS), glycol etherdiaminetetraacetic acid (EGTA), diethylenetriaminopentaacetic acid (DTPA), citric acid, hydroxyethylethylenediaminetetraacetic acid (HEDTA), polyacrylic acid, and / or salts thereof.

[0031] Step b is a step in which an oxidizing agent is added to the mixed solution obtained in step a to form cerium oxide nanoparticles. Examples of oxidizing agents used in step b include nitric acid, potassium nitrate, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, halogens, hydrogen halides, permanganates, chromic acid, dichromate, oxalic acid, hydrogen sulfide, sulfur dioxide, sodium thiosulfate, sulfuric acid, and hydrogen peroxide. Among these, hydrogen peroxide is particularly preferred. The amount added should be between 0.1 and 10 molar equivalents relative to the cerium(III) ions, and preferably between 0.5 and 2 molar equivalents.

[0032] When an oxidizing agent is added to a solution containing a boron compound and cerium(III) ions, the cerium(III) ions are oxidized to cerium(IV), initiating the synthesis reaction of cerium oxide particles composed of a mixture of Ce2O3 and CeO2. During this reaction, the solution turns yellow, orange, red, or brown. This coloration is due to the conversion of cerium(III) ions to cerium(IV), and the degree of coloration is determined by the ratio of cerium(III) to cerium(IV) present on the surface of the cerium oxide nanoparticles. The end of the reaction can be determined when the color stops changing.

[0033] The hydrodynamic diameter of the cerium oxide nanoparticles in this invention is calculated by measuring dynamic light scattering to derive the autocorrelation function, analyzing it using the Marquadt method, and then calculating the average particle diameter from the number-converted histogram. The ELS-Z from Otsuka Electronics Co., Ltd. is used for measuring dynamic light scattering. The hydrodynamic diameter of the cerium oxide nanoparticles should be between 1 and 1000 nm, and preferably between 1 and 200 nm. The hydrodynamic diameter of the cerium oxide nanoparticles can be controlled by the reaction temperature. The temperature can be arbitrarily set between approximately 4°C and 90°C; lower temperatures yield smaller particle sizes, while higher temperatures yield larger particle sizes. The synthesis reaction of cerium oxide nanoparticles can be carried out at any pH, but since the reaction proceeds more easily in weakly acidic to basic conditions, it is preferable to keep the pH of the solution when adding the oxidizing agent at 5 or higher, more preferably at 6 or higher, and even more preferably at 7 or higher. Sodium hydroxide aqueous solution or ammonia aqueous solution can be used to adjust the pH. Furthermore, as the reaction progresses, the pH of the solution becomes more acidic, so the pH of the reaction solution may be maintained at 5 or higher from the time the oxidizing agent is added until the end of the reaction. The reaction usually finishes in about 5 minutes to 1 hour, and a dispersion containing cerium oxide nanoparticles of the present invention is obtained. For example, if 1 ml of 10% by mass aqueous solution of cerium(III) nitrate hexahydrate is added to 284 mg / 50 ml of boric acid aqueous solution adjusted to pH 8, and then 1 ml of 1.2% by mass aqueous solution of hydrogen peroxide is added and stirred at room temperature, the solution will turn orange, and the particle formation reaction will finish in about 10 minutes, and a dispersion will be obtained.

[0034] The dispersion used in this invention may have its pH adjusted after the reaction is complete. The pH of the dispersion should be in the range of pH 1 to 10, preferably pH 2 to 8. The pH may be adjusted by adding a buffer solution, or by adding an acid such as nitric acid, sulfuric acid, or hydrochloric acid, or a base such as sodium hydroxide or potassium hydroxide. Alternatively, the pH of the dispersion may be adjusted after purification of the dispersion by filtration using an ultrafiltration membrane or dialysis using a semipermeable membrane, as described later.

[0035] The dispersion used in this invention can be filtered with an ultrafiltration membrane or dialyzed with a semipermeable membrane after the reaction is complete to remove any unreacted oxidizing agent, cerium(III) ions, and excess boron compounds remaining in the dispersion. Subsequently, cerium oxide nanoparticles can be isolated from the dispersion by the method described later.

[0036] Cerium oxide nanoparticles can be isolated by drying the dispersion obtained in the above process using an evaporator or freeze-dryer. Alternatively, the dispersion can be dropped onto a substrate such as glass, plastic, or ceramic and air-dried, dried in a desiccator, or dried with a dryer or oven. It can also be isolated by dropping the dispersion onto a heat block and heating it to volatilize the solvent. Furthermore, it can be isolated by drying the dispersion with a spray dryer to volatilize the solvent. Finally, the dispersion can be centrifuged to precipitate the cerium oxide nanoparticles, and the supernatant can be removed. The dispersion can also be filtered by ultrafiltration or suction filtration to completely remove water, thereby isolating the cerium oxide nanoparticles onto a filtration membrane. To improve the efficiency of the drying process in the above operations, an azeotropic solvent may be added to the dispersion, or the solvent in the dispersion may be replaced with a solvent with a lower boiling point. Furthermore, to improve the efficiency of the centrifugation operation, a coprecipitant may be added to the dispersion, or a solvent that improves ionic strength or reduces the dispersibility of nanoparticles may be added. In addition, before the above operation, the dispersion may be fractionated by ultrafiltration or centrifugation to separate the nanoparticle sizes.

[0037] The dispersion used in the present invention may contain, in addition to cerium oxide nanoparticles and water as the solvent, other solvent components that are compatible with water. Examples of other solvent components include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, tetrahydrofuran, acetone, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), glycerol, ethylene glycol, and oligoethylene glycol. These solvent components may be included in an amount of 90% by volume or less. These solvent components may be added to the dispersion after the reaction is complete, added after filtration with an ultrafiltration membrane, used as a dialysate, or added to the dispersion after dialysate. They may also be added to dried cerium oxide nanoparticles to form a dispersion.

[0038] The dispersion used in this invention may contain ionic components. As ionic components, the following are used to provide buffering performance: acetic acid, phthalic acid, succinic acid, carbonic acid, Tris(hydroxymethyl)aminomethane (Tris), 2-Morpholinoethanesulfonic acid, monohydrate (MES), Bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane (Bis-Tris), N-(2-Acetamido)iminodiacetic acid (ADA), Piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-Acetamido)-2-aminoethanesulfonic acid (ACES), 2-Hydroxy-3-morpholinopropanesulfonic acid (MOPSO), N,N-Bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES), 3-Morpholinopropanesulfonic acid (MOPS), N-Tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid(TES), 2-[4-(2-Hydroxyethyl)-1-piperazinyl]ethanesulfonic acid(HEPES), 2-Hydroxy-N-tris(hydroxymethyl)methyl-3-aminopropanesulfonic(TAPSO), Piperazine-1,4-bis(2-hydroxy-3-propanesulfonic acid)(POPSO), 2-Hydroxy-3-[4-(2-hydroxyethyl)-1-piperazinyl]propanesulfonic acid(HEPSO), 3-[4-(2-Hydroxyethyl)-1-piperazinyl]propanesulfonic acid(HEPPS), (Tricine), N,Examples include N-Bis(2-hydroxyethyl)glycine (Bicine) and N-Tris(hydroxymethyl)methyl-3-aminopropanesulfonic acid (TAPS), while sodium chloride and potassium chloride are examples of components that do not impart buffering capacity. These ionic components can be added to a final concentration in the range of 0.1 mM to 1 M. These ionic components may be added to the dispersion after the reaction is complete, added after filtration with an ultrafiltration membrane, used as a dialysate, or added to the dispersion after dialysate. They may also be added to dried cerium oxide nanoparticles to form a dispersion.

[0039] The dispersion used in this invention may be stored as the dispersion after the reaction is complete, or as a purified product obtained by filtering the dispersion after the reaction through an ultrafiltration membrane or by dialyzing through a semipermeable membrane, or as isolated cerium oxide nanoparticles obtained by drying using an evaporator, spray dryer, freeze dryer, etc.

[0040] When the product is in the form of a dried powder, a dispersant may be added before or after drying to suppress the aggregation of the cerium oxide nanoparticles of the present invention. Preferred dispersants include hydrophilic polymers such as starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polyethylene oxide, and polyacrylamide, cationic surfactants such as quaternary ammonium salts, anionic surfactants such as higher fatty acid salts and alkyl sulfate ester salts, amphoteric surfactants such as alkyl betaine, and nonionic surfactants such as polyoxyethylene sorbitan fatty acid salts and polyoxyethylene alkyl ethers. More preferably, the dispersant is polyvinyl alcohol, polyvinylpyrrolidone, a cationic surfactant, and a nonionic surfactant.

[0041] Furthermore, the dispersion of the present invention may be stored as a dispersion containing additional solvent components such as the azeotropic solvent described above, or as a pH-adjusted dispersant. Refrigeration is preferred for storage.

[0042] The dispersion used in this invention may be sterilized before use. One method of sterilization is to pass it through a sterilization filter.

[0043] The film, resin composition, and fiber material of the present invention will be described in detail below.

[0044] <film> The film of the present invention is a film containing the surface-treated cerium oxide particles described above. By adding the cerium oxide particles or dispersion containing cerium oxide particles obtained above, a film containing such particles can be made, which can exhibit oxidative decomposition performance of harmful substances and antiviral properties. In particular, a film having a laminated structure of two or more layers, in which at least one surface layer contains the surface-treated cerium oxide particles described above, can be made into a film with even better decomposition properties. In the surface layer containing cerium oxide particles, the content of cerium oxide particles is preferably 20% by mass or more and 80% by mass or less, relative to the total mass of the surface layer. More preferably, it is 25% by mass or more and 75% by mass or less, and even more preferably 30% by mass or more and 70% by mass or less. By setting the content of cerium oxide particles to 20% by mass or more and 80% by mass or less, relative to the total mass of the surface layer, a uniform layer can be provided without impairing the film properties of the surface layer. As a result, it is possible to fully exhibit the desired decomposition properties. Furthermore, when cerium oxide particles are included at a high concentration, the layer containing the cerium oxide particles may become non-uniform. However, by forming the film using the manufacturing method described later, the uniformity of the layer containing cerium oxide particles can be improved, thereby increasing the resolution.

