JP7289141B2 - Antifouling coating film-forming composition, antifouling coating film, and industrial material sheet with antifouling coating film - Google Patents

Description

The present invention relates to a composition for forming an antifouling coating film on various articles, an antifouling coating film formed from the composition, and an industrial material sheet attached with this antifouling coating film, specifically films and synthetic resins. Sheets, veneers, building material panels, glass products (parts), plastic moldings (parts), etc. Industrial materials such as flexible synthetic resin sheets (tarpaulins, canvas, mesh sheets, synthetic leather, etc.) sheet), an invention of an antifouling coating film formed from this composition, and an industrial material sheet (tarpaulin , canvas, mesh sheet, synthetic leather, etc.), and relates to the invention of industrial material sheets with less damage such as cracks in the antifouling coating film when subjected to stress such as bending, folding, and fluttering.

Membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for architectural spaces, stadium sunshade tents, architectural curing sheets, flexible container bags, and tarpaulin materials used for these , truck hoods, truck bed sheets, roof tents, sheet houses, etc., and canvas materials used for these, mesh sheets used for building construction coverings, etc. An industrial sheet material coated with a thermoplastic resin layer such as is used. In particular, membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for architectural spaces, and stadium sunshade tents are required to maintain a clean appearance without compromising aesthetics. It is essential to impart antifouling properties to tarpaulins, which are the raw materials for these products.

As means for imparting antifouling properties to such industrial sheets mainly made of soft vinyl chloride resin, the present applicant has developed medium- and large-sized tents, tent warehouses, eaves tents, hoods for trucks, and backs for signboards. As a sheet for industrial materials such as lit, an antifouling sheet having a hydrophilic film layer containing at least one selected from organic silicates and condensates thereof (Patent Document 1: Claim 1) was proposed. The antifouling layer of this film material is certainly excellent in antifouling properties, and since it expresses hydrophilicity, it was also effective in preventing rain streaks. Since the film layer lacks stretchability, there is a drawback that cracks become more pronounced as the film thickness increases. For industrial material sheets that require outdoor durability, the antifouling layer must be provided with a certain thickness in order to obtain a long-term antifouling effect. For this requirement, paragraph [0062 ] proposed. However, even with this countermeasure, the coating layer using the organic silicate as the antifouling layer of the industrial material sheet was still fragile and susceptible to cracking due to stretching stress such as bending and fluttering. Therefore, a hydrophilic coating layer using an organic silicate can form a durable antifouling coating film on rigid articles such as glass, metal products, and thick plastic products whose substrates are difficult to deform. However, for flexible and stretchable film or sheet substrates, the hydrophilic coating layer cannot follow the deformation and elongation of the substrate, causing cracks and reducing the antifouling effect. turned out to be something. On the other hand, it has been proposed to use an acrylic resin in combination with an organic silicate compound, such as a stain-resistant water-based resin composition (Patent Document 2) in which an organic silicate compound, a partial hydrolyzed condensate thereof, etc. are blended into an acrylic resin emulsion. . Certainly, if such a combined system is applied to the antifouling layer of industrial material sheets, it can be an effective countermeasure against stretching stress such as bending and fluttering, but the original antifouling performance due to the hydrophilicity of the organic silicate compound (Especially the effect of preventing stains from rain streaks) is accompanied by the demerit of being halved. Therefore, a composition for forming an antifouling coating film suitable for industrial material sheets, an antifouling coating film formed from this composition, and an industrial material sheet (tarpaulin) attached with this antifouling coating film , canvas, mesh sheet, synthetic leather, etc.), there has been a demand for an industrial material sheet with less damage such as cracks in the antifouling coating film when subjected to stress such as bending, folding, and fluttering.

JP 2003-191386 A JP 2012-207115 A

The present invention is particularly suitable for forming a robust antifouling coating film suitable for flexible synthetic resin sheets (industrial material sheets such as tarpaulins, canvas, mesh sheets, synthetic leather, etc.) containing textiles as a core material. Providing a coating composition, providing a robust antifouling coating film formed from this coating composition, and industrial material sheets (tarpaulins, canvas, mesh sheets, synthetic leather, etc.) with this robust antifouling coating film ), and particularly to provide an industrial material sheet with less damage such as cracks in the antifouling coating film when subjected to stress such as bending, bending, and fluttering. If this problem is solved and a composition capable of forming a robust antifouling coating film is provided, an antifouling coating film with excellent robustness can be obtained, and this antifouling coating film can be applied to industrial material sheets. As a result, it is possible to obtain industrial material sheets (tarpaulins, canvas, mesh sheets, synthetic leather, etc.) with excellent bending resistance, bending resistance, and fluttering resistance, as well as long-term antifouling and abrasion resistance. superior in terms of The coating composition for forming an antifouling coating film of the present invention can be applied not only to industrial material sheets, but also to films, synthetic resin sheets, decorative panels, building material panels, glass products (parts), and plastic moldings (parts). It can be applied to various uses, form a robust antifouling coating film, and attach it to products and parts.

As a result of repeated studies in consideration of such points, the present invention has found that 1) a composition containing at least an organic silicate compound or an organic titanate compound and a modified cellulose nanomaterial is used as a paint, and 2) an organic silicate compound or an organic titanate. 3) using an antifouling coating film containing at least a modified cellulose nanomaterial in the hydrolytic condensate of the compound; By using an industrial material sheet with a dirty coating film, it is possible to obtain a robust antifouling coating film with less damage such as cracks when subjected to stress such as bending, bending, and fluttering. By attaching the coating film to the industrial material sheet, it is possible to obtain an industrial material sheet with less damage such as cracks in the antifouling coating film when subjected to stress such as bending, folding, and fluttering. The inventors have found that the antifouling effect of the industrial material sheet can be maintained for a long period of time, and have completed the present invention.

That is, the composition for forming an antifouling coating film of the present invention is a composition containing at least an organic silicate compound or an organic titanate compound and a modified cellulose nanomaterial, wherein the modification of the modified cellulose nanomaterial is esterification ( One or more selected from borate esterification, phosphate esterification, and silicate esterification ), silane coupling agent treatment (aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylsilane modification, acrylicsilane modification, chlorosilane modification, mercaptosilane modification, isocyanurate silane modification, isocyanate silane modification), and organic titanate treatment. The antifouling coating film obtained by using this composition for forming an antifouling coating film in a paint contains a modified cellulose nanomaterial, so that the antifouling coating film itself has excellent bending resistance, bending resistance, fluttering resistance, Excellent wear resistance. Then, by applying this composition for forming an antifouling coating film and attaching an antifouling coating film formed from this composition to an industrial material sheet (tarpaulin, canvas, mesh sheet, synthetic leather, etc.), bending, When subjected to stress such as bending and fluttering, the presence of the modified cellulose nanomaterial (stress relaxation effect, sliding effect) can make the antifouling coating film less susceptible to damage such as cracks.

The composition for forming an antifouling coating film of the present invention comprises photocatalytic titanium oxide, photocatalytic titanium peroxide (peroxotitanic acid), photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic strontium titanate, It preferably contains one or more photocatalytic metal oxides selected from photocatalytic tungsten oxide, photocatalytic bismuth oxide, and photocatalytic iron oxide. By including these photocatalytic metal oxides in the antifouling coating film, decomposition of organic substances (soot dust, tar, finger marks, mold, algae, etc.) is promoted by photocatalytic activity, and self-cleaning antifouling properties due to rainfall can be exhibited.

The antifouling coating film of the present invention is an antifouling coating film containing at least a modified cellulose nanomaterial in a hydrolytic condensate of an organic silicate compound or an organic titanate compound, wherein the modification of the modified cellulose nanomaterial is an ester modification (one or more selected from borate esterification, phosphate esterification, and silicate esterification ), silane coupling agent treatment (aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylsilane modification, acrylsilane modification , chlorosilane-modified, mercaptosilane-modified, isocyanurate silane-modified, isocyanate silane-modified), and organic titanate treatment. As a result, by incorporating the modified cellulose nanomaterial into the condensed structure of the antifouling coating film (hydrolytic condensate of organic silicate compound or organic titanate compound), the antifouling coating film itself has improved bending resistance, bending resistance, and resistance. It should be excellent in flapping property and abrasion resistance. When industrial material sheets (tarpaulins, canvas, mesh sheets, synthetic leather, etc.) with this antifouling coating film are subjected to stress such as bending, bending, and fluttering, the presence of modified cellulose nanomaterials ( (stress relaxation effect, sliding effect) can make the antifouling coating film less susceptible to damage such as cracks.

In the antifouling coating film of the present invention, the antifouling coating film comprises photocatalytic titanium oxide, photocatalytic titanium peroxide (peroxotitanic acid), photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic strontium titanate, and photocatalytic It preferably contains one or more photocatalytic metal oxides selected from tungsten oxide, photocatalytic bismuth oxide, and photocatalytic iron oxide. By containing these photocatalytic metal oxides in the condensed structure of the antifouling coating film (hydrolytic condensate of organic silicate compound or organic titanate compound), organic substances (dust, tar, finger marks, mold, algae) due to photocatalytic activity etc.) is promoted, and self-cleaning antifouling properties due to rainfall can be stably exhibited over the long term.

