Composition, coating material, water-resistance-imparted base material, and method for producing water-resistance-imparted base material

Abstract

The present invention provides: a composition which is capable of imparting excellent water resistance to a base material; a coating material which contains the composition; and a method for producing a base material to which water resistance has been imparted. The composition contains a polyphenol, a fat or oil, and casein. The content of the fat or oil with respect to the composition is 2 mass% or more. The polyphenol is, for example, tannin, and casein is, for example, not limited to isolated casein. For example, casein contained in milk and products obtained by processing milk such as fermented milk products and processed milk are used and therefore a coating material which uses any of those dairy products directly is also included. The composition can be obtained by emulsifying a mixture of these components. A base material to which excellent water resistance has been imparted can be obtained by impregnating the base material with the composition and performing a drying treatment by means of UV irradiation or overheating.

Description

Composition, paint, water-resistant substrate, and method for producing water-resistant substrate

[0001] The present disclosure relates to a composition for waterproofing a substrate, a coating material containing the composition, a waterproofed substrate obtained by applying the composition, and a method for producing the waterproofed substrate.

[0002] Conventionally, impregnated materials obtained by impregnating cellulose cloth and paper with a thermosetting material have been used in the manufacture of various molded products such as laminates for semiconductor substrates, decorative sheets, oil filters, and sliding members. The cured products obtained by curing such impregnated materials have superior strength compared to cellulose cloth and paper.

[0003] Japanese Patent Application Laid-Open Publication No. 2014-095049 (Patent Document 1) discloses a molded sheet (cellulose fiber-reinforced thermoplastic resin composite molded body) made by adding trehalose to commercially available odorless persimmon tannin to prepare a persimmon tannin liquid, immersing a fabric (a blend of 65% polyester and 35% cotton) in the persimmon tannin liquid, and thoroughly drying the resulting fabric. Japanese Patent Application Laid-Open Publication No. 2023-124508 (Patent Document 2) discloses a water-resistant cellulose cloth / paper using a cellulose cloth / paper impregnation kit comprising a first container containing a primary impregnation agent containing a carbohydrate, a phenol, and an organic acid ammonium salt, and a second container containing a secondary impregnation agent containing a drying oil. Japanese Patent Application Laid-Open Publication No. 2001-081686 (Patent Document 3) discloses a cellulose fiber sheet formed from cellulose fibers and a powder or fiber of a weakly alkali-soluble resin. Japanese Patent Application Laid-Open No. 2003-013391 (Patent Document 4) discloses a paper sheet characterized in that a biodegradable resin layer is formed on at least one surface of a paper substrate by coating or impregnating the surface with a biodegradable resin.

[0004] JP 2014-095049 A JP 2023-124508 A JP 2001-081686 A JP 2003-013391 A

[0005] In recent years, the use of cellulose cloth and paper has become increasingly important from the perspectives of the SDGs and carbon neutrality. However, cellulose cloth and paper has poor water resistance. Therefore, by improving the water resistance of cellulose cloth and paper, it is expected that it will be used in everyday consumable products such as paper bags as an alternative to plastic bags, paper plates, paper cups, and paper molded products such as straws.

[0006] In Patent Document 1, the fabric is immersed in persimmon tannin solution to improve water repellency. However, the cellulose-based fiber-reinforced thermoplastic resin composite molding contains a thermoplastic resin, which is a petroleum-derived material, and is not based solely on cellulose fibers. In other words, the cellulose-based fiber-reinforced thermoplastic resin composite molding does not take into consideration the improvement of water resistance of cellulose fibers alone.

[0007] In Patent Document 2, a water-resistant cellulose cloth / paper is obtained by impregnating a cellulose cloth / paper with a primary impregnation agent, hardening the cellulose cloth / paper, and then impregnating the cellulose cloth / paper with a secondary impregnation agent. However, the impregnation process requires two steps, and the heat treatment after impregnation takes 10 to 60 minutes each, for a total of 20 to 120 minutes, making the manufacturing method complicated. Furthermore, the use of carbohydrates results in problems such as brittleness and reduced processability of the water-resistant cellulose cloth / paper made using the cellulose cloth / paper impregnation agent kit.

[0008] In Patent Document 3, cellulose acetate phthalate or casein powder is heated in a heating press device, and a sample is subjected to a pressure of 200 kg / cm. ２ However, there is no mention of cloth paper. Patent Document 4 describes impregnating a biodegradable paper sheet with an aqueous solution of casein resin, but because the purpose is to form a coating film of casein resin, it cannot be said that the appearance and mechanical properties are the same as when casein, a type of protein, is applied.