[0045] The resin constituting the film of the present invention is not particularly limited and may be either a thermoplastic resin or a thermosetting resin, and may be a homopolymer, copolymer, or a blend of two or more types. From the viewpoint of good moldability, a thermoplastic resin is preferred.

[0046] Examples of thermoplastic resins that can be used include polyethylene, polypropylene, polystyrene, polymethylpentene and other polyolefins, alicyclic polyolefins, polyamides such as nylon 6 and nylon 66, aramids, polyimides, polyesters, polycarbonates, polyarylates, polyacetals, polyphenylene sulfide, tetrafluoroethylene, trifluoroethylene, trifluoroethylene chloride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride and other fluorines, acrylics, methacrylics, polyacetals, polyglycolic acid, and polylactic acid. Examples of thermosetting resins that can be used include phenolic resins, epoxy resins, urea resins, melamine resins, unsaturated polyesters, polyurethanes, polyimides, and silicone resins. From the viewpoint of mechanical properties and moldability, polyester is particularly preferred.

[0047] When the film of the present invention is a laminated film having a laminated structure of two or more layers, it is preferable that at least one layer is a layer mainly composed of polyester (hereinafter sometimes referred to as a polyester film; where "main component" means that it is the most abundant component among the components that make up the layer). Polyester has excellent mechanical properties and thermal properties. Therefore, a preferred embodiment of the film of the present invention is a laminated film in which a polyester film is used as the base film and a layer containing cerium oxide particles is provided on the outermost surface of the base film.

[0048] In the film of the present invention, the polyester film that serves as the base film will be described in detail. Polyester is a general term for polymers whose main chain is an ester bond, and it is preferable to use one which has at least one component selected from ethylene terephthalate, propylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, propylene-2,6-naphthalate, ethylene-α,β-bis(2-chlorophenoxy)ethane-4,4-dicarboxylate, etc., as its main component. In the present invention, it is preferable to use polyethylene terephthalate as the polyester film. Furthermore, when heat or shrinkage stress is applied to the polyester film, polyethylene-2,6-naphthalate, which has excellent heat resistance and rigidity, is particularly preferable.

[0049] Polyester films may also contain various additives, such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic particles, fillers, antistatic agents, nucleating agents, etc., to an extent that does not impair their properties.

[0050] It is preferable that the polyester film is biaxially oriented. A biaxially oriented polyester film is generally a polyester sheet or film that has been stretched by approximately 2.5 to 5 times in both the longitudinal direction and the width direction perpendicular to the longitudinal direction, and then heat-treated to complete the crystal orientation, resulting in a film that exhibits a biaxial orientation pattern when measured by wide-angle X-ray diffraction. If the polyester film is not biaxially oriented, it is undesirable because the thermal stability of the film, especially its dimensional stability and mechanical strength, may be insufficient, and its flatness may be poor.

[0051] Furthermore, the polyester film used in the present invention may be a laminated structure of two or more layers. The laminated structure may be, for example, a composite film having an inner layer and a surface layer, wherein the inner layer and the surface layer may be made of chemically different polymers or the same polymer.

[0052] The thickness of the polyester film is not particularly limited and is selected appropriately depending on the application and type, but from the viewpoint of mechanical strength and handling properties, it is usually preferably 10 μm to 500 μm, more preferably 23 μm to 125 μm, and most preferably 38 μm to 75 μm. Furthermore, the polyester film may be a composite film produced by co-extrusion, or a film obtained by laminating the resulting films by various methods.

[0053] If the film of the present invention is a laminated film having two or more layers, a layer containing cerium oxide particles can be provided on the surface layer. The surface layer can be provided by applying a coating composition containing cerium oxide particles to the base film. In the film of the present invention, the surface layer is a layer having been provided on at least one air side of the laminated film. That is, in the case of a single-layer film or a two-layer laminated film, any of the layers constituting the film are considered the surface layer. If the polyester film that serves as the base film is a laminated film of two or more layers, cerium oxide particles may be included in the surface layer of the polyester film.

[0054] From the viewpoint of uniformly dispersing cerium oxide particles in the layer and uniformly forming a layer containing cerium oxide particles, it is preferable to apply a coating composition containing cerium oxide particles to a substrate film, and then solidify the resin or compound (B) contained in the coating composition by heat or ultraviolet light, thereby providing a resin layer containing cerium oxide particles on the surface.

[0055] In the present invention, examples of resins or compounds (B) that can be used in a coating composition containing cerium oxide particles include epoxy resins, melamine resins, oxazoline compounds, carbodiimide compounds, polyester resins, acrylic resins, urethane resins, and polyamide resins. Among these, melamine resins, acrylic resins, urethane resins, and polyamide resins are preferred because they allow for easy control of hydroxyl group interactions and the resin layer is easily modified by high-temperature heating.

[0056] Examples of epoxy resins that can be used as resin or compound (B) include sorbitol polyglycidyl ether-based crosslinking agents, polyglycerol polyglycidyl ether-based crosslinking agents, diglycerol polyglycidyl ether-based crosslinking agents, and polyethylene glycol diglycidyl ether-based crosslinking agents. Commercially available epoxy resins may also be used, such as the epoxy compounds "Denacol" (registered trademark) EX-611, EX-614, EX-614B, EX-512, EX-521, EX-421, EX-313, EX-810, EX-830, EX-850 etc. manufactured by Nagase Chemtec Corporation, diepoxy / polyepoxy compounds (SR-EG, SR-8EG, SR-GLG etc.) manufactured by Sakamoto Pharmaceutical Co., Ltd., and the epoxy crosslinking agent "EPICLON" (registered trademark) EM-85-75W or CR-5L manufactured by Dainippon Ink & Industries, Ltd., among which water-soluble ones are preferred.

[0057] Examples of melamine resins that can be used as resin or compound (B) include melamine, methylolated melamine derivatives obtained by condensing melamine with formaldehyde, compounds partially or completely etherified by reacting methylolated melamine with a lower alcohol, and mixtures thereof. The melamine resin may be a monomer or a condensate consisting of two or more polymers, or a mixture thereof. Examples of lower alcohols used for etherification include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butanol, and isobutanol. Functional groups include imino groups, methylol groups, or alkoxymethyl groups such as methoxymethyl groups and butoxymethyl groups in one molecule, and include imino-type methylated melamine resins, methylol-type melamine resins, methylol-type methylated melamine resins, and fully alkyl-type methylated melamine resins. Among these, methylolated melamine resins are most preferably used.

[0058] Furthermore, the oxazoline compound that can be used as a resin or compound (B) is preferably one that has an oxazoline group as a functional group in the compound, and is composed of an oxazoline group-containing copolymer obtained by copolymerizing at least one monomer containing an oxazoline group with at least one other monomer.

[0059] Examples of monomers containing an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. One or more of these can be used as a mixture. Among these, 2-isopropenyl-2-oxazoline is preferred because it is readily available industrially.

[0060] In oxazoline compounds, at least one other monomer used with a monomer containing an oxazoline group is a monomer copolymerizable with the oxazoline group-containing monomer, such as acrylic acid esters or methacrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid; acrylonitrile; and methacrylonitrile. Any unsaturated nitriles, unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide, and N-methylolmethacrylamide, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, olefins such as ethylene and propylene, halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride, and α,β-unsaturated aromatic monomers such as styrene and α-methylstyrene can be used, and one or more of these can be used as mixtures.

[0061] Furthermore, carbodiimide compounds that can be used as resins or compound (B) are compounds that have one or more carbodiimide groups or cyanamide groups in a tautomer relationship therewith as functional groups within the molecule. Specific examples of such carbodiimide compounds include dicyclohexylmethanecarbodiimide, dicyclohexylcarbodiimide, tetramethylxylylenecarbodiimide, and urea-modified carbodiimide, and these can be used individually or as a mixture of two or more.

[0062] Furthermore, the polyester resin that can be used as the resin or compound (B) is preferably one that has ester bonds in the main chain or side chains and is obtained by polycondensation of a dicarboxylic acid and a diol.

[0063] Aromatic, aliphatic, and alicyclic dicarboxylic acids can be used as raw materials for the polyester resin. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, phthalic acid, 2,5-dimethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bisphenoxyethane-p-p'-dicarboxylic acid, and phenylindanedicarboxylic acid. Examples of aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedionic acid, dimer acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and their ester-forming derivatives.

[0064] The diol components used as raw materials for the polyester resin include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl- 1,6-Hexanediol, 1,2-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, 1,4-Cyclohexanedimethanol, 2,2,4,4-Tetramethyl-1,3-Cyclobutanediol, 4,4'-Thiodiphenol, Bisphenol A, 4,4'-Methylenediphenol, 4,4'-(2-Norbornylidene)diphenol, 4,4'-Dihydroxybiphenol, o-, m-, and p-Dihydroxybenzene, 4,4'-Isopropylidenephenol, 4,4'-Isopropylidenebinediol, Cyclopentane-1,2-Diol, Cyclohexane-1,2'-Diol, Cyclohexane-1,2-Diol, Cyclohexane-1,4-Diol, etc. can be used.

[0065] Furthermore, as the polyester resin, it is also possible to use modified polyester copolymers, such as block copolymers or graft copolymers modified with acrylic, urethane, epoxy, etc.

[0066] The acrylic resin that can be used as the resin or compound (B) is not particularly limited, but one composed of alkyl methacrylate and / or alkyl acrylate is preferred.

[0067] Preferably, alkyl methacrylates and / or alkyl acrylates include methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, maleic acid, itaconic acid, acrylamide, N-methylolacrylamide, and diacetoneacrylamide. One or more of these can be used.

[0068] Furthermore, the urethane resin that can be used as the resin or compound (B) is preferably a resin obtained by reacting a polyhydroxy compound and a polyisocyanate compound by known polymerization methods for urethane resins, such as emulsion polymerization or suspension polymerization.

[0069] Examples of polyhydroxy compounds include polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polytetramethylene glycol, hexamethylene glycol, tetramethylene glycol, 1,5-pentanediol, diethylene glycol, triethylene glycol, polycaptolactone, polyhexamethylene adipate, polyhexamethylene sebacate, polytetramethylene adipate, polytetramethylene sebacate, trimethylolpropane, trimethylolethane, pentaerythritol, polycarbonate diol, and glycerin.