The industrial material sheet provided with an antifouling coating film of the present invention is an industrial material sheet provided with an antifouling coating film containing at least a modified cellulose nanomaterial on a hydrolytic condensate of an organic silicate compound or an organic titanate compound. , The modification of the modified cellulose nanomaterial is esterification (one or more selected from borate esterification, phosphate esterification, silicic acid esterification ), silane coupling agent treatment (aminosilane modification, vinylsilane modification , epoxysilane-modified, methacrylsilane-modified, acrylsilane-modified, chlorosilane-modified, mercaptosilane-modified, isocyanurate silane-modified, isocyanatesilane-modified), and one or more selected from organic titanate treatment. It is preferable to accompany the antifouling coating film. By incorporating modified cellulose nanomaterials into the condensed structure of the antifouling coating film (hydrolytic condensate of an organic silicate compound or an organic titanate compound), the antifouling coating film itself has flex resistance, bending resistance, and flutter resistance. Since it has excellent abrasion resistance, industrial material sheets (tarpaulin, canvas, mesh sheet, synthetic leather, etc.) attached with this antifouling coating film are subjected to stress such as bending, folding, and fluttering. In this case, the presence of the modified cellulose nanomaterial (stress relaxation effect, sliding effect) can provide an industrial material sheet that is less susceptible to damage such as cracks in the antifouling coating film.

In the industrial material sheet with the antifouling coating film of the present invention, the antifouling coating film is photocatalytic titanium oxide, photocatalytic titanium peroxide (peroxotitanic acid), photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic It preferably contains one or more photocatalytic metal oxides selected from strontium titanate, photocatalytic tungsten oxide, photocatalytic bismuth oxide, and photocatalytic iron oxide. By attaching an antifouling coating film containing these photocatalytic metal oxides in the condensed structure of the antifouling coating film (hydrolytic condensate of an organic silicate compound or an organic titanate compound) to an industrial material sheet, The industrial material sheet can promote the decomposition of organic matter (soot dust, tar, finger marks, mold, algae, etc.) and stably exhibit self-cleaning antifouling properties due to rainfall over a long period of time.

According to the present invention, for forming a robust antifouling coating film suitable for flexible synthetic resin sheets (industrial material sheets such as tarpaulins, canvases, mesh sheets, synthetic leathers, etc.) especially containing textiles as core materials Providing a coating composition, providing a robust antifouling coating film formed from this coating composition, and industrial material sheets (tarpaulins, canvas, mesh sheets, synthetic leather, etc.) with this robust antifouling coating film ), and it is possible to provide an industrial material sheet with less damage such as cracks in the antifouling coating film when subjected to stress such as bending, bending, and fluttering. A composition capable of forming such a robust antifouling coating film is provided, and an antifouling coating film having excellent robustness can be obtained. , It is possible to obtain industrial material sheets (tarpaulin, canvas, mesh sheet, synthetic leather, etc.) with excellent bending resistance, bending resistance, and fluttering resistance. be excellent. The composition for forming an antifouling coating film of the present invention is applied not only to industrial material sheets, but also to a wide range of applications such as films, synthetic resin sheets, decorative boards, building material panels, glass products (parts), and plastic molded products (parts). It becomes possible to attach a strong antifouling coating film.

1) The composition for forming an antifouling coating film of the present invention is a paint containing at least an organic silicate compound or an organic titanate compound and a modified cellulose nanomaterial, and optionally containing a photocatalytic metal oxide. 2) The antifouling coating film of the present invention is a composition for forming an antifouling coating film containing at least an organic silicate compound or an organic titanate compound and a modified cellulose nanomaterial, and optionally a photocatalytic metal oxide. It is a sol-gel coating film obtained by coating and drying the product, containing at least a modified cellulose nanomaterial in a hydrolytic condensate of an organic silicate compound or an organic titanate compound, and optionally a photocatalytic metal oxide It is an embodiment containing 3) The industrial material sheet of the present invention is a composition for forming an antifouling coating film containing at least an organic silicate compound or an organic titanate compound and a modified cellulose nanomaterial, and optionally containing a photocatalytic metal oxide. is applied to one or more surfaces of the industrial material sheet, and this is dried to complete a sol-gel coating film to attach an antifouling coating film to the industrial material sheet. Hydrolysis of the organic silicate compound or organic titanate compound In this embodiment, the condensate contains at least a modified cellulose nanomaterial and, if necessary, a photocatalytic metal oxide.

The composition for forming an antifouling coating film of the present invention contains at least an organic silicate compound or an organic titanate compound and a modified cellulose nanomaterial, and optionally contains a photocatalytic metal oxide. The organic silicate compound is a tetrafunctional hydrolyzable silane compound represented by the chemical formula: SiO(OR) ₄ , where R is an alkyl group having 1 to 10 carbon atoms (especially a lower alkyl group having 1 to 3 carbon atoms). group), or an aryl group (especially a phenyl group), specifically tetramethoxysilane (Si(OCH ₃ ) ₄ : aka tetramethyl silicate), tetraethoxysilane (Si(OC ₂ H ₅ ) ₄ : aka tetraethyl silicate) , tetrapropoxysilane (Si(OC ₃ H ₇ ) ₄ : aka tetrapropyl silicate), tetrabutoxysilane (Si(OC ₄ H ₉ ) ₄ : aka tetrabutyl silicate), tetraphenoxysilane (Si(OC ₆ H ₆ ) ₄ : tetraphenyl silicate), dimethoxydiethoxysilane (Si(OCH ₃ ) ₂ (OC ₂ H ₅ ) ₂ : dimethyldiethyl silicate). The multimer of the organic silicate compound is a condensate represented by the chemical formula: Si _n O _n-1 (OR) _{2 (n+1)} , where R is an alkyl group having 1 to 10 carbon atoms (especially 1 to 3 lower alkyl groups), or aryl groups (especially phenyl groups), n is the degree of polymerization (so-called n-mer) representing the number of condensed molecules of the tetrafunctional hydrolyzable silane compound, and n is 2 or more organic The silicate compound multimer is a multimer formed by condensation of two or more molecules in a reaction between silanol groups produced by hydrolysis of a tetrafunctional hydrolyzable silane compound. It means the number of Si atoms contained in the molecule. In the present invention, a sol-gel coating film of an organic silicate compound multimer (Si _n O _n−1 (OR) _2(n+1) ) having a multimerization degree of 2 to 10, preferably 4 to 6, is used as a barrier film containing a modified cellulose nanomaterial. A dirty coating is preferred. If the atomic arrangement of this antifouling coating film is modeled as a square lattice network consisting of horizontal and vertical axes, Si atoms are arranged at the intersections of the horizontal and vertical axes, and between the Si—Si atoms that are adjacent vertically and horizontally. It is an image in which O atoms are arranged.

The composition for forming an antifouling coating film of the present invention contains at least an organic titanate compound and a modified cellulose nanomaterial, and optionally contains a photocatalytic metal oxide. The organic titanate compound is a tetrafunctional hydrolyzable titanium compound represented by the chemical formula: TiO(OR) ₄ , where R is an alkyl group having 1 to 10 carbon atoms (especially a lower alkyl group having 1 to 3 carbon atoms). group), or an aryl group (especially a phenyl group), specifically tetramethoxytitanium (Ti(OCH ₃ ) ₄ : aka tetramethyl titanate), tetraethoxytitanium (Ti(OC ₂ H ₅ ) ₄ : aka tetraethyl titanate) , tetrapropoxy titanium (Ti(OC ₃ H ₇ ) ₄ : aka tetrapropyl titanate), tetrabutoxy titanium (Ti(OC ₄ H ₉ ) ₄ : aka tetrabutyl titanate), tetraphenoxy titanium (Ti(OC ₆ H ₆ ) ₄ : alias tetraphenyl titanate), titanium alkoxide compounds such as dimethoxydiethoxy titanium (Ti(OCH ₃ ) ₂ (OC ₂ H ₅ ) ₂ : alias dimethyldiethyl titanate), tributoxy titanium stearate, isopropoxy titanium tri Titanium acylate compounds such as stearates: Ti(OOCR) _n , and also titanium chelate compounds such as diisopropoxytitanium bisacetylacetonate, diisopropoxytitanium bisethylacetoacetate: (ROO) _2Ti (OR) ₂ complexes, etc. . The polymer of the organic titanate compound is a condensate represented by the chemical formula: Ti _n O _n-1 (OR) _{2 (n+1)} , where R is an alkyl group having 1 to 10 carbon atoms (especially -3 lower alkyl groups), or aryl groups (especially phenyl groups), n is the degree of polymerization (so-called n-mer) representing the number of condensed molecules of the tetrafunctional hydrolyzable titanium compound, and n is an organic titanate of 2 or more The compound multimer is a multimer formed by condensation of two or more molecules in a reaction between titanol groups produced by hydrolysis of a tetrafunctional hydrolyzable titanium compound, and the degree of multimerization represented by n is one molecule of the multimer. It means the number of Ti atoms contained therein. In the present invention, a sol-gel coating film of an organic titanate compound multimer (Ti _n O _n−1 (OR) _2(n+1) ) having a multimerization degree of 2 to 10, preferably 4 to 6, is used as a barrier film containing a modified cellulose nanomaterial. A dirty coating is preferred. If the atomic arrangement of this antifouling coating film is modeled as a square lattice network consisting of horizontal and vertical axes, Ti atoms are arranged at the intersections of the horizontal and vertical axes, and between Ti—Ti atoms that are adjacent vertically and horizontally. It is an image in which O atoms are arranged.