[0070] Examples of polyisocyanate compounds that can be used include hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, isophorone diisocyanate, adducts of tolylene diisocyanate and trimethylenepropane, and adducts of hexamethylene diisocyanate and trimethylolethane.

[0071] Furthermore, the resin layer of the film of the present invention may contain an isocyanate compound as the resin or compound. Examples of isocyanate compounds include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, metaxylylene diisocyanate, hexamethylene-1,6-diisocyanate, 1,6-diisocyanate hexane, adducts of tolylene diisocyanate and hexanetriol, adducts of tolylene diisocyanate and trimethylolpropane, polyol-modified diphenylmethane-4,4'-diisocyanate, carbodiimide-modified diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-vitrylene-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, and metaphenylene diisocyanate.

[0072] Furthermore, since isocyanate groups readily react with water, in terms of the pot life of the coating agent, blocked isocyanate compounds, in which the isocyanate groups are masked with a blocking agent, can be suitably used. In this case, when heat is applied during the drying process after coating the polyester film with the coating composition, the blocking agent dissociates, exposing the isocyanate groups, and as a result, the crosslinking reaction proceeds.

[0073] Furthermore, the polyamide resin that can be used as the resin or compound (B) is preferably a polymer having a heterocyclic amine skeleton in its main chain. The polyamide resin may also have substituents at any position on the main chain or side chains, or substituents at any position on the heterocyclic amine skeleton such as piperazine, pyridine, imidazole, or carbazole. When the main chain has a piperazine skeleton, it is preferable that the piperazine skeleton is located between the carbonyl groups of the main chain, and that the nitrogen in the heterocycle of the piperazine skeleton and the carbonyl group constitute an amide bond. When the main chain has another heterocyclic amine skeleton having two or more primary or secondary amino groups, such as pyridine, imidazole, or carbazole skeletons, it is also preferable that the heterocyclic amine skeleton is located between the carbonyl groups.

[0074] If the polyamide resin used as the resin or compound (B) of the present invention has a piperazine skeleton, the piperazine skeleton may be directly bonded to the carbon linking the amide group, or it may be bonded via an alkyl group or an amino group. If it has a heterocyclic amine skeleton other than a piperazine skeleton, such as a pyridine, imidazole, or carbazole skeleton, the heterocyclic amine skeleton such as a pyridine, imidazole, or carbazole skeleton may be directly bonded to the carbon linking the amide group, or it may be bonded via an alkyl group or an amino group.

[0075] The polyamide resin used as the resin or compound (B) of the present invention is preferably a polymer having a piperazine skeleton in its main chain or side chains, and more preferably a polymer having a piperazine skeleton in its main chain. The polyamide having a piperazine skeleton in its main chain used in the present invention is preferably obtained by a polycondensation reaction between an amine having a piperazine skeleton and a dicarboxylic acid.

[0076] Preferred examples of amines having a piperazine skeleton include piperazine, aminomethylpiperazine, aminoethylpiperazine, aminopropylpiperazine, aminobutylpiperazine, 1,4-bis(aminomethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, and 1,4-bis(4-aminobutyl)piperazine. Among these, aminoethylpiperazine and 1,4-bis(3-aminopropyl)piperazine are more preferred. Furthermore, these amines may have substituents at any position other than the nitrogen atom that can form an amide bond.

[0077] Preferred examples of dicarboxylic acids include 1H-imidazole-2,4-dicarboxylic acid, 1H-imidazole-2,5-dicarboxylic acid, 1H-imidazole-4,5-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, pyridine-2,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, adipic acid, sebacic acid, dodecadicarboxylic acid, terephthalic acid, and isophthalic acid. Furthermore, these dicarboxylic acids may have substituents at any position other than the carboxyl group that can form an amide bond.

[0078] The polyamide resin used as the resin or compound (B) of the present invention can preferably be any polyamide obtained from the above-mentioned combination of amine and dicarboxylic acid, and a polyamide obtained from the combination of aminoethylpiperazine and adipic acid is particularly preferred.

[0079] Furthermore, the polyamide resin used as the resin or compound (B) of the present invention may have a polyalkylene glycol structure in its main chain. Specifically, examples include polyamides having a skeleton of aminoethylpiperazine, adipic acid, and bisaminopropyl polyethylene glycol.

[0080] Furthermore, the polyamide resin used as the resin or compound (B) of the present invention may be a mixture or copolymer of a polyamide having a piperazine, pyridine, imidazole, or carbazole skeleton and other polymers. In this case, specific examples of other polymers include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polypentamethylene adipamide (nylon 56), polypentamethylene sevacamide (nylon 510), polyhexamethylene sevacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), and polyhexamethylene adipamide. Examples include pamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), and polyxylylene adipamide (nylon XD6).

[0081] <Film manufacturing method> The manufacturing method for the film of the present invention is not particularly limited. When manufacturing a film having a laminated structure of two or more layers, preferred methods for creating the laminated structure include a method of co-extruding two or more raw materials and laminating them, a method of bonding two or more films together, an in-line coating method, and an off-coat method. Among these, the in-line coating method is the most suitable considering productivity.

[0082] Here, the in-line coating method refers to a method in which coating is performed within the manufacturing process of the base film. When a polyester film is used as the base film, it is preferable to manufacture the film by applying a coating composition containing surface-treated cerium oxide particles to at least one surface layer of the polyester film before crystal orientation is completed, stretching it in at least one axial direction, and then heat-treating it to complete the crystal orientation of the polyester film. The off-coat method, on the other hand, is a method in which the aforementioned coating composition is applied to at least one surface layer of the completed polyester film, and then dried and cured to form the film.

[0083] Any known coating method can be used to apply the resin composition to the substrate film. Examples include wire bar coating, reverse coating, gravure coating, die coating, blade coating, dip coating, air knife coating, curtain coating, and roller coating.

[0084] In the present invention, it is preferable to apply a coating composition to at least one side of a polyester film that serves as a base film, and then dry it to form a surface layer. In the present invention, when the coating composition contains a solvent, it is preferable to use an aqueous solvent. Using an aqueous solvent suppresses the rapid evaporation of the solvent during the drying process, which not only allows for the formation of a uniform resin layer but also has advantages in terms of environmental impact.

[0085] Here, an aqueous solvent refers to a mixture of water or an organic solvent that is soluble in water, such as water and alcohols (e.g., methanol, ethanol, isopropyl alcohol, butanol), ketones (e.g., acetone, methyl ethyl ketone), or glycols (e.g., ethylene glycol, diethylene glycol, propylene glycol), in any ratio.

[0086] The method of applying the coating composition to the film is not particularly limited, but as mentioned above, an in-line coating method is preferred. Specifically, this refers to a method in which the coating is performed at any stage from melt extrusion of the polyester resin to biaxial stretching, heat treatment, and winding. Typically, the coating is applied to one of the following films: a substantially amorphous unstretched (unoriented) film (A film) obtained by melt extrusion and rapid cooling, a uniaxially stretched (uniaxially oriented) film (B film) which is subsequently stretched in the longitudinal or width direction, or a biaxially stretched (biaxially oriented) film (C film) before heat treatment which is further stretched in the width or longitudinal direction.

[0087] In the present invention, it is preferable to employ a method in which a coating composition is applied to either film A or film B before crystal orientation is completed, the film is then stretched in a uniaxial or biaxial direction, and heat treatment is performed at a temperature higher than the boiling point of the solvent to complete the crystal orientation of the film and to form a resin layer. This method offers advantages in terms of manufacturing costs because film formation and coating and drying of the coating composition (i.e., formation of the resin layer) can be performed simultaneously.

[0088] Among these methods, the method of applying the coating composition to a film (B film) that has been uniaxially stretched in the longitudinal direction, then stretching it in the width direction and heat-treating it, is superior. In this method, compared to the method of applying the coating composition to an unstretched film and then biaxially stretching it, there is one less stretching step after the coating composition is applied, so defects and cracks in the resin layer due to stretching are less likely to occur, and a surface layer with excellent smoothness can be formed. In addition, as mentioned above, by applying the coating composition to the film before the crystal orientation is complete, adhesion between the surface layer and the film can be imparted.

[0089] Therefore, a preferred method for forming the surface layer in the present invention is to apply a coating composition using an aqueous solvent onto a substrate film using an in-line coating method, followed by drying and heat treatment. More preferably, the coating composition is applied in-line to a B film after uniaxial stretching. In the film manufacturing method of the present invention, drying can be carried out in a temperature range of 80°C to 130°C to complete the removal of the solvent from the coating composition. Heat treatment can be carried out in a temperature range of 160°C to 240°C to complete the crystal orientation of the film, complete the thermal curing of the coating composition, and complete the formation of the resin layer.

[0090] Furthermore, it is preferable that the solid content concentration of the paint composition be 40% by mass or less. By setting the solid content concentration to 40% by mass or less, good coatability can be imparted to the paint composition, and a laminated film having a uniform resin layer can be manufactured.

[0091] The solids content concentration represents the ratio of the mass of the paint composition to the mass of the paint composition, excluding the mass of the solvent (i.e., [solids content concentration (mass%)] = [(mass of paint composition) - (mass of solvent)] / [mass of paint composition] × 100).

[0092] <Method for manufacturing a film in which the base film is a polyester film> Next, the method for manufacturing the film of the present invention will be explained using a polyester film as an example, but the present invention is not limited to this example. First, pellets of the raw material resin, for example polyethylene terephthalate (hereinafter abbreviated as PET), are thoroughly vacuum-dried and then supplied to an extruder, where they are melt-extruded into a sheet at approximately 280°C, cooled and solidified to produce an unstretched (unoriented) PET film (film A). This film is stretched 2.5 to 5.0 times in the longitudinal direction on a roll heated to 80°C to 120°C to obtain a uniaxially oriented PET film (film B). At this time, surface-treated cerium oxide particles prepared to a predetermined concentration may be included in the PET film. If a resin layer is further provided on the PET film and surface-treated cerium oxide particles are included in this resin layer, a coating composition having surface-treated cerium oxide particles prepared to a predetermined concentration may be applied to one side of film B, and furthermore, a surface treatment such as corona discharge treatment may be performed on the coated surface of the PET film before application. By performing surface treatments such as corona discharge treatment, the wettability of the resin composition to the PET film can be improved, preventing the resin composition from repelling and achieving a uniform coating thickness.

[0093] After coating, the edges of the PET film are held with clips and guided to a heating zone (preheating zone) at 80°C to 130°C to dry the solvent of the coating composition. After drying, the film is stretched 1.1 to 5.0 times in the width direction. Subsequently, it is guided to a heating zone (heat treatment zone) at 150°C to 250°C and heat-treated for 1 to 30 seconds to complete crystal orientation and complete the formation of the resin layer. During this heating process (heat treatment process), a relaxation treatment of 3% to 15% in the width direction or longitudinal direction may be applied as needed.

[0094] As another example, in a composite film-making apparatus having two uniscrew or twin-screw extruders, a main extruder and a sub-extruder, the resin that will be the raw material for the core layer is fed into the main extruder, and the resin that will be the raw material for the surface layer and surface-treated cerium oxide particles are fed into the sub-extruder. Preferably, each raw material is dried so that its moisture content is 50 ppm or less. By supplying the raw materials to each extruder in this way, a two-layer laminated film of a core layer and a surface layer can be made, for example, using two extruders and a feed block or multi-manifold installed above the T-die. The extruded unstretched sheet is cooled and solidified in close contact on a cooled drum to obtain an unstretched laminated film. This unstretched film is stretched 2.5 to 5.0 times in the longitudinal direction on a roll heated to 80°C to 120°C to obtain a uniaxially oriented film. The uniaxially oriented film is then guided to a heating zone (preheating zone) at 80°C to 130°C by gripping the ends with clips, and stretched 1.1 to 5.0 times in the width direction. The material is then guided to a heating zone (heat treatment zone) at 150°C to 250°C for 1 to 30 seconds to complete the crystal orientation. During this heating process (heat treatment process), a relaxation treatment of 3% to 15% in the width direction or length direction may be applied as needed.

[0095] <Resin composition> The resin composition of the present invention is a resin composition containing the surface-treated cerium oxide particles described above. That is, not only can the aforementioned resin be used as a film, but a resin composition containing such particles can also be obtained by adding the cerium oxide particles obtained above or a dispersion containing cerium oxide particles to a base resin (base resin), and a resin composition that exhibits oxidative decomposition performance against harmful substances such as viruses can be obtained. The type of base resin is not limited and may be either a thermoplastic resin or a thermosetting resin, and may be a homopolymer, a copolymer, or a blend of two or more polymers. From the viewpoint of good moldability, thermoplastic resins are preferred.

[0096] Examples of thermoplastic resins that can be used include polyethylene, polypropylene, polystyrene, polymethylpentene and other polyolefins, alicyclic polyolefins, styrene-based resins such as acrylonitrile styrene resin (AS resin) and acrylonitrile butadiene styrene resin (ABS resin), polyamides such as nylon 6 and nylon 66, polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and polybutylene succinate, polycarbonate, polyarylate, polyacetal, polyphenylene sulfide, vinyl chloride, tetrafluoroethylene, trifluoroethylene, trifluoroethylene chloride, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride and other fluorinated resins, aramid, polyimide, acrylic, methacrylic, polyacetal, polyglycolic acid, and polylactic acid. Examples of thermosetting resins that can be used include phenolic resin, epoxy resin, urea resin, melamine resin, unsaturated polyester, polyurethane, polyimide, and silicone resin.

[0097] The resin composition of the present invention is obtained by adding surface-treated cerium oxide particles to a base resin. However, the method of addition is not particularly limited. For example, the particles may be added to a base resin that has been molten by heat and kneaded, or they may be mixed with the base resin in a predetermined ratio and then melt-kneaded. Surface-treated cerium oxide particles may also be added to the base resin together with additives such as flame retardants, plasticizers, antistatic agents, antioxidants, lightfast agents, hydrolysis inhibitors, pigments, and lubricants. Furthermore, by exposing and unevenly distributing the surface-treated cerium oxide particles on the resin surface, the contact efficiency with harmful substances such as viruses is improved, thus exhibiting a sufficient effect. The method of uneven distribution is not particularly limited, but when additives are used in combination, the uneven distribution efficiency can be increased by selecting an additive that has a relatively higher affinity for surface-treated cerium oxide particles than the base resin. Examples of such additives include higher fatty acids, acid esters, acid amides, higher alcohols, and low-molecular-weight or high-molecular-weight polymers of surfactants. However, any additive that has an affinity for surface-treated cerium oxide particles is not particularly limited and can be preferably applied. In addition, one or more of these may be added in combination.

[0098] The surface-treated cerium oxide particles added to the base resin can be melt-kneaded by known methods in any form, such as powder, pellet, slurry, aqueous dispersion, or organic solvent dispersion, without any particular limitations. Alternatively, the surface-treated cerium oxide particles may be added to the base resin together with a dispersant or as a mixture with a dispersant. The dispersant for the surface-treated cerium oxide particles is not particularly limited, but surfactants are preferred. Cationic surfactants such as quaternary ammonium salts, anionic surfactants such as higher fatty acid salts and alkyl sulfate ester salts, amphoteric surfactants such as alkyl betaines, and nonionic surfactants such as polyoxyethylene sorbitan fatty acid salts and polyoxyethylene alkyl ethers are all applicable, but cationic and nonionic surfactants are more preferred. The mixing ratio of the dispersant to the surface-treated cerium oxide particles is not particularly limited, as long as the compatibility with the base resin and oxidative activity are not significantly impaired.

[0099] The content of surface-treated cerium oxide particles in the total resin composition of the present invention is not particularly limited as long as it can decompose harmful substances such as viruses, but it is preferably 0.01% by mass or more and 60% by mass or less. If the content is less than 0.01% by mass, sufficient effects will not be achieved, and if it is more than 60% by mass, the mechanical properties such as the strength and durability of the resin may be impaired. Preferably, it is 0.05% by mass or more and 50% by mass or less. More preferably, it is 0.1% by mass or more and 30% by mass or less. Even more preferably, it is 3% by mass or more and 10% by mass or less. Alternatively, the resin composition of the present invention may be used as a masterbatch and kneaded with the same or a different resin as the base resin in a predetermined ratio. When used as a masterbatch, the content of surface-treated cerium oxide particles is preferably 10% by mass or more.

[0100] The method for producing the resin composition of the present invention is not particularly limited, and examples include mixing each component constituting the resin composition using a mixer, or uniformly melt-kneading them. Examples of mixers include V-type blenders, super mixers, super floaters, and Henschel mixers. The melt-kneading temperature is preferably 200°C to 320°C, and more preferably 200°C to 300°C. The obtained resin composition can be used after being pelletized using a pelletizer.

[0101] The resin composition of the present invention can be molded by any molding method. Examples of molding methods include injection molding, extrusion molding, inflation molding, blow molding, vacuum molding, compression molding, and gas-assisted molding.

[0102] The resin composition of the present invention can be widely used as molded articles of any shape. Examples of molded articles include injection molded articles, extruded articles, vacuum pressure molded articles, blow molded articles, sheets, fibers, cloths, nonwoven fabrics, and composites with other materials.

[0103] The resin composition of the present invention can be used as a raw material to produce resin products such as automotive interior materials, electrical appliance casings, straps, handrails, doorknobs, and partition panels.

[0104] <Textile materials> The fibrous material containing cerium oxide nanoparticles of the present invention can be obtained by immobilizing the cerium oxide nanoparticles of the present invention onto a fibrous substrate, or by spinning a resin composition into which the cerium oxide nanoparticles of the present invention are kneaded. The method of immobilizing the cerium oxide nanoparticles of the present invention onto a fibrous substrate is preferred because the cerium oxide nanoparticles are exposed on the surface of the obtained fibrous material, making it easier for them to exhibit antiviral and antibacterial properties.

[0105] Methods for immobilizing the cerium oxide nanoparticles of the present invention onto a fibrous substrate include immobilizing them onto a base fibrous substrate using a dipping method, a spraying method, or a coating method with cerium oxide particles or a dispersion containing cerium oxide particles of the present invention.

[0106] When immobilizing the cerium oxide nanoparticles of the present invention onto the aforementioned fibrous substrate, it is preferable to add a binder component that acts as an adhesive to the fibrous substrate to the dispersion, as this can suppress the detachment of the cerium oxide nanoparticles from the fibrous substrate.

[0107] Examples of binder components include acrylic resins, epoxy resins, melamine resins, urethane resins, polyamide resins, polyimide resins, polyester resins, urea resins, phenolic resins, and silicone resins, but are not limited to these and can be preferably applied.

[0108] Furthermore, when immobilizing the cerium oxide nanoparticles of the present invention onto the aforementioned fibrous substrate, additives for controlling the dispersibility and viscosity of the cerium oxide nanoparticles of the present invention may be added to the dispersion.

[0109] As additives, surfactants are preferred, and any of the following can be applied: cationic surfactants such as quaternary ammonium salts, anionic surfactants such as higher fatty acid salts and alkyl sulfate ester salts, amphoteric surfactants such as alkyl betaines, and nonionic surfactants such as polyoxyethylene sorbitan fatty acid salts and polyoxyethylene alkyl ethers. However, cationic surfactants and nonionic surfactants are more preferred.

[0110] The mixing ratio of the additive to the cerium oxide nanoparticles of the present invention is not particularly limited and can be adjusted arbitrarily as long as the antiviral and antibacterial properties are not significantly impaired.

[0111] When spinning using the resin composition of the present invention, a thermoplastic resin is preferred as the base resin. As an example of the spinning method, the resin composition of the present invention is made into a molten polymer and guided to a spinning pack via piping. The polymer introduced from the polymer inlet of the spinning pack passes through a filter layer consisting of filter material and a filter, and is extruded from the discharge hole of the spinning die to obtain fibers.