The concentration of the hydrolysis product of the organic silicate or organic titanate compound contained in the antifouling coating film-forming composition (water/alcohol solvent) is in the range of 0.01 to 30% by mass, particularly 0.1 to 5% by mass. is preferred. In order to further enhance the abrasion resistance and durability of the antifouling coating film, the composition for forming an antifouling coating film contains an inorganic colloid (silica sol, antimony sol, alumina sol, zirconia sol, etc.) as an organic silicate compound or It can be contained in an amount of 0.1 to 25% by mass based on the concentration of the hydrolysis product of the organic titanate compound. For promoting hydrolysis, metal alkoxides in which an alkoxy group is bonded to metals such as aluminum, titanium, and zirconium, or metal chelate compounds capable of forming keto-enol tautomers on these metal alkoxides, inorganic acids (hydrochloric acid, Nitric acid, phosphoric acid, etc.), organic acids (formic acid, acetic acid, benzenesulfonic acid, etc.), ammonia, organic amines, dibutyltin dilaurate, dibutyltin dioctyate, etc., are preferably used as hydrolysis catalysts in arbitrary amounts.

In order to further enhance the wear resistance and durability of the antifouling coating film, the composition for forming the antifouling coating film includes modified cellulose nanomaterials treated with a silane coupling agent and organic titanate-treated To incorporate modified cellulose nanomaterials, esterified (borate esterified, phosphate esterified, silicicate esterified) modified cellulose nanomaterials into the antifouling coating film (organic/inorganic condensate) structure in some state In addition, a silane coupling agent (alkoxysilane compound) can be used in combination in an amount of 0.1 to 25% by mass based on the concentration of the hydrolysis product of the organic silicate compound or organic titanate compound. A hydrolysis product of an organic silicate compound or an organic titanate compound, or a silanol group-containing organic silane compound and a silane coupling agent (alkoxysilane compound), or a titanol group-containing organic titanium compound and a silane coupling agent (alkoxysilane compound), etc. Sol-gel polycondensation forms an antifouling coating that is resistant to bending. Silane coupling agents, i.e., alkoxysilane compounds, include aminosilane, vinylsilane, epoxysilane, methacrylsilane, acrylsilane, chlorosilane, mercaptosilane, isocyanuratesilane, isocyanatesilane, etc., and those described in paragraph [0020]. can also be used in combination of multiple types.

The modified cellulose nanomaterial contained in the antifouling coating film-forming composition is contained in an amount of 0.01 to 5% by mass, particularly 0.1 to 3% by mass relative to the antifouling coating film. It enhances the resistance resistance of the antifouling coating film, prevents deterioration such as cracks in the antifouling coating film, and prevents the antifouling coating film from easily wearing out and falling off, resulting in an antifouling effect. long-term sustainability. Modified cellulose nanomaterials are powders obtained by mechanically defibrating cellulose raw materials (chemically treated pulp, mechanically shredded pulp, waste paper pulp, etc.) (coarse defibration/fine fibrillation) and making the fiber diameter nano-sized. Cellulose nanofibers in the form of solids, slurries, or liquid dispersions, particularly chemically modified ones, are preferred. In addition, the average aspect ratio (average fiber length/average fiber diameter ) 50 or less, an average fiber diameter of 10 nm to 50 nm, and an average fiber length of 300 nm to 500 nm, cellulose nanocrystals in the form of powder, slurry, or liquid dispersion, and chemically modified ones are particularly preferable. Modification of the modified cellulose nanomaterial suitable for the present invention includes esterification (one or more selected from boric acid esterification, phosphoric acid esterification, and silicic acid esterification ), silane coupling agent treatment (aminosilane modification , vinylsilane-modified, epoxysilane-modified, methacrylsilane-modified, acrylsilane-modified, chlorosilane-modified, mercaptosilane-modified, isocyanurate silane-modified, isocyanatesilane-modified, and subjected to a chemical reaction treatment in an aqueous hydrolyzed solution. ), and organic titanate treatment (chemical reaction treatment in an aqueous solution of hydrolysis of the organic titanate compound described in paragraph [0016]), and two or more of these modifications can be used in combination. In particular, the modified cellulose nanofibers have an average aspect ratio (average fiber length/average fiber diameter) of 50 to 10000, an average fiber diameter of 3 nm to 100 nm, and an average fiber length of 2 μm to 100 μm. It has excellent dispersibility in the forming composition and stabilizes its presence in the antifouling coating film.

In the modified cellulose nanomaterials to be used, especially silane coupling agent treatment (aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylsilane modification, acrylsilane modification, chlorosilane modification, mercaptosilane modification, isocyanurate silane modification, isocyanate silane modification, Selected one or more types) Modification is performed by treating cellulose nanofibers, cellulose nanocrystals, etc. with an aqueous solution having a concentration of 1 to 10% by mass containing one or more silane coupling agents for 24 hours, and hydrolyzing the silane coupling agents. Entity: XR—Si(OH) ₃ (X and Y are shown below) is one or more reactants bound to hydroxyl groups, carboxy groups, etc. of the modified cellulose nanomaterial. Such a reactant may be vinylsilane/methacrylsilane-modified, aminosilane/mercaptosilane-modified, or the like by using two kinds of silane coupling agents in combination, or modification by using three or more kinds of silane coupling agents in combination. may The silane coupling agent is an alkoxysilane compound having two or more different reactive groups in the molecule represented by the general formula: XR—Si(Y) ₃ , for example, X=amino group, vinyl group, epoxy group, Methacryl group, acryl group, chloro group, mercapto group, isocyanurate group, isocyanate group, etc. (R=alkyl chain), Y=methoxy group, ethoxy group and the like. Vinylsilanes include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc. Epoxysilanes include β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane and the like, γ-methacryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane as methacrylsilanes, and N-β (aminoethyl) γ-aminopropyltrimethoxysilane as aminosilanes Silane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. Chlorosilane, γ-chloropropyltrimethoxysilane, etc. Mercaptosilane can be exemplified by γ-mercaptopropyltrimethoxysilane, isocyanurate silanes such as tris-(trimethoxysilylpropyl)isocyanurate, and isocyanate silanes such as 3-isocyanatopropyltriethoxysilane. By using a modified product treated with such a silane coupling agent, a sol-gel coating film that constitutes an antifouling coating film for industrial sheet materials (atomic arrangement is modeled on a square lattice network consisting of horizontal and vertical axes). For example, Si atoms are arranged at the intersection of the horizontal axis and the vertical axis, and O atoms are arranged between Si—Si atoms adjacent vertically and horizontally, or Ti atoms are arranged at the intersection of the horizontal axis and the vertical axis, and are arranged vertically and horizontally. O atoms are arranged between adjacent Ti—Ti atoms), and these silane coupling agent-treated modified bodies are incorporated in some state to form a state changed to a complex structure different from the lattice network structure. , It improves the resistance of the antifouling coating film against bending and abrasion loads, and prevents damage such as cracks in the antifouling coating film, and prevents the antifouling coating film from easily wearing off Allows longer lasting staining effect. Modification by organic titanate treatment is treated in the same manner as the silane coupling agent, and the organic titanate compounds described in paragraph [0016], particularly titanium acylate compounds such as tributoxytitanium stearate and isopropoxytitanium tristearate. : Ti(OOCR) _n , isopropoxytitanium triisostearate, isopropoxytitanium dimethacrylate isostearate, isopropoxytitanium trisdioctylphosphate, bisdioctylphosphate ethylene glycolate titanium, dibutoxybistriethanolaminatotitanium, etc. from 1 to A cellulose nanomaterial is subjected to a chemical reaction treatment for 24 hours in a hydrolyzed aqueous solution having a concentration of 10% by mass.