[0112] The type of fiber base material is not limited and may be natural fibers, synthetic fibers, or inorganic fibers, or a mixture of two or more of these or a composite fiber. Examples of natural fibers include cellulose fibers such as cotton, linen, and rayon, and animal fibers such as wool, silk, and down, but are not limited to these and can be preferably applied. Examples of synthetic fibers include polyolefin fibers, polyester fibers, polyamide fibers, acrylic fibers, polyurethane fibers, and polyvinyl alcohol fibers, but are not limited to these and can be preferably applied. Examples of inorganic fibers include glass fibers, carbon fibers, and ceramic fibers, but are not limited to these and can be preferably applied. Furthermore, it can be preferably applied to fibers that have been processed to have irregular cross-sections or hollow shapes. Examples of fiber forms include yarn, woven fabric, and nonwoven fabric, but are not limited to these and can be preferably applied.

[0113] The content of the cerium oxide nanoparticles of the present invention in the total fiber material of the present invention is not particularly limited as long as it can decompose harmful substances such as viruses and bacteria, but it is preferably 0.01% by mass or more and 60% by mass or less. If the content is less than 0.01% by mass, sufficient effects will not be achieved, and if it is more than 60% by mass, mechanical properties such as the strength and durability of the fibers may be impaired, or the breathability when made into a fabric may be impaired. Preferably, it is 0.05% by mass or more and 50% by mass or less. More preferably, it is 0.1% by mass or more and 30% by mass or less. Even more preferably, it is 3% by mass or more and 10% by mass or less.

[0114] The fibrous material obtained in this manner is characterized by its ability to oxidize and decompose harmful substances such as viruses and bacteria.

[0115] <Applications of films, resin compositions, and fiber materials> The film, resin composition, molded articles, and fiber materials of the present invention can be used as oxidizing agents. For example, by utilizing their oxidizing properties, they can be used to decompose and remove dirt, odors, allergens, viruses, bacteria, fungi, and mold.

[0116] Specifically, the film of the present invention can be used by applying it to the surfaces of tableware, kitchens, toilets, washrooms, bathrooms, medical equipment, etc. It can also be used as a disinfectant by laminating it to the walls of various swimming pools, bathtubs, hot springs, etc. By molding the resin composition and preferably using it in places that people mainly touch, such as home appliance casings, automobile interior materials, straps, handrails, general goods, and pachinko machine handles, contact-type infections can be prevented. The fibrous material of the present invention and fibrous products using it can prevent droplet-type and contact-type infections by being processed into, for example, masks, filters, mats, chairs, gowns, lab coats, curtains, sheets, automobile interior materials, wipes, etc.

[0117] Its performance as an oxidizing agent can be evaluated by the fading reaction of organic dyes, as described later.

[0118] The fading reaction of organic dyes is also used to evaluate the photocatalytic performance of titanium dioxide, and the decomposition rate of the obtained dyes is used as an indicator of the property of oxidative decomposition of organic substances. Since low molecular weight substances such as acetaldehyde and ammonia, and harmful substances such as allergens are organic substances, titanium dioxide is expected to be used not only as an antibacterial agent but also for applications that decompose various harmful substances due to these properties. Similarly, if the cerium oxide nanoparticles or dispersions of the present invention have a high dye decomposition rate, it is thought that they can be used not only as an antibacterial agent but also for applications that decompose various harmful substances.

[0119] The decomposition rate of the dye is calculated as follows: First, molded articles of the film or resin composition of the present invention, or processed fiber materials into a cloth form, are brought into contact with an organic dye such as Acid Red 94 (AR94), and allowed to stand for a predetermined time. As a control, the same treatment is performed on molded articles of film or resin that do not contain surface-treated cerium oxide particles. After the reaction, the absorption spectra of all solutions are measured. For analysis, the absorbance at 552 nm, the maximum absorption wavelength of AR94, is used. The difference between the absorbance of the control (Ic) and the absorbance of the solution containing cerium oxide nanoparticles of the present invention (Ic-I) is taken, and the decomposition rate is calculated as the ratio to the absorbance of the control [((Ic-I) / Ic)×100].

[0120] Furthermore, a preferred embodiment of the dispersant for surface-treated cerium oxide particles used in the present invention is a dispersion containing a boron compound and cerium oxide nanoparticles, wherein the cerium oxide nanoparticles have a decomposition rate of 25% or more in the decomposition reaction of Acid Red 94 at 40°C for 1 hour. The decomposition rate of 25% or more in the decomposition reaction of Acid Red 94 at 40°C for 1 hour allows it to be used as an oxidizing agent. The decomposition rate in the decomposition reaction of Acid Red 94 at 40°C for 1 hour is preferably 50% or more, and particularly preferably 70% or more.

[0121] Furthermore, the film, resin composition, molded articles, and fiber materials of the present invention can be used as antiviral materials. Viruses that can be inactivated using the antiviral properties of the film, resin composition, molded articles, and fiber materials of the present invention include, for example, rhinovirus, poliovirus, foot-and-mouth disease virus, rotavirus, norovirus, enterovirus, hepatovirus, astrovirus, sapovirus, hepatitis E virus, influenza A, B, and C viruses, parainfluenza virus, mumps virus, measles virus, human metapneumovirus, respiratory syncytial virus (RSV), Nipah virus, Hendra virus, yellow fever virus, dengue virus, Japanese encephalitis virus, West Nile virus, hepatitis B and C viruses, eastern and western equine encephalitis virus, Onyonnyon virus, and rubella virus. Examples include Lassa virus, Junin virus, Machupo virus, Guanalito virus, Sabia virus, Crimean-Congo hemorrhagic fever virus, sandfly fever, Hantavirus, Sin Nombre virus, rabies virus, Ebola virus, Marburg virus, bat lyssavirus, human T-cell leukemia virus, human immunodeficiency virus, human coronavirus, SARS coronavirus, SARS coronavirus 2, human porvovirus, polyomavirus, human papillomavirus, adenovirus, herpesvirus, varicella-zoster virus, EB virus, cytomegalovirus, smallpox virus, monkeypox virus, cowpox virus, morasipox virus, and parapoxvirus.

[0122] To evaluate the performance as an antiviral material, the film, resin composition, molded articles, or fiber materials of the present invention are brought into contact with a virus, and the amount of virus is quantified. Methods for quantifying the virus include measuring the amount of viral antigen by ELISA, quantifying viral nucleic acid by PCR, measuring the infectivity titer by plaque assay, and measuring the infectivity titer by 50% infectious dose assay. In the present invention, the antiviral performance is preferably evaluated by measuring the infectivity titer by plaque assay or 50% infectious dose assay. In the 50% infectious dose assay, the unit of viral infectivity titer is expressed as TCID50 (Tissue culture infectious dose 50) when tested on cultured cells, EID50 (Egg infectious dose 50) when using hatched chicken eggs, and LD50 (Lethal dose 50) for animals. In addition, in the 50% infectious dose assay, there are methods for calculating the infectivity titer from the obtained data, such as the Reed-Muench method, Behrens-Kaeber method, and Spearman-Karber method, but the present invention uses the Reed-Muench method. Generally, the criteria for determining antiviral performance is that if the logarithmic reduction in the infectivity titer before the application of the cerium oxide nanoparticles of the present invention, or compared to a control without the nanoparticles of the present invention, is 2.0 or higher, then the antiviral performance is judged to be effective.

[0123] Furthermore, a preferred embodiment of the dispersant for surface-treated cerium oxide particles used in the present invention is a dispersion containing cerium oxide nanoparticles comprising a boron compound and cerium oxide nanoparticles, wherein the logarithmic reduction value of the viral infectivity titer TCID50 in a 50% infectious dose measurement method in a virus inactivation test targeting cell culture is 2.0 or higher compared to the infectivity titer before the application of the cerium oxide nanoparticles of the present invention and to a control that does not contain the nanoparticles of the present invention. Because the logarithmic reduction value of the viral infectivity titer TCID50 in the virus inactivation test is 2.0 or higher, it can be used as an antiviral agent. The logarithmic reduction value of the viral infectivity titer is preferably 2.5 or higher, and particularly preferably 3.0 or higher.

[0124] As mentioned above, when molded articles of the film or resin composition of the present invention are used as oxidizing agents or antiviral agents, for example, drain covers for kitchen sinks, drain plugs, gaskets for fixing window glass, gaskets for fixing mirrors, waterproof gaskets for bathrooms, washbasins and kitchens, door lining gaskets for refrigerators, bath mats, non-slip rubber for washbasins and chairs, hoses, shower heads, gaskets used in water purifiers, plastic products for water purifiers, gaskets used in washing machines, plastic products for washing machines, masks, medical caps, medical shoe covers, air conditioner filters, and air purifier filters. Examples of applications include filters for vacuum cleaners, ventilation fans, vehicles, air conditioning systems, plastic parts such as air conditioner fins and air conditioner vent louvers, and blower fans, plastic parts such as car air conditioner fins and car air conditioner vent louvers, and blower fans, clothing, bedding, nets for screen doors, nets for chicken coops, nets for mosquito nets, wallpaper, windows, blinds, interior materials for buildings such as hospitals, interior materials for trains and automobiles, vehicle seats, blinds, chairs, sofas, equipment for handling viruses, doors, ceiling panels, floor panels, windows, and other building materials. Furthermore, the fibrous material of the present invention can be used as a raw material to produce textile products such as masks, filters, mats, chairs, gowns, lab coats, curtains, sheets, automobile interior materials, and wipes. Thus, the film products, molded articles of resin compositions, and fiber materials of the present invention can be used as sanitary materials in various fields.

[0125] <Methods for measuring characteristics and evaluating effects> The method for measuring the properties and evaluating the effects in this invention is as follows.

[0126] (1) Thickness of the film surface The laminated film was stained with RuO4 and / or OsO4. Next, the laminated film was frozen and cut in the film thickness direction to obtain 10 ultrathin section samples for observation of the resin layer cross-section. Each sample cross-section was observed at 10,000x to 1,000,000x magnification using a TEM (transmission electron microscope: Hitachi H7100FA), and cross-sectional images were obtained. The measured resin layer thickness of these 10 samples was averaged to determine the resin layer thickness of the film.

[0127] (2) Hydrodynamic diameter of surface-treated cerium oxide particles Measurements were performed using the ELS-Z zeta potential and particle measurement system from Otsuka Electronics Co., Ltd. The hydrodynamic diameter of cerium oxide particles surface-treated with a boron compound was measured using the ELS-Z system from Otsuka Electronics Co., Ltd. Water was used as the solvent during measurement, and the average particle diameter was obtained by converting the hydrodynamic diameter to a number of particles.

[0128] (3) Measurement of oxidation performance by pigment decomposition test The film was cut into 2cm x 2cm squares and placed in a plastic petri dish. 10 μl of 0.02 mg / ml Acid Red 94 (AR94) was added dropwise to the organic-containing sample, and the mixture was allowed to stand at 40°C for 1 hour to allow the dye to decompose. A wet Kimwipe was placed in the petri dish to prevent the AR94 solution from evaporating. A control film without cerium oxide nanoparticles was treated in the same manner. After the reaction, the organic dye-containing sample and the control solution were taken from the laminated film sample, diluted with 0.99 ml of distilled water, and the absorption spectra were measured.

[0129] The absorbance at 552 nm, the maximum absorption wavelength of AR94, was used for the analysis.

[0130] The absorbance at 552 nm (Ic) of the control and the absorbance at 552 nm (I) of the sample containing the organic dye dropped onto the film sample were measured, and the dye decomposition rate (%) was calculated using the following formula.

[0131] Dye decomposition rate (%)=|I-Ic| / Ic×100 For molded resin compositions, measurements were taken using a 50mm x 50mm x 1mm rectangular plate, employing the same method as for films.

[0132] For fibrous materials, measurements were taken using a 5cm square piece of cloth, employing the same method as for films.

[0133] (4) Virus inactivation test (evaluation of antiviral activity by logarithmic reduction of infectivity titer) The film was cut into 5cm x 5cm squares and placed in a humidified petri dish. 0.4 ml of virus solution (feline calicivirus, F-9, ATCC, VR-782, norovirus surrogate) was dropped onto the film, and a 4cm x 4cm film (made of PP) was placed on top. The mixture was allowed to react for 24 hours. Then, PBS was added as a stopping solution to stop the reaction with the virus, and the virus on the film was washed off and collected. This collected solution was used as the stock solution for viral titer measurement, and the infectivity titer was measured using the TCID50 method.

[0134] The antiviral activity was evaluated using the difference between the common logarithm of the viral infectivity titer when tested with the film of the present invention and the common logarithm of the viral infectivity titer when tested with a film without cerium oxide nanoparticles (blank), as the viral inactivation index. A larger viral inactivation index indicates higher antiviral activity. Specifically, a logarithmic reduction in infectivity titer (viral inactivation index) of 2.0 or higher was judged to indicate effective antiviral performance. A: Virus inactivation index is 2.0 or higher B: Virus inactivation index is less than 2.0.

[0135] For molded resin compositions, measurements were taken using a 50mm x 50mm x 1mm rectangular plate, employing the same method as for films.

[0136] For fibrous materials, measurements were taken using a 5cm square piece of cloth, employing the same method as for films. [Examples]

[0137] The laminated film, resin composition, resin product, fiber material, and fiber product of the present invention will be described in detail below based on specific examples, but the present invention is not limited to these examples.

[0138] <Materials and Methods> Cerium(III) nitrate hexahydrate, boric acid, sodium tetraborate decahydrate (borax), ethylene glycol, and 30% hydrogen peroxide solution were obtained from Fujifilm Wako Pure Chemical Industries, Ltd. Acid Red 94, trimethyl borate, triethyl borate, isopropyl borate, methylboronic acid, ethylboronic acid, phenylboronic acid, EDTA-2Na, and DL-lactic acid were obtained from Tokyo Chemical Industry Co., Ltd. The commercially available cerium oxide dispersion (796077) used in the comparative example was obtained from Merck. Amicon Ultra 15 (30kD) used for purification was obtained from Merck Millipore.

[0139] Other reagents were purchased from Fujifilm Wako Pure Chemical Corporation, Tokyo Chemical Industry Co., Ltd., and Sigmar-Aldrich Japan LLC, and were used as is without any special purification. For measuring the hydrodynamic diameter of cerium oxide nanoparticles, we used the ELS-Z zeta potential / particle measurement system from Otsuka Electronics Co., Ltd., and for absorbance measurements, we used the SpectraMax iD3 plate reader from Molecular Devices.

[0140] <Preparation of surface-treated cerium oxide particles> Preparation of cerium oxide particles (A-1) surface-treated with boric acid. 50 ml of water was added to a round-bottom flask, and 284 mg of boric acid was dissolved. The pH was adjusted to 8.0 with sodium hydroxide. 1 ml of 10% by mass cerium(III) nitrate hexahydrate aqueous solution was added, and the mixture was stirred at room temperature for 10 minutes. Then, 1 ml of 1.2% by mass hydrogen peroxide aqueous solution was added dropwise, and the mixture was reacted at room temperature for 1 hour. After the reaction, nitric acid was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was purified using an ultrafiltration membrane with a molecular weight cutoff of 10 kD to obtain an orange dispersion containing nanoparticles of cerium oxide surface-treated with boric acid. This was diluted with water to a concentration of 1% by mass.

[0141] Preparation of cerium oxide particles (A-2) surface-treated with trimethyl borate. The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that 388 mg of trimethyl borate was used as the boron compound, to obtain an orange aqueous solution of cerium oxide particles (A-2) surface-treated with trimethyl borate. This was diluted with water to a concentration of 1% by mass.

[0142] Preparation of cerium oxide particles (A-3) surface-treated with triethyl borate. The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that 545 mg of triethyl borate was used as the boron compound, to obtain an orange aqueous solution of cerium oxide particles (A-3) surface-treated with triethyl borate. This was diluted with water to a concentration of 1% by mass.

[0143] Preparation of cerium oxide particles (A-4) surface-treated with triisopropyl borate. The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that 702 mg of triisopropyl borate was used as the boron compound, and 50 ml of 50% ethylene glycol water was used instead of 50 ml of water, to obtain an orange aqueous solution of cerium oxide particles (A-4) surface-treated with triisopropyl borate. This was diluted with water to adjust to 1% by mass.

[0144] Preparation of cerium oxide particles (A-5) surface-treated with sodium tetraborate. The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that 1.42 g of sodium tetraborate decahydrate (borax) was used as the boron compound, to obtain an orange aqueous solution of cerium oxide particles (A-5) surface-treated with sodium tetraborate. This was diluted with water to a concentration of 1% by mass.

[0145] Preparation of cerium oxide particles (A-6) surface-treated with methylboronic acid. The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that 223 mg of methylboronic acid was used as the boron compound, to obtain a light brown aqueous solution of cerium oxide particles (A-6) surface-treated with methylboronic acid. This was diluted with water to a concentration of 1% by mass.

[0146] Preparation of cerium oxide particles (A-7) surface-treated with ethylboronic acid. The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that 276 mg of ethylboronic acid was used as the boron compound, to obtain a light brown aqueous solution of cerium oxide particles (A-7) surface-treated with ethylboronic acid. This was diluted with water to a concentration of 1% by mass.

[0147] Preparation of cerium oxide particles (A-8) surface-treated with phenylboronic acid. The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that 455 mg of phenylboronic acid was used as the boron compound, and 50 ml of 50% ethylene glycol water was used instead of 50 ml of water, to obtain a brown aqueous solution of cerium oxide particles (A-8) surface-treated with phenylboronic acid. This was diluted with water to adjust to 1% by mass.

[0148] Preparation of cerium oxide particles (A-9) surface-treated with boric acid (boric acid solution with a pH of 4.0) The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that the pH of the boric acid solution was adjusted to 4.0, to obtain a brown aqueous solution of cerium oxide particles (A-9) surface-treated with boric acid (boric acid solution pH 4.0). This was diluted with water to adjust to 1% by mass.

[0149] Preparation of cerium oxide particles (A-10) surface-treated with boric acid (boric acid solution with a pH of 5.0) The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that the pH of the boric acid solution was adjusted to 5.0, to obtain a brown aqueous solution of cerium oxide particles (A-10) surface-treated with boric acid (boric acid solution pH 5.0). This was diluted with water to adjust to 1% by mass.

[0150] Preparation of cerium oxide particles (A-11) surface-treated with boric acid (boric acid solution heated to 70°C). The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that stirring after the addition of nitric acid was performed at 70°C, to obtain a brown aqueous solution of cerium oxide particles (A-11) surface-treated with boric acid (boric acid solution heated to 70°C). This was diluted with water to a concentration of 1% by mass.

[0151] Preparation of cerium oxide particles (A-12) surface-treated with boric acid (boric acid solution heated to 90°C). The reaction was carried out under the same conditions as for cerium oxide particles (A-1), except that stirring after the addition of nitric acid was performed at 90°C, to obtain a brown aqueous solution of cerium oxide particles (A-12) surface-treated with boric acid (boric acid solution heated to 90°C). This was diluted with water to a concentration of 1% by mass.

[0152] Preparation of cerium oxide particles (A-13) surface-treated with polyacrylic acid. To 50 ml of 1% by mass aqueous solution of sodium polyacrylate, 1 ml of 10% by mass aqueous solution of cerium(III) nitrate hexahydrate was added and the mixture was stirred at room temperature for 5 minutes. Then, 1 ml of 1.2% by mass aqueous solution of hydrogen peroxide was added and the mixture was heated to 40°C and reacted for 1 hour. The reaction solution was purified using an ultrafiltration membrane with a molecular weight cutoff of 30 kD to obtain a yellow dispersion containing cerium oxide particles (A-13) surface-treated with polyacrylic acid. This was diluted with water to a concentration of 1% by mass.

[0153] Preparation of cerium oxide particles (A-14) with post-addition of boric acid. A dispersion was prepared by a manufacturing method in which boric acid was added to a dispersion of cerium oxide nanoparticles and adsorbed. A commercially available dispersion of cerium oxide nanoparticles (IV) (Merck, 796077) was diluted to 0.2 mg / ml, and 284 mg of boric acid was added to 50 ml of the diluted solution and stirred at 60°C for 2 hours. The reaction solution was then purified using an ultrafiltration membrane with a molecular weight cutoff of 10 kD to obtain a brown dispersion containing cerium oxide particles (A-14) to which boric acid was added. This was diluted with water to adjust to 1% by mass.