In the modified cellulose nanomaterials to be used, among the modification by esterification, boric acid esterification is performed by adding boric acid such as orthoboric acid (H ₃ BO ₃ ) and metaboric acid (HBO ₂ ) to cellulose nanofibers and cellulose nanocrystals. and sodium tetraborate hydrate (Na ₂ B ₄ O ₇ ·10H ₂ O), sodium pentaborate (NaB ₅ O ₈ ), etc., with a borate aqueous solution having a concentration of 1 to 10% by mass for 24 hours, It is a modification in which boric acid components are reacted with carboxy groups and carboxymethyl groups of cellulose nanofibers and _{cellulose nanocrystals} . acid, polyphosphoric acid (HPO ₃ )n, phosphorous acid, phosphoric acids such as phosphinic acid, and metal salts and ammonium salts derived from these phosphoric acids in an aqueous phosphate solution having a concentration of 1 to 10% by mass. It is a modification in which the carboxyl groups of cellulose nanofibers and cellulose nanocrystals are reacted with a phosphoric acid component after time treatment. glass), lithium silicate, potassium silicate, or other silicate solution with a concentration of 1 to 10% by mass for 24 hours to react the carboxy groups of cellulose nanofibers or cellulose nanocrystals with silicic acid components. . These modifications include boric acid/phosphate esterification by combined treatment with an aqueous borate solution and an aqueous phosphate solution, boric acid/silicate esterification by combined treatment with an aqueous borate solution and an aqueous silicate solution, and phosphoric acid esterification. Phosphoric acid/silicic acid esterification by combined treatment with an aqueous salt solution and an aqueous silicate solution may also be used. By using a modified product obtained by such an esterification treatment in an antifouling coating film-forming composition, the molecular structure of the sol-gel coating that constitutes the antifouling coating film of industrial sheet materials (atomic arrangement is horizontal and vertical) Assuming a square lattice network consisting of axes as a model, Si atoms are arranged at the intersections of the horizontal and vertical axes, and O atoms are arranged between the Si—Si atoms adjacent to each other in the vertical and horizontal directions, or at the intersections of the horizontal and vertical axes. Ti atoms are arranged in the upper and lower left and right, and O atoms are arranged between the Ti-Ti atoms adjacent to each other in the vertical and horizontal directions). By being in such a state, the resistance resistance of the antifouling coating film to the load of bending and abrasion is improved, damage such as cracks does not easily occur in the antifouling coating film, and the antifouling coating film is easily worn and worn. It enables further long-term durability of antifouling property without falling off. In addition, these modifications can impart antiseptic properties to cellulose nanofibers and cellulose nanocrystals.

Photocatalytic titanium oxide, photocatalytic titanium peroxide (peroxotitanic acid), photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic strontium titanate, photocatalytic tungsten oxide, and photocatalytic Photocatalytic metal oxide having an average particle size of 50 nm or less, particularly 20 nm or less, selected from photocatalytic bismuth oxide and photocatalytic iron oxide. In the antifouling coating film obtained from the composition for forming a fouling coating film, the content of the photocatalytic metal oxide is contained in an amount of 5 to 50% by mass based on the antifouling coating film, so that the self-cleaning antifouling effect due to photocatalytic activity is obtained. can be expressed. Metals and metal oxides such as Pt, Rh, RuO ₂ , Nb, Cu, Sn and NiO can be added to these photocatalytic metal oxides as synergists. By using such a photocatalytic metal oxide in the antifouling coating film-forming composition, the molecular structure of the sol-gel coating film constituting the antifouling coating film of industrial sheet materials (atomic arrangement is horizontal axis and vertical axis Assuming a square lattice network modeled from Ti atoms are arranged, and O atoms are arranged between the Ti—Ti atoms that are adjacent vertically and horizontally). These photocatalytic metal oxides are incorporated in some state to change into a complex structure different from the lattice network structure. In this state, the antifouling coating improves resistance to bending and abrasion loads, and the antifouling coating does not easily wear off or come off, making it possible to maintain the antifouling property for a longer period of time. . Self-cleaning antifouling property means that photocatalytic activity decomposes organic dirt such as finger marks, dust, tar, bird droppings, mold, algae, etc. with active oxygen radicals, and the mechanism of superhydrophilization by photocatalyst. It is a washing mechanism that does not require manual labor because dirt residue is easily washed away by rainfall, so that the appearance of the article is recovered before the dirt adheres. By applying such an antifouling coating film to tarpaulins (industrial material sheets) that are used as materials for membrane structures such as large tents (pavilions), circus tents, tent warehouses, and membrane roofs (ceilings) for architectural spaces. To maintain a clean appearance without impairing the appearance of a membrane structure.

The composition for forming an antifouling coating film of the present invention forms a robust antifouling coating film on substrates such as films, synthetic resin sheets, decorative panels, building material panels, glass products (parts), and plastic moldings (parts). do. In particular, since this antifouling coating film is resistant to bending and abrasion, and hardly cracks, it can be widely applied regardless of whether or not the base material has elongation or flexibility, and whether it is large or small. Among them, the composition for forming an antifouling coating film of the present invention is suitable for flexible synthetic resin sheets (industrial material sheets such as tarpaulin, canvas, mesh sheet, synthetic leather, etc.) containing fabric as a core material, and is suitable for industrial material sheets. By forming the antifouling coating film of the present invention, the aesthetic appearance of membrane structures such as large tents (pavilions), circus tents, tent warehouses, and membrane roofs (ceilings) of architectural spaces constructed using these industrial material sheets. can be maintained in a clean state for a long time. Industrial sheet materials include tarpaulins made by laminating a thermoplastic resin film on the front and back of a slightly open fabric, canvas made by impregnating and coating the front and back of a tightly woven fabric with a thermoplastic resin, and woven fabric. A mesh sheet obtained by impregnating and coating a thermoplastic resin on the entire open weave fabric, and a synthetic leather obtained by laminating a thermoplastic resin film on one side of a densely textured fabric.

Textiles used for industrial material sheets include plain weaves (warp/weft biaxial weave, warp/upper left bias/upper right bias triaxial weave, warp/weft/upper left bias/upper right bias quadriaxial weave), basket weave, twill weave, Fabrics such as satin fabrics, Mojiri fabrics (gauze fabrics, silk fabrics), and double fabrics can be used. Suitable fabric weight is 100 to 500 g/m ² and porosity is 0 to 25%. In that case, the porosity is preferably 20 to 50%. These fabrics may be subjected to known dyeing and finishing treatments such as scouring, bleaching, dyeing, softening, water repellency, mildewproofing, flameproofing, calendering, and the like. As for the thread constituting the woven fabric, any fiber such as synthetic fiber, natural fiber, semi-synthetic fiber, inorganic fiber, and mixed fiber composed of two or more of these can be used, but polypropylene fiber and polyethylene are generally used. Synthetic fibers such as fibers, polyvinyl alcohol fibers, polyester (polyethylene terephthalate: PET, polybutylene terephthalate: PBT, polynaphthalene terephthalate: PNT, etc.) fibers, nylon fibers, and mixed fibers of these (mixed twist / plied twist) Fineness 125 ~2000 denier (139-2222 dtex) multifilament yarn, staple spun yarn (10-30 count single yarn or 15-30 count double yarn), covering yarn, etc. can be used. Multifilament yarn is suitable for tarpaulin fabrics and mesh sheet fabrics, short fiber spun yarns and covering yarns are suitable for canvas fabrics, and noncombustible materials certified by the Minister of Land, Infrastructure, Transport and Tourism ), fabrics made of inorganic multifilament yarns such as glass fiber, silica fiber, alumina fiber, silica-alumina fiber, carbon fiber, and mixed fibers (mixed twist / plied twist) are suitable. .

The thermoplastic resin film laminated on the front and back of these fabrics, the thermoplastic resin impregnated and coated on the front and back of the fabric, and the thermoplastic resin impregnated and coated on the entire surface of the fabric are specifically soft vinyl chloride resin ( plasticizer), vinyl chloride copolymer resin, chlorinated vinyl chloride resin, olefin resin (PE, PP), olefin copolymer resin, ethylene-vinyl acetate copolymer resin (EVA), ethylene-(meth ) Acrylic acid (ester) copolymer resin, urethane resin, vinyl acetate copolymer resin, styrene copolymer resin, polyester copolymer resin, fluorine-containing copolymer resin, Shore A hardness 35 to 85 degree of thermoplastic, or elastomer. An elastomer is a block copolymer resin composed of two or more kinds of monomers, and each block component constitutes a hard segment and a soft segment. These thermoplastic resins include stabilizers, fillers, colorants, pigments, metallic pigments, phosphorescent pigments, flame retardants, flame retardants, UV absorbers, light stabilizers, antifungal agents, antibacterial agents, antistatic agents, Any known additives such as cross-linking agents can be used in combination.

The front and back thermoplastic resin films that make up the tarpaulin are obtained by hot-kneading a thermoplastic resin composition (preferably vinyl chloride resin/plasticizer, etc.) and melt-rolling them by a calendar method or a T-die extrusion method to a thickness of 100 to 100. A tarpaulin having a thickness of 0.4 to 1.5 mm and a weight of 500 to 2000 g/m is obtained by forming a film (sheet) of 300 μm and thermally laminating it on the front and back of the open fabric. The tarpaulin is suitable for membrane structures such as large tents (pavilions), circus tents, tent warehouses, membrane roofs (ceilings) for building spaces, and sunshade tents, as well as for building protection sheets and flexible container bags. On the other hand, the thermoplastic resin-impregnated coating on the front and back constituting the canvas is applied by a coating method such as knife coating to the front and back of the fabric with a thermoplastic resin composition in solution (preferably a paste of vinyl chloride resin / plasticizer). The woven fabric is immersed in a liquid bath filled with a film having a thickness of 30 to 150 μm or a thermoplastic resin composition (preferably vinyl chloride resin paste) in the form of a solution by heating and gelling it. Then, it was pulled up and squeezed between a pair of rubber rolls, immediately after which a film was formed to a thickness of 30 to 150 µm by a dipping method of heating and gelling. For canvas, the dipping method using a paste made of vinyl chloride resin/plasticizer is suitable, and those with a thickness of 0.3 to 0.8 mm and a mass of 400 to 1000 g/m are used for truck hoods, truck bed sheets, roof tents, sheet houses, etc. Suitable for use in In addition, the thermoplastic resin-impregnated coating on the entire surface constituting the mesh sheet is obtained by immersing a textured fabric in a liquid bath filled with a solution-like thermoplastic resin composition (preferably vinyl chloride resin paste), A coating of 30 to 150 μm in thickness was formed by a dipping method in which this was pulled up and at the same time compressed between a pair of rubber rolls and then heat-gelled. The mesh sheet is suitable for the dipping method with a paste of vinyl chloride resin/plasticizer, etc., and the mesh sheet with a thickness of 0.3 to 0.8 mm and a weight of 200 to 500 g/m is suitable for applications such as protective covering sheets at construction sites. there is

The present invention will be further described with reference to the following examples and comparative examples, but embodiments of the present invention are not limited to the scope of these examples.
Bending and kneading resistance: JIS L1096 8.19.2 B method) Scott method
2.5 cm (vertical) x 12 cm (horizontal) and 2.5 cm (horizontal) x 12 cm (vertical) taken from the sheet are used as test pieces, and attached to a Scott type testing machine (stroke 4 cm), 1 kgfg load x 300 times After bending and kneading, a digital microscope (VHX-1000: Keyence Corporation) is used to observe an enlarged image of the antifouling coating film at a magnification of 500 times. The presence or absence of dropout was determined.
1: No cracks, peeling, or falling off of the antifouling coating film
2: Cracks are observed in the antifouling coating film, but neither peeling nor falling off is observed.
3: Cracks, peeling, and falling off are observed in the antifouling coating film
Abrasion resistance: JIS L1096 8.19.3 C method) Taber type method
A disk with a diameter of 13 cm taken from the sheet was used as a test piece, and mounted on a Taber type abrasion tester (wear wheel CS-10). In the city, outdoor exposure for 3 months from July to September 2019 is performed, and the degree of contamination of the antifouling coating film (abrasion test part) is determined by color difference ΔE (JIS Z8730) (measured without wiping or washing. )bottom.
1: ΔE = 0 to 2.9 Good results maintaining the initial state (no problem)
2: ΔE = 3 to 4.9 Slightly dark but not noticeable (no problem)
3: ΔE = 5 to 7.9 Dark and disturbing
4: ΔE = 8 to 9.9 Darkening, dirty
5: ΔE = 10 ~ Pretty dark and dirty

[Example 1]
<fabric>
Made of 1000 denier (1111 dtex) polyethylene terephthalate (PET) fibers (192 filaments), PET multifilament yarns with S twist of 50 T / m are used for the warp group and the weft group, and the warp group is 1 inch apart. A plain weave with 16 weaves and a weft group of 16 wefts per inch was used. This fabric had a mass of 150 g/m ² and a porosity (total void area) of 14%.
<Tarpaulin base material>
Using this woven fabric as a base material, a 0.2 mm-thick calendered film made of a soft vinyl chloride resin composition of the following [Formulation 1] was used as a front and back coating layer on both sides of the fabric, and melt lamination was performed by thermocompression bonding with a laminator. Thus, a tarpaulin base material having a thickness of 0.7 mm and a mass of 830 g/m ² was obtained.
[Formulation 1]: Soft vinyl chloride resin composition (compound)
Vinyl chloride resin (K value 71.5) 100 parts by mass 4-cyclohexene-1,2-dicarboxylic acid bis (2-ethylhexyl) (plasticizer)
55 parts by mass tricresyl phosphate (flame retardant plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass Barium/zinc composite stabilizer 2 parts by mass Antimony trioxide (flame retardant) 10 parts by mass Rutile type Titanium oxide (white pigment) 5 parts by mass Benzotriazole skeleton compound (ultraviolet absorber) 0.3 parts by mass
<Industrial sheet (1): tarpaulin>
A composition for forming an antifouling coating film was obtained by blending the composition of the following [Formulation 2].
Next, on one surface of the tarpaulin base material, this composition for forming an antifouling coating film is gravure-coated using a 100-mesh gravure roll, and dried by heating in a hot air oven at 120° C. for 2 minutes to form an antifouling coating film. The composition was sol-gel cured to form an organic/inorganic polymer antifouling coating. Then, an industrial sheet ( ¹ ).
[Formulation 2] Composition for forming an antifouling coating film
5% by mass of ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ), and
A mixture containing 95% by mass of a tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ]
100 parts by mass Hydrolysis catalyst: 2% hydrochloric acid 5 parts by mass Photocatalytic titanium oxide sol 50 parts by mass Acidic acid with nitric acid: particle diameter 10 nm: solid content 30% by mass ethanol solution Vinyl silane coupling agent 5 parts by mass
* Vinyltrimethoxysilane silica sol (particle diameter 12 nm: solid content 30% by mass ethanol solution) 50 parts by mass Modified cellulose nanofiber (2% by mass aqueous solution) 500 parts by mass * 3-Mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent )
Hydrolyzate of cellulose nanofiber reacted with hydroxyl groups Modified product by silane coupling treatment: fiber width 3-10 nm, fiber length 30-100 μm

[Example 2]
The antifouling coating of [Formulation 3] was prepared in the same manner as in Example 1 except that the composition for forming an antifouling coating film of Example 1 [Formulation 2] was changed to the composition for forming an antifouling coating film of [Formulation 3]. An industrial sheet (2) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
[Formulation 3] Composition for forming an antifouling coating film
Ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) 5% by mass, and
A mixture containing 95% by mass of a tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ]
100 parts by mass Hydrolysis catalyst: 2% hydrochloric acid 5 parts by mass Photocatalytic titanium oxide sol 50 parts by mass Nitric acid: particle diameter 10 nm: solid content 30% by mass ethanol solution
Epoxy silane coupling agent 5 parts by mass * 3-Glycidoxypropyltrimethoxysilane Silica sol (particle size 12 nm: solid content 30% by mass ethanol solution) 50 parts by mass Modified cellulose nanofiber (2% by mass aqueous solution) 500 parts by mass * Silane-coupling-treated modified product in which the hydrolyzate of 3-aminopropyltrimethoxysilane (amino-silane coupling agent) is reacted with the hydroxyl groups of cellulose nanofibers: fiber width 3-10 nm, fiber length 30-100 μm

[Example 3]
The antifouling coating of [Formulation 4] was prepared in the same manner as in Example 1 except that the composition for forming an antifouling coating film of Example 1 [Formulation 2] was changed to the composition for forming an antifouling coating film of [Formulation 4]. An industrial sheet (3) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
[Formulation 4] Composition for forming an antifouling coating film
Ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) 5% by mass, and
A mixture containing 95% by mass of a tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ]
100 parts by mass Hydrolysis catalyst: 2% hydrochloric acid 5 parts by mass Photocatalytic titanium oxide sol 50 parts by mass Acidic acid with nitric acid: Particle diameter 10 nm: Solid content 30% by mass ethanol solution Methacryl-based silane coupling agent 5 parts by mass *3-Methacryloxypropyltri Methoxysilane Silica sol (particle diameter 12 nm: solid content 30% by mass ethanol solution) 50 parts Modified cellulose nanofiber (2% by mass aqueous solution) 500 parts Silane-coupling-treated modified product in which the decomposed product is reacted with the hydroxyl groups of cellulose nanofibers: fiber width 3-10 nm, fiber length 30-100 μm

[Example 4]
The antifouling coating of [Formulation 5] was prepared in the same manner as in Example 1 except that the composition for forming an antifouling coating film of Example 1 [Formulation 2] was changed to the composition for forming an antifouling coating film of [Formulation 5]. An industrial sheet (4) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
[Formulation 5] Composition for forming an antifouling coating film
Ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) 5% by mass, and
A mixture containing 95% by mass of a tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ]
100 parts by mass Hydrolysis catalyst: 2% hydrochloric acid 5 parts by mass Photocatalytic titanium oxide sol 50 parts by mass Acidic acid with nitric acid: particle diameter 10 nm: solid content 30% by mass ethanol solution Vinyl silane coupling agent 5 parts by mass
* Vinyltrimethoxysilane silica sol (particle diameter 12 nm: solid content 30% by mass ethanol solution) 50 parts by mass Modified cellulose nanofiber (2% by mass aqueous solution) 500 parts by mass * Tri-n-butoxytitanium monostearate (organic titanate compound) Silane-coupling-treated modified product obtained by reacting the hydrolyzate of cellulose nanofibers with hydroxyl groups: fiber width 3-10 nm, fiber length 30-100 μm