[0154] Preparation of cerium oxide particles (A-15) surface-treated with EDTA / lactic acid. 0.8 g of cerium(III) nitrate hexahydrate, 0.25 g of EDTA-2Na, and 0.25 g of DL-lactic acid were dissolved in 50 ml of water, and the pH was adjusted to 9.5 with 30% aqueous ammonia. 640 μl of 30% hydrogen peroxide was added dropwise, and the mixture was stirred for 1 hour to obtain a brown aqueous solution. The reaction solution was then purified using an ultrafiltration membrane with a molecular weight cutoff of 3 kD to obtain a brown dispersion of cerium oxide particles (A-15) stabilized with EDTA / lactic acid. This dispersion was diluted with water to a concentration of 1% by mass.

[0155] Preparation of cerium oxide particles (A-16) surface-treated with EDTA / lactic acid with post-addition of boric acid. A dispersion of cerium oxide particles (A-15) stabilized with EDTA / lactic acid was diluted to 0.2 mg / ml, and 284 mg of boric acid was added to 50 ml of the diluted solution. The reaction solution was then purified using an ultrafiltration membrane with a molecular weight cutoff of 3 kD to obtain a brown aqueous solution of cerium oxide particles (A-16) surface-treated with EDTA / lactic acid to which boric acid was added later. This was diluted with water to a concentration of 1% by mass.

[0156] Preparation of untreated cerium oxide particles (A-17) A commercially available dispersion of cerium oxide nanoparticles (IV) (Merck, 796077) was diluted 10-fold and purified using a 30 kD ultrafiltration membrane to obtain a brown solution of untreated cerium oxide particles (A-17). This solution was diluted with water to a concentration of 1% by mass.

[0157] • Polyester resin (a) 105 parts by mass of bishydroxyethyl terephthalate (equivalent to 100 parts by mass of polyethylene terephthalate) were charged into an esterification reaction vessel and dissolved at 255°C. After dissolution, 86 parts by mass of terephthalic acid and 37 parts by mass of ethylene glycol were supplied to the reaction vessel, and the esterification reaction proceeded at 255°C, allowing water to be discharged. Based on the amount of water discharged, the esterification reaction was terminated when the reaction rate reached 95%.

[0158] [Polymerization process] 105 parts by mass of the esterification reaction product (100 parts by mass of polyethylene terephthalate) was transferred to a polymerization reaction vessel. While maintaining the temperature at 235°C, a slurry mixture of 0.09 parts by mass of magnesium acetate and 0.03 parts by mass of antimony trioxide in 1.6 parts by mass of ethylene glycol, and a solution of 0.02 parts by mass of phosphoric acid dissolved in 1.6 parts by mass of ethylene glycol were added to the esterification reaction product. Subsequently, the temperature inside the polymerization reaction vessel was raised from 235°C to 280°C over 90 minutes, while the pressure inside the vessel was gradually reduced from atmospheric pressure to 150 Pa to allow the reaction to proceed. The reaction was terminated when the intrinsic viscosity (IV) reached 0.55 dl / g, and polyester resin (a) was obtained. The amount of carboxylic acid terminal groups was 33 equivalents / ton.

[0159] • Master pellet (a) of cerium oxide particles (A-1) surface-treated with boric acid. 50 parts by mass of polyester resin (a) and 50 parts by mass of cerium oxide particles (A-1) surface-treated with boric acid were kneaded in a twin-screw extruder to obtain a master pellet (a) of cerium oxide particles (A-1) surface-treated with boric acid.

[0160] • Resin or compound (B): Acrylic resin In a stainless steel reaction vessel, methyl methacrylate (α), hydroxyethyl methacrylate (β), and urethane acrylate oligomer (manufactured by Negami Kogyo Co., Ltd., Art Resin® UN-3320HA, with 6 acryloyl groups) (γ) were charged in a mass ratio of (α) / (β) / (γ) = 94 / 1 / 5. As an emulsifier, 2 parts by mass of sodium dodecylbenzenesulfonate were added to 100 parts by mass of the total of (α) to (γ), and the mixture was stirred to prepare Mixture 1. Next, a reaction apparatus equipped with a stirrer, reflux condenser, thermometer, and dropping funnel was prepared. 60 parts by mass of the above Mixture 1, 200 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate as a polymerization initiator were charged into the reaction apparatus and heated to 60°C to prepare Mixture 2. Mixture 2 was maintained at 60°C for 20 minutes. Next, a mixture 3 was prepared consisting of 40 parts by mass of mixture 1, 50 parts by mass of isopropyl alcohol, and 5 parts by mass of potassium persulfate. Subsequently, mixture 3 was added dropwise to mixture 2 over 2 hours using a dropping funnel to prepare mixture 4. After that, mixture 4 was heated to 60°C and maintained for 2 hours. After the obtained mixture 4 was cooled to below 50°C, it was transferred to a container equipped with a stirrer and a vacuum device. 60 parts by mass of 25% aqueous ammonia and 900 parts by mass of pure water were added, and the isopropyl alcohol and unreacted monomers were recovered under reduced pressure while heating to 60°C to obtain an acrylic resin dispersed in pure water.

[0161] (Example 1) ·Paint composition: As cerium oxide particles (A), cerium oxide particles (A-1) surface-treated with boric acid were used, and as the resin or compound (B), an acrylic resin was used, and they were mixed so that the solid content mass ratio was (A) / (B) = 50 / 50. Furthermore, in order to improve the applicability to the film, a fluorine-based surfactant ("Pluscoat" (registered trademark) RY-2, manufactured by Go-O Chemical Industry Co., Ltd.) was added in an amount of 0.1 parts by mass per 100 parts by mass of the total mixture to obtain a paint composition.

[0162] • Uniaxially oriented polyester film: PET pellets containing two types of particles (4% by mass of silica particles with a primary particle size of 0.3 μm and 2% by mass of calcium carbonate particles with a primary particle size of 0.8 μm) (intrinsic viscosity 0.64 dl / g) were thoroughly vacuum dried, then supplied to an extruder and melted at 280°C. The pellets were extruded into a sheet through a T-shaped die and wrapped around a mirror-finish casting drum with a surface temperature of 25°C using an electrostatic casting method, where they were cooled and solidified. This unstretched film was heated to 90°C and stretched 3.1 times in the longitudinal direction to obtain a uniaxially oriented polyester film (film B).

[0163] • Laminated film: A uniaxially oriented polyester film was coated with the coating composition containing the components shown in Table 1 using a wire bar coat to a thickness of approximately 6 μm. Subsequently, both ends of the uniaxially oriented film coated with the coating composition were gripped with clips in the width direction and guided to a preheating zone. The ambient temperature of the preheating zone was set to 90°C to 100°C to dry the solvent of the coating composition. Subsequently, the film was continuously stretched 3.6 times in the width direction in a stretching zone at 100°C, followed by heat treatment for 20 seconds in a heat treatment zone at 240°C to form a surface layer, and then a 5% relaxation treatment in the width direction was performed at the same temperature to obtain a laminated film in which the crystal orientation of the polyester film was completed. In the obtained laminated film, the thickness of the polyester film was 50 μm, and the thickness of the surface layer was 50 nm.

[0164] The characteristics of the obtained laminated film are shown in Table 2.

[0165] (Examples 2-16) A laminated film was obtained in the same manner as in Example 1, except that the coating composition was as shown in Table 1. The solid content mass ratio represents the ratio to the total mass of the resin and compound listed in the table.

[0166] (Example 17) A PET pellet (intrinsic viscosity 0.64 dl / g) containing two types of particles (4% by mass of silica particles with a primary particle size of 0.3 μm and 2% by mass of calcium carbonate particles with a primary particle size of 0.8 μm), in addition to a master pellet (a) of cerium oxide particles (A-1) surface-treated with boric acid, was thoroughly vacuum-dried, then supplied to an extruder and melted at 280°C. It was extruded into a sheet through a T-shaped die and wrapped around a mirror-finish casting drum with a surface temperature of 25°C using an electrostatic casting method, where it was cooled and solidified. This unstretched film was heated to 90°C and stretched 3.1 times in the longitudinal direction to obtain a uniaxially oriented film (film B).

[0167] Subsequently, the uniaxially oriented film was gripped at both ends in the width direction with clips and guided to the preheating zone. The ambient temperature of the preheating zone was set to 90°C to 100°C. Subsequently, the film was continuously stretched 3.6 times in the width direction in the stretching zone at 100°C, followed by heat treatment for 20 seconds in the heat treatment zone at 240°C. Finally, a 5% relaxation treatment was performed in the width direction at the same temperature to obtain a single-layer film in which the crystal orientation of the polyester film was completed. The properties of the obtained film are shown in Table 2.

[0168] (Comparative Examples 1-5) A laminated film was obtained in the same manner as in Example 1, except that the cerium oxide particles (A) in the paint composition were those listed in Table 1. The properties of the obtained laminated film are shown in Table 2.

[0169] [Table 1]

[0170] [Table 2]

[0171] ·Resin composition (Example 18) 97 parts by mass of ABS resin pellets (Toray Industries, general-purpose resin "Toyolac®" 100322), 3 parts by mass of cerium oxide particles (A-1) surface-treated with boric acid, and 0.5 parts by mass of pure water as a spreading agent were mixed using a Henschel mixer at 23°C for 60 seconds. The resulting mixture was then melt-kneaded in a 40 mmφ vented extruder at an extrusion temperature of 230°C, extruded into a gut-like form, and pelletized to obtain a resin composition. Next, the obtained pellets were molded into 3 mm thick brown rectangular plates using an injection molding machine set to a cylinder temperature of 230°C. The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained rectangular plates were measured using the method described above. The evaluation results are shown in Table 3.

[0172] (Example 19) A brown rectangular plate was obtained in the same manner as in Example 18, except that 97 parts by mass of ABS resin pellets (Toray Industries, long-lasting antistatic resin "Toyolac Parel®" TP10) were used, 3 parts by mass of cerium oxide particles (A-1) surface-treated with boric acid were used as cerium oxide particles (A), and 0.5 parts by mass of pure water was used as a spreading agent. The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained rectangular plate were measured using the method described above. The evaluation results are shown in Table 3.