[Example 5]
The antifouling coating of [Formulation 6] was prepared in the same manner as in Example 1 except that the composition for forming an antifouling coating film of Example 1 [Formulation 2] was changed to the composition for forming an antifouling coating film of [Formulation 6]. An industrial sheet (5) having a thickness of 0.7 mm and a weight of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
[Formulation 6] Composition for forming an antifouling coating film
Ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) 5% by mass, and
A mixture containing 95% by mass of a tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ]
100 parts by mass Hydrolysis catalyst: 2% hydrochloric acid 5 parts by mass Photocatalytic titanium oxide sol 50 parts by mass Acidic acid with nitric acid: particle diameter 10 nm: solid content 30% by mass ethanol solution Epoxy silane coupling agent 5 parts by mass *3-Glycidoxypropyl Trimethoxysilane silica sol (particle diameter 12 nm: solid content 30% by mass ethanol solution) 50 parts by mass Modified cellulose nanofiber (2% by mass aqueous solution) 500 parts by mass *Hydration of di-i-propoxytitanium distearate (organic titanate compound) Silane-coupling-treated modified product obtained by reacting decomposition products with hydroxyl groups of cellulose nanofibers: fiber width 3-10 nm, fiber length 30-100 μm

[Example 6]
The antifouling coating of [Formulation 7] was prepared in the same manner as in Example 1 except that the composition for forming an antifouling coating film of Example 1 [Formulation 2] was changed to the composition for forming an antifouling coating film of [Formulation 7]. An industrial sheet (6) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 7] contains 5 mass of ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) in the composition for forming an antifouling coating film of [Formulation 2]. 100 parts by mass of a mixture of 95% by mass of tetraethoxysilane pentamer of Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ] and tetra-i-propoxytitanium [Ti(OCH(CH ₃ ) ₂ ] ₄ : 37% by mass in terms of TiO ₂ ) 5% by mass, and 95% by mass of tetra-i-propoxy titanium tetramer of iC ₃ H ₇ -[TiO(O-iC ₃ H ₇ ) ₂ ] ₄ -iC ₃ H ₇ % of the mixture was changed to 100 parts by mass.

[Example 7]
The antifouling coating of [Formulation 8] was prepared in the same manner as in Example 2 except that the composition for forming an antifouling coating film of Example 2 [Formulation 3] was changed to the composition for forming an antifouling coating film of [Formulation 8]. An industrial sheet (7) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 8] contains 5 mass of ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) in the composition for forming an antifouling coating film of [Formulation 3]. %,as well as
100 parts by mass of a mixture of 95% by mass of tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ], tetra-i-propoxytitanium [Ti(OCH(CH ₃ ) ₂ ] ₄ : 37% by mass in terms of TiO ₂ ) and 95% by mass of the tetra-i-propoxytitanium tetramer of iC ₃ H ₇ -[TiO(O-iC ₃ H ₇ ) ₂ ] ₄ -iC ₃ H ₇ The mixture was changed to 100 parts by mass, and the composition for forming an antifouling coating film of [Formulation 3] was the same as the composition other than this change.

[Example 8]
The antifouling coating of [Formulation 9] was prepared in the same manner as in Example 3 except that the composition for forming an antifouling coating film of Example 3 [Formulation 4] was changed to the composition for forming an antifouling coating film of [Formulation 9]. An industrial sheet (8) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 9] contains 5 mass of ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) in the composition for forming an antifouling coating film of [Formulation 4]. %,as well as
100 parts by mass of a mixture of 95% by mass of tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ], tetra-i-propoxytitanium [Ti(OCH(CH ₃ ) ₂ ] ₄ : 37% by mass in terms of TiO ₂ ) and 95% by mass of the tetra-i-propoxytitanium tetramer of iC ₃ H ₇ -[TiO(O-iC ₃ H ₇ ) ₂ ] ₄ -iC ₃ H ₇ The mixture was changed to 100 parts by mass, and the composition for forming an antifouling coating film of [Formulation 4] was the same as the composition other than this change.

[Example 9]
The antifouling coating of [Formulation 10] was prepared in the same manner as in Example 4 except that the composition for forming an antifouling coating film of Example 4 [Formulation 5] was changed to the composition for forming an antifouling coating film of [Formulation 10]. An industrial sheet (9) having a thickness of 0.7 mm and a weight of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 10] contains 5 mass of ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) in the composition for forming an antifouling coating film of [Formulation 5]. %,as well as
100 parts by mass of a mixture of 95% by mass of tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ], tetra-i-propoxytitanium [Ti(OCH(CH ₃ ) ₂ ] ₄ : 37% by mass in terms of TiO ₂ ) and 95% by mass of the tetra-i-propoxytitanium tetramer of iC ₃ H ₇ -[TiO(O-iC ₃ H ₇ ) ₂ ] ₄ -iC ₃ H ₇ The mixture was changed to 100 parts by mass, and the composition for forming an antifouling coating film of [Formulation 5] was the same as the composition other than this change.

[Example 10]
The antifouling coating of [Formulation 11] was prepared in the same manner as in Example 5 except that the composition for forming an antifouling coating film of Example 5 [Formulation 6] was changed to the composition for forming an antifouling coating film of [Formulation 11]. An industrial sheet (10) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 11] contains 5 mass of ethyl silicate (Si(OC ₂ H ₅ ) ₄ : 40% by mass in terms of SiO ₂ ) in the composition for forming an antifouling coating film of [Formulation 6]. %,as well as
100 parts by mass of a mixture of 95% by mass of tetraethoxysilane pentamer of [Si ₅ O ₄ (OC ₂ H ₅ ) ₁₂ ], tetra-i-propoxytitanium [Ti(OCH(CH ₃ ) ₂ ] ₄ : 37% by mass in terms of TiO ₂ ) and 95% by mass of the tetra-i-propoxytitanium tetramer of iC ₃ H ₇ -[TiO(O-iC ₃ H ₇ ) ₂ ] ₄ -iC ₃ H ₇ The mixture was changed to 100 parts by mass, and the composition for forming an antifouling coating film of [Composition 6] was the same as the composition other than this change.

[Example 11]
The antifouling coating of [Formulation 12] was prepared in the same manner as in Example 1, except that the composition for forming an antifouling coating film of Example 1 [Formulation 2] was changed to the composition for forming an antifouling coating film of [Formulation 12]. An industrial sheet (11) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 12] is obtained by replacing the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) in the composition for forming an antifouling coating film of [Formulation 2] with cellulose. 500 parts by mass of a silane coupling-treated modified product (2% by mass aqueous solution) reacted with the hydroxyl groups of nanofibers, and an aqueous solution of 3% by mass boric acid + 78% by mass ethyl cellosolve was added to carboxymethylated cellulose nanofibers (1st grade of cellulose, Boric acid ester modified product in which secondary hydroxyl groups (2, 3, 6 positions) are carboxymethylated) reacted with carboxymethyl group: fiber width 3-10 nm, fiber length 30-100 μm (2% by mass aqueous solution) 500 mass Other than this change, the composition for forming an antifouling coating film of [Formulation 2] is the same.

[Example 12]
The antifouling coating of [Formulation 12] was prepared in the same manner as in Example 1, except that the composition for forming an antifouling coating film of Example 1 [Formulation 2] was changed to the composition for forming an antifouling coating film of [Formulation 13]. An industrial sheet (12) having a thickness of 0.7 mm and a weight of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 13] is obtained by replacing the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) in the composition for forming an antifouling coating film of [Formulation 2] with cellulose. 500 parts by mass of silane coupling-treated modified product (2% by mass aqueous solution) reacted with hydroxyl groups of nanofibers, 3% by mass of phosphoric acid + 78% by mass of ethyl cellosolve aqueous solution was added to carboxymethylated cellulose nanofibers (1st grade of cellulose, Secondary hydroxyl group (2, 3, 6 positions) reacted with carboxymethyl group of carboxymethylation) Phosphate ester modified product: fiber width 3-10 nm, fiber length 30-100 μm (2% by mass aqueous solution) 500 parts by mass Except for this change, the composition for forming an antifouling coating film of [Formulation 2] is the same.

[Example 13]
The antifouling coating of [Formulation 12] was prepared in the same manner as in Example 1 except that the composition for forming an antifouling coating film of Example 1 [Formulation 2] was changed to the composition for forming an antifouling coating film of [Formulation 14]. An industrial sheet (13) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 14] is obtained by replacing the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) in the composition for forming an antifouling coating film of [Formulation 2] with cellulose. 500 parts by mass of a silane coupling-treated modified product (2% by mass aqueous solution) reacted with the hydroxyl groups of nanofibers, and an aqueous solution of 3% by mass silicic acid + 78% by mass ethyl cellosolve was added to carboxymethylated cellulose nanofibers (1st grade of cellulose, Secondary hydroxyl groups (2, 3, 6 positions) are reacted with carboxymethyl groups of carboxymethylation) to form silicic acid ester modified product: fiber width 3-10 nm, fiber length 30-100 μm (2% by mass aqueous solution) 500 parts by mass Except for this change, the composition for forming an antifouling coating film of [Formulation 2] is the same.

[Example 14]
The antifouling coating of [Formulation 15] was prepared in the same manner as in Example 6 except that the composition for forming an antifouling coating film of Example 6 [Formulation 7] was changed to the composition for forming an antifouling coating film of [Formulation 15]. An industrial sheet (14) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 15] is obtained by replacing the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) in the composition for forming an antifouling coating film of [Formulation 7] with cellulose. 500 parts by mass of a silane coupling-treated modified product (2% by mass aqueous solution) reacted with the hydroxyl groups of nanofibers, and an aqueous solution of 3% by mass boric acid + 78% by mass ethyl cellosolve was added to carboxymethylated cellulose nanofibers (1st grade of cellulose, Boric acid ester modified product in which secondary hydroxyl groups (2, 3, 6 positions) are carboxymethylated) reacted with carboxymethyl group: fiber width 3-10 nm, fiber length 30-100 μm (2% by mass aqueous solution) 500 mass Other than this change, the composition for forming an antifouling coating film of [Formulation 7] is the same.

[Example 15]
The antifouling coating of [Formulation 16] was prepared in the same manner as in Example 6 except that the composition for forming an antifouling coating film of Example 6 [Formulation 7] was changed to the composition for forming an antifouling coating film of [Formulation 16]. An industrial sheet (15) having a thickness of 0.7 mm and a weight of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 16] is obtained by replacing the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) in the composition for forming an antifouling coating film of [Formulation 7] with cellulose. 500 parts by mass of silane coupling-treated modified product (2% by mass aqueous solution) reacted with hydroxyl groups of nanofibers, 3% by mass of phosphoric acid + 78% by mass of ethyl cellosolve aqueous solution was added to carboxymethylated cellulose nanofibers (1st grade of cellulose, Phosphoric acid ester modified product obtained by reacting secondary hydroxyl groups (2,3,6 positions) with carboxymethyl groups: fiber width 3-10 nm, fiber length 30-100 μm (2% by mass aqueous solution) 500 mass Other than this change, the composition for forming an antifouling coating film of [Formulation 7] is the same.

[Example 16]
The antifouling coating of [Formulation 17] was prepared in the same manner as in Example 6 except that the composition for forming an antifouling coating film of Example 6 [Formulation 7] was changed to the composition for forming an antifouling coating film of [Formulation 17]. An industrial sheet (16) having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained, which was accompanied by an antifouling coating film formed from the film-forming composition.
The composition for forming an antifouling coating film of [Formulation 17] is obtained by replacing the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) in the composition for forming an antifouling coating film of [Formulation 7] with cellulose. 500 parts by mass of a silane coupling-treated modified product (2% by mass aqueous solution) reacted with the hydroxyl groups of nanofibers, and an aqueous solution of 3% by mass silicic acid + 78% by mass ethyl cellosolve was added to carboxymethylated cellulose nanofibers (1st grade of cellulose, Silicic acid ester modified product in which secondary hydroxyl groups (2, 3, 6 positions) are carboxymethylated) reacted with carboxymethyl group: fiber width 3-10 nm, fiber length 30-100 μm (2% by mass aqueous solution) 500 mass Other than this change, the composition for forming an antifouling coating film of [Formulation 7] is the same.

The composition for forming an antifouling coating film of the present invention (Examples 1 to 16) is a paint containing an organic silicate compound or an organic titanate compound, a modified cellulose nanomaterial, and a photocatalytic metal oxide. The composition for forming an antifouling coating film (Examples 1 to 16) is coated on a tarpaulin base material, and the antifouling coating film (Examples 1 to 16) obtained by sol-gel curing is obtained by using an organic silicate compound or The tarpaulin base of the composition for forming an antifouling coating film (Examples 1 to 16) is a coating film containing a modified cellulose nanomaterial in a hydrolytic condensate of an organic titanate compound and a photocatalytic metal oxide. By coating on the material, industrial material sheets (Examples 1 to 16) with an antifouling coating film are obtained. In the industrial material sheets (tarpaulins) of Examples 1 to 16, the antifouling coating film has improved resistance to bending and abrasion loads, and damage such as cracks easily occurs in the antifouling coating film. It was confirmed by the JIS L1096 8.19.2 B method: bending resistance test by the Scott method. In addition, JIS L1096 8.19.3 C method: Outdoor exposure of the sample after abrasion resistance test by Taber method ( 3 months in summer). This is because when the atomic arrangement model in the antifouling coating films of Examples 1 to 5 and 11 to 13 is a square lattice network consisting of horizontal and vertical axes, Si atoms are arranged at the intersections of the horizontal and vertical axes, It is a structure in which O atoms are arranged between Si—Si atoms adjacent to each other vertically and horizontally. Modified cellulose nanomaterials are somehow incorporated into a part of this lattice network structure model to create a complex structure different from the lattice network structure. It is considered that the effect is obtained by changing the state, and further, by taking in the photocatalytic metal oxide in some state and changing to a complicated structure different from the lattice network structure. Similarly, in the antifouling coating films of Examples 6 to 10 and 14 to 16, when the atomic arrangement model is a square lattice network model consisting of horizontal and vertical axes, Ti atoms are arranged at the intersections of the horizontal and vertical axes. , a structure in which O atoms are arranged between Ti—Ti atoms adjacent to each other vertically and horizontally, and modified cellulose nanomaterials are incorporated in some state into a part of this lattice network structure model to create a complex structure different from the lattice network structure. It is considered that the effect is obtained by changing to a complex structure different from the lattice network structure by incorporating the photocatalytic metal oxide in some state. Also, on the industrial sheets (1 to 16) of Examples 1 to 16, the characters ABCDE were drawn with a commercially available permanent pen (red), dried at room temperature for 60 seconds, and then wiped off with DRY tissue paper (rubbed back and forth 10 times). were carried out to evaluate the antifouling properties of these sheet materials. As a result, in the industrial sheet materials 1 to 16, red ink marks remained slightly, but as a result of adding wet tissue paper wiping off property (rubbing back and forth 10 times), the red ink marks were completely removed. Removed. Separately from this, when ABCDE was drawn with a commercially available oil-based pen (red), a sheet piece was subjected to a 120-hour accelerated weather resistance test (JIS K5600-7-7) using a xenon weather meter. In the industrial sheet materials 1 to 16 contained in the coating film, the red ink letters almost disappeared. Therefore, it can be seen that the industrial sheet materials of Examples 1 to 16 are suitable for outdoor permanent applications such as membrane structures such as large tents (pavilions), circus tents, tent warehouses, and membrane roofs (ceilings) of architectural spaces. It became clear.

[Comparative Example 1]
From the antifouling coating film-forming composition [formulation 2] of Example 1, silane coupling was performed by reacting the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) with the hydroxyl groups of the cellulose nanofibers. A tarpaulin of 0.7 mm and a mass of 832 g/m ² was prepared in the same manner as in Example 1 except that 500 parts by mass of the treated modified product (2% by mass aqueous solution) was omitted and replaced with 500 parts by mass of water [Formulation 18]. Obtained. Compared to the tarpaulins of Examples 1 to 16, the antifouling performance of the antifouling coating film was not inferior, but by omitting the modified cellulose nanomaterial, the antifouling coating in the Scott-type bending resistance rubbing test The effect on the film (--Si--O--based sol-gel condensate) became remarkable, and abnormalities such as cracks, peeling and falling off of the antifouling coating film were confirmed. In addition, the abrasion damage in the Taber abrasion test (50 rotations, 100 rotations) is greater than the antifouling coating film of Example 1 [conversion from formulation 2], and the antifouling coating film is exposed to the extent that the surface of the tarpaulin base material is exposed. It was missing, and when exposed to the outdoors, the amount of dirt adhered increased remarkably and it became dirty black. In other words, there was concern about the durability of the antifouling property for articles that were subjected to rubbing and dragging during the sewing and construction of the industrial material sheet.

[Comparative Example 2]
From the antifouling coating film-forming composition [formulation 7] of Example 6, silane coupling was performed by reacting the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) with the hydroxyl groups of the cellulose nanofibers. A tarpaulin of 0.7 mm and a mass of 832 g/m ² was prepared in the same manner as in Example 6, except that 500 parts by mass of the treated modified product (2% by mass aqueous solution) was omitted and replaced with 500 parts by mass of water [Formulation 19]. Obtained. Compared to the tarpaulins of Examples 1 to 16, the antifouling performance of the antifouling coating film was not inferior, but by omitting the modified cellulose nanomaterial, the antifouling coating in the Scott-type bending resistance rubbing test The effect on the film (--Ti--O--based sol-gel condensate) became remarkable, and abnormalities such as cracks, peeling and falling off of the antifouling coating film were confirmed. In addition, the abrasion damage in the Taber abrasion test (50 rotations, 100 rotations) is greater than the antifouling coating film of Example 1 [conversion from formulation 2], and the antifouling coating film is exposed to the extent that the surface of the tarpaulin base material is exposed. It was missing, and when exposed to the outdoors, the amount of dirt adhered increased remarkably and it became dirty black. In other words, there was concern about the durability of the antifouling property for articles that were subjected to rubbing and dragging during the sewing and construction of the industrial material sheet.