[0173] (Example 20) A brown rectangular plate was obtained in the same manner as in Example 18, except that 90 parts by mass of ABS resin pellets (Toray Industries, long-lasting antistatic resin "Toyolac Parel®" TP10), 10 parts by mass of cerium oxide particles (A-1) surface-treated with boric acid as cerium oxide particles (A), and 0.5 parts by mass of pure water as a spreading agent were added. The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained rectangular plate were measured using the method described above. The evaluation results are shown in Table 3.

[0174] (Comparative Example 6) Yellow square plates were obtained in the same manner as in Example 18, except that 97 parts by mass of ABS resin pellets (Toray Industries, general-purpose resin "Toyolac®" 100322) were used, 3 parts by mass of cerium oxide particles (A-13) surface-treated with polyacrylic acid as cerium oxide particles (A), and 0.5 parts by mass of pure water as a spreading agent. The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained square plates were measured using the method described above. The evaluation results are shown in Table 3.

[0175] (Comparative Example 7) Yellow square plates were obtained in the same manner as in Example 18, except that 90 parts by mass of ABS resin pellets (Toray Industries, long-lasting antistatic resin "Toyolac Parel®" TP10), 10 parts by mass of cerium oxide particles (A-13) surface-treated with polyacrylic acid as cerium oxide particles (A), and 0.5 parts by mass of pure water as a spreading agent were added. The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained square plates were measured using the method described above. The evaluation results are shown in Table 3.

[0176] [Table 3]

[0177] (Example 21) A polypropylene spunbond nonwoven fabric (manufactured by Toray) was cut into 5 cm squares and immersed for 1 hour in an aqueous dispersion containing 1 part by mass of cerium oxide particles (A-1) surface-treated with boric acid as cerium oxide particles (A), 1 part by mass of a self-crosslinking acrylic binder (Boncoat AN-1170, manufactured by DIC Corporation), and 98 parts by mass of water. After lightly squeezing, the fabric was dried in an oven at 130°C for 2 hours to obtain a yellow nonwoven fabric. The oxidation performance (pigment decomposition rate) and antiviral properties of the nonwoven fabric with immobilized cerium oxide nanoparticles were measured using the method described above. The evaluation results are shown in Table 4.

[0178] (Example 22) A yellow nonwoven fabric with immobilized cerium oxide nanoparticles was obtained in the same manner as in Example 21, except that instead of the aqueous dispersion in Example 22, an aqueous dispersion containing 5 parts by mass of cerium oxide particles (A-1) surface-treated with boric acid, 5 parts by mass of a self-crosslinking acrylic binder (Boncoat AN-1170, manufactured by DIC Corporation), and 90 parts by mass of water was used as the cerium oxide particles (A). The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained nonwoven fabric with immobilized cerium oxide nanoparticles were measured using the method described above. The evaluation results are shown in Table 4.

[0179] (Example 23) A yellow nonwoven fabric was obtained in the same manner as in Example 21, except that a rayon nonwoven fabric (manufactured by Claflex) was used instead of a polypropylene spunbond nonwoven fabric (manufactured by Toray), with cerium oxide particles (A-1) immobilized on the surface treated with boric acid. The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained nonwoven fabric with immobilized cerium oxide nanoparticles were measured using the method described above. The evaluation results are shown in Table 4.

[0180] (Example 24) Except for using a rayon nonwoven fabric (manufactured by Claflex) instead of a polypropylene spunbond nonwoven fabric (manufactured by Toray), and using an aqueous dispersion containing 5 parts by mass of cerium oxide particles (A-1) surface-treated with boric acid, 5 parts by mass of a self-crosslinking acrylic binder (Boncoat AN-1170, manufactured by DIC), and 90 parts by mass of water instead of the aqueous dispersion used in Example 21, a yellow nonwoven fabric with immobilized cerium oxide particles (A-1) surface-treated with boric acid was obtained in the same manner as in Example 21. The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained nonwoven fabric with immobilized cerium oxide nanoparticles were measured using the method described above. The evaluation results are shown in Table 4.

[0181] (Comparative Example 8) A brown nonwoven fabric with immobilized polyacrylic acid-surface-treated cerium oxide particles (A-13) was obtained in the same manner as in Example 21, except that instead of the aqueous dispersion in Example 21, an aqueous dispersion containing 1 part by mass of polyacrylic acid-surface-treated cerium oxide particles (A-13), 1 part by mass of a self-crosslinking acrylic binder (Boncoat AN-1170, manufactured by DIC Corporation), and 98 parts by mass of water was used as the cerium oxide particles (A). The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained nonwoven fabric with immobilized cerium oxide nanoparticles were measured using the method described above. The evaluation results are shown in Table 4.

[0182] (Comparative Example 9) A brown nonwoven fabric with immobilized polyacrylic acid-surface-treated cerium oxide particles (A-13) was obtained in the same manner as in Example 21, except that instead of the aqueous dispersion in Example 21, an aqueous dispersion containing 5 parts by mass of polyacrylic acid-surface-treated cerium oxide particles (A-13), 5 parts by mass of a self-crosslinking acrylic binder (Boncoat AN-1170, manufactured by DIC Corporation), and 90 parts by mass of water was used as the cerium oxide particles (A). The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained nonwoven fabric with immobilized cerium oxide nanoparticles were measured using the method described above. The evaluation results are shown in Table 4.

[0183] (Comparative Example 10) A brown nonwoven fabric with immobilized polyacrylic acid-surface-treated cerium oxide particles (A-13) was obtained in the same manner as in Example 21, except that a rayon nonwoven fabric (manufactured by Claflex) was used instead of a polypropylene spunbond nonwoven fabric (manufactured by Toray), and instead of the aqueous dispersion in Example 21, an aqueous dispersion containing 1 part by mass of polyacrylic acid-surface-treated cerium oxide particles (A-13), 1 part by mass of a self-crosslinking acrylic binder (Boncoat AN-1170, manufactured by DIC Corporation), and 98 parts by mass of water was used as the cerium oxide particles (A). The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained nonwoven fabric with immobilized cerium oxide nanoparticles were measured using the method described above. The evaluation results are shown in Table 4.

[0184] (Comparative Example 11) A brown nonwoven fabric with immobilized polyacrylic acid-surface-treated cerium oxide particles (A-13) was obtained in the same manner as in Example 21, except that a rayon nonwoven fabric (manufactured by Claflex) was used instead of a polypropylene spunbond nonwoven fabric (manufactured by Toray), and instead of the aqueous dispersion in Example 21, an aqueous dispersion containing 5 parts by mass of cerium oxide particles (A-13) surface-treated with polyacrylic acid, 5 parts by mass of a self-crosslinking acrylic binder (Boncoat AN-1170, manufactured by DIC Corporation), and 90 parts by mass of water was used as the cerium oxide particles (A). The oxidation performance (pigment decomposition rate) and antiviral properties of the obtained nonwoven fabric with immobilized cerium oxide nanoparticles were measured using the method described above. The evaluation results are shown in Table 4.

[0185] [Table 4]

Claims

1. A film containing cerium oxide particles (A) surface-treated with a boron compound, The cerium oxide particle (A) has a structure in which a cerium oxide particle forms the core and its surface is coated with the boron compound. A film characterized in that the boron compound is a boron compound represented by the following general formula (I). BR n (OR') 3-n (I) (In formula (I), n is an integer from 0 to 2, R represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group, and R' represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. If there are multiple R or R', they may be the same or different.)

2. The film according to claim 1, having a laminated structure of two or more layers, wherein at least one surface layer contains the cerium oxide particles (A).

3. The film according to claim 2, wherein the content of cerium oxide particles (A) in the surface layer is 20% by mass or more and 80% by mass of the total mass of the surface layer.

4. The film according to any one of claims 1 to 3, characterized in that the cerium oxide particles (A) are cerium oxide particles produced by adding an oxidizing agent to a solution containing a boron compound represented by the general formula (I) and cerium(III) ions.

5. The film according to any one of claims 1 to 4, wherein the boron compound represented by the general formula (I) is boric acid, boric acid ester, boronic acid, boronic acid ester, boric acid, boric acid ester, or borate.

6. The film according to any one of claims 1 to 5, wherein at least one layer is a polyester-based layer.

7. A resin composition comprising cerium oxide particles (A) surface-treated with a boron compound, The cerium oxide particle (A) has a structure in which a cerium oxide particle forms the core and its surface is coated with the boron compound. A resin composition characterized in that the boron compound is a boron compound represented by the following general formula (I). BR n (OR') 3-n (I) (In formula (I), n is an integer from 0 to 2, R represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group, and R' represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. If there are multiple R or R', they may be the same or different.)

8. The resin composition according to claim 7, characterized in that the cerium oxide particles (A) are cerium oxide particles produced by adding an oxidizing agent to a solution containing a boron compound represented by the general formula (I) and cerium(III) ions.

9. The resin composition according to claim 7 or 8, wherein the boron compound represented by the general formula (I) is boric acid, boric acid ester, boronic acid, boronic acid ester, boric acid, boric acid ester, or borate.

10. A resin product comprising the resin composition described in any one of claims 7 to 9.

11. The resin product according to claim 10, wherein the resin product is selected from the group consisting of automotive interior materials, electrical appliance casings, straps, handrails, door knobs, and partition boards.

12. A fibrous material containing cerium oxide particles (A) surface-treated with a boron compound, The cerium oxide particle (A) has a structure in which a cerium oxide particle forms the core and its surface is coated with the boron compound. A fibrous material characterized in that the boron compound is a boron compound represented by the following general formula (I). BR n (OR') 3-n (I) (In formula (I), n is an integer from 0 to 2, R represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group, and R' represents hydrogen, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a tolyl group. If there are multiple R or R', they may be the same or different.)

13. The fiber material according to claim 12, characterized in that the cerium oxide particles (A) are cerium oxide particles produced by adding an oxidizing agent to a solution containing a boron compound represented by the general formula (I) and cerium(III) ions.

14. The fiber material according to claim 12 or 13, wherein the boron compound represented by the general formula (I) is boric acid, boric acid ester, boronic acid, boronic acid ester, boric acid, boric acid ester, or borate.

15. A textile product made using the fibrous material described in any one of claims 12 to 14.

16. The textile product according to claim 15, wherein the textile product is selected from the group consisting of masks, filters, mats, chairs, gowns, lab coats, curtains, sheets, automotive interior materials, and wipes.

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