[Comparative Example 3]
A silane cup obtained by reacting the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) used in the antifouling coating film-forming composition [formulation 2] of Example 1 with the hydroxyl groups of cellulose nanofibers. Omit 500 parts by mass of ring-treated modified product (2% by mass aqueous solution), and 500% by mass of 2% by mass aqueous solution of cellulose nanofibers (fiber width 3 to 10 nm, fiber length 30 to 100 μm) before silane coupling treatment modification. A tarpaulin having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained in the same manner as in Example 1, except that [Formulation 20] was used. Compared to the tarpaulins of Examples 1 to 16, the antifouling performance of the antifouling coating film was not inferior, but by using cellulose nanofibers without silane coupling treatment modification, the Scott type bending endurance The effect on the antifouling coating film (-Si-O-based sol-gel condensate) was observed in the rubbing test, and slight abnormalities such as peeling and falling off and the presence of countless cracks were confirmed in the antifouling coating film. It is considered that this is because the cellulose nanofibers are not somehow incorporated into the chemical structure of the —Si—O—-based sol-gel condensate. In addition, by using cellulose nanofibers without silane coupling treatment modification, the abrasion damage in the Taber abrasion test (100 rotations) is greater than the antifouling coating film of Example 1 [conversion from formulation 2], and the tarpaulin The antifouling coating film was missing to the extent that the surface of the base material was exposed, and when exposed to the outdoors, the amount of dirt adhered increased significantly and the surface became black. It is considered that this is also caused by the fact that the cellulose nanofibers are not somehow incorporated into the chemical structure of the —Si—O—-based sol-gel condensate. In other words, there was concern about the durability of the antifouling property for objects that were subjected to extreme rubbing and dragging during the sewing and construction of the industrial material sheet.

[Comparative Example 4]
A silane cup obtained by reacting the hydrolyzate of 3-mercaptopropyltrimethoxysilane (mercapto-based silane coupling agent) used in the composition for forming an antifouling coating film of Example 6 [Formulation 7] with the hydroxyl groups of cellulose nanofibers. Omit 500 parts by mass of ring-treated modified product (2% by mass aqueous solution), and 500% by mass of 2% by mass aqueous solution of cellulose nanofibers (fiber width 3 to 10 nm, fiber length 30 to 100 μm) before silane coupling treatment modification. A tarpaulin having a thickness of 0.7 mm and a mass of 832 g/m ² was obtained in the same manner as in Example 6, except that [Formulation 21] was used. Compared to the tarpaulins of Examples 1 to 16, the antifouling performance of the antifouling coating film was not inferior, but by using cellulose nanofibers without silane coupling treatment modification, the Scott type bending endurance The effect on the antifouling coating film (-Ti-O-based sol-gel condensate) was observed in the rubbing test, and slight abnormalities such as peeling and falling off and the presence of countless cracks were confirmed in the antifouling coating film. It is considered that this is because the cellulose nanofibers are not somehow incorporated into the chemical structure of the —Ti—O—-based sol-gel condensate. In addition, by using cellulose nanofibers without silane coupling treatment modification, the abrasion damage in the Taber abrasion test (100 rotations) is greater than the antifouling coating film of Example 1 [conversion from formulation 2], and the tarpaulin The antifouling coating film was missing to the extent that the surface of the base material was exposed, and when exposed to the outdoors, the amount of dirt adhered increased significantly and the surface became black. It is considered that this is also caused by the fact that the cellulose nanofibers are not incorporated in some state in the chemical structure of the -Ti-O--based sol-gel condensate. In other words, there was concern about the durability of the antifouling property for objects that were subjected to extreme rubbing and dragging during the sewing and construction of the industrial material sheet.

[Reference example 1]
The composition for forming an antifouling coating film of Example 1 [Formulation 2] was prepared in the same manner as in Example 1 except that 50 parts by mass of the photocatalytic titanium oxide sol was omitted and replaced with 50 parts by mass of silica sol [Formulation 22]. , 0.7 mm and a mass of 832 g/m ² was obtained. Compared to the tarpaulins of Examples 1 to 16, the antifouling performance of the antifouling coating film (oil-based ink wiping test) was not inferior, but by omitting the photocatalytic titanium oxide sol, the oil-based The letters (ink) of the pen (red) were not completely erased and remained clear even after a 120-hour accelerated weather resistance test (JIS K5600-7-7) using a xenon weather meter. In outdoor exposure, the antifouling coating does not contain photocatalytic titanium oxide, so the self-cleaning effect is not exhibited, and dirt accumulates on the antifouling coating, requiring regular cleaning work. It was intended to be.

A coating composition for forming a robust antifouling coating film that is particularly suitable for flexible synthetic resin sheets (sheets for industrial materials such as tarpaulins, canvas, mesh sheets, synthetic leather, etc.) containing textiles as the core material. It is possible to provide, provide a robust antifouling coating film formed from this coating composition, and provide industrial material sheets (tarpaulins, canvas, mesh sheets, synthetic leather, etc.) with this robust antifouling coating film. As a result, it is possible to provide an industrial material sheet with less damage such as cracks in the antifouling coating film, especially when subjected to stress such as bending, bending, and fluttering. A composition capable of forming such a robust antifouling coating film is provided, and an antifouling coating film having excellent robustness can be obtained. , It is possible to obtain industrial material sheets (tarpaulin, canvas, mesh sheet, synthetic leather, etc.) with excellent bending resistance, bending resistance, and fluttering resistance. be excellent. The composition for forming an antifouling coating film of the present invention is applied not only to industrial material sheets, but also to a wide range of applications such as films, synthetic resin sheets, decorative boards, building material panels, glass products (parts), and plastic molded products (parts). It becomes possible to attach a strong antifouling coating film.

Claims (6)

A composition containing at least an organic silicate compound or an organic titanate compound and a modified cellulose nanomaterial, wherein the modification of the modified cellulose nanomaterial is esterification (borate esterification, phosphate esterification, silicate esterification , one or more selected from ), silane coupling agent treatment (aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylsilane modification, acrylicsilane modification, chlorosilane modification, mercaptosilane modification, isocyanurate silane modification, isocyanate silane modification , and organic titanate treatment. The composition comprises photocatalytic titanium oxide, photocatalytic titanium peroxide (peroxotitanic acid), photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic strontium titanate, photocatalytic tungsten oxide, photocatalytic bismuth oxide, and photocatalytic 2. The composition for forming an antifouling coating film according to claim 1, containing at least one photocatalytic metal oxide selected from iron oxide. An antifouling coating film containing at least a modified cellulose nanomaterial in a hydrolytic condensate of an organic silicate compound or an organic titanate compound, wherein the modification of the modified cellulose nanomaterial is esterification (borate esterification, phosphoric acid One or more selected from esterification, silicate esterification ), silane coupling agent treatment (aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylsilane modification, acrylicsilane modification, chlorosilane modification, mercaptosilane modification, isocyanate One or more selected from nurate silane-modified, isocyanate silane-modified), and one or more selected from organic titanate treatment. The antifouling coating film includes photocatalytic titanium oxide, photocatalytic titanium peroxide (peroxotitanic acid), photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic strontium titanate, photocatalytic tungsten oxide, photocatalytic bismuth oxide, and 4. The antifouling coating film according to claim 3, containing at least one photocatalytic metal oxide selected from photocatalytic iron oxide. An industrial material sheet comprising a hydrolytic condensate of an organic silicate compound or an organic titanate compound and an antifouling coating film containing at least a modified cellulose nanomaterial, wherein the modification of the modified cellulose nanomaterial is esterification (boron One or more selected from acid esterification, phosphate esterification, and silicate esterification ), silane coupling agent treatment (aminosilane modification, vinylsilane modification, epoxysilane modification, methacrylsilane modification, acrylicsilane modification, chlorosilane modification , mercaptosilane-modified, isocyanurate silane-modified, isocyanate silane-modified), and organic titanate treatment, and an industrial material sheet attached with an antifouling coating film. The antifouling coating film includes photocatalytic titanium oxide, photocatalytic titanium peroxide (peroxotitanic acid), photocatalytic zinc oxide, photocatalytic tin oxide, photocatalytic strontium titanate, photocatalytic tungsten oxide, photocatalytic bismuth oxide, and 6. The industrial material sheet according to claim 5, containing at least one photocatalytic metal oxide selected from photocatalytic iron oxide.