[0009] The present disclosure has been made in consideration of the above circumstances, and an object of the present disclosure is to provide a composition, a paint, a water-resistant substrate made water-resistant with the composition, and a method for manufacturing a water-resistant substrate, which can more easily impart excellent water resistance to a substrate such as cellulose cloth or paper without using petroleum-derived materials.

[0010] In order to solve the above problems, the present disclosure is configured as follows: That is, a composition according to the present disclosure includes polyphenols, an oil and fat, and casein, and the content F of the oil and fat in the composition is 2% by mass or more.

[0011] According to the present disclosure, excellent water resistance can be easily imparted to a substrate such as cellulose cloth or paper without using petroleum-derived materials.

[0012] FIG. 1 is a diagram showing a method for manufacturing a water-resistant substrate.

[0013] (Configuration 1) A composition according to an embodiment of the present disclosure is a composition for making a substrate waterproof, and includes polyphenols, an oil and fat, and casein. The content of the oil and fat in the composition is 2% by mass or more.

[0014] By applying such a composition to a substrate, excellent water resistance can be imparted to the substrate, such as wood, cellulose cloth or paper, or a three-dimensional molded object.

[0015] (Configuration 2) In the composition of Configuration 1, the oil or fat may have an iodine value of 130 to 250. This can facilitate solidification.

[0016] (Configuration 3) In the composition of Configuration 1 or 2, the composition may satisfy the following formulas (1) and (2): 10<F / C<150 (1) 1.0<F / P<70 (2) In the above formulas (1) and (2), P represents the content (% by mass) of polyphenols in the composition, C represents the content (% by mass) of casein in the composition, and F represents the content (% by mass) of fats and oils in the composition. The composition is emulsified by mixing the ingredients. By satisfying the above formulas (1) and (2), the stability of the emulsion of the composition can be ensured.

[0017] (Configuration 4) In the composition of Configuration 1 or 2, the composition may satisfy the following formulas (3) and (4): 18.903≦F / C≦76.048 (3) 6.256≦F / P≦48.4 (4) This can ensure better water resistance and better paint stability.

[0018] (Configuration 5) In the composition of any one of Configurations 1 to 4, the composition may satisfy the following formula (5): F / C≧30 (5) In the above formula (5), C represents the casein content (% by mass) in the composition, which can impart better water resistance.

[0019] (Configuration 6) In the composition of any one of Configurations 1 to 5, the content of the oil or fat in the composition may be 50% by mass or less, thereby making it possible to suppress the transfer of the oil or fat contained in the water-resistant substrate.

[0020] (Configuration 7) In the composition of Configuration 3 or 4, C may be 0.05 to 6 mass %. P may be 0.2 to 4 mass %, thereby ensuring emulsion stability and improving the water resistance of the substrate.

[0021] (Configuration 8) In the composition of any one of Configurations 1 to 7, the polyphenols may be at least one of tannins and flavonoids, thereby further improving water resistance.

[0022] (Configuration 9) In the composition of any one of Configurations 1 to 8, the composition may further include an alcohol. The alcohol may have 2 to 40 carbon atoms in its molecular structure. The alcohol may have less than 10 carbon atoms in its molecular structure.

[0023] (Configuration 10) A paint according to an embodiment of the present disclosure may include the composition of any one of configurations 1 to 9 described above.

[0024] (Configuration 11) A water-resistant substrate according to an embodiment of the present disclosure may be constructed by applying the composition of any one of configurations 1 to 10 described above to a substrate.

[0025] (Configuration 12) In the water-resistant substrate of Configuration 11, the substrate may be a cellulose cloth paper.

[0026] (Configuration 13) A method for producing a water-resistant substrate according to the present disclosure may include a step of applying to a substrate the composition of any one of the above-described configurations 1 to 9. This allows a water-resistant substrate with excellent water resistance to be produced in a short period of time.

[0027] (Configuration 14) The method for producing a water-resistant substrate according to Configuration 13 may include a step of irradiating the composition applied to the substrate with ultraviolet light. This allows a water-resistant substrate with excellent water resistance to be obtained in a short period of time. Here, the integrated light dose of the ultraviolet light irradiation is 600 mJ / cm. ２ This makes it possible to obtain a water-resistant substrate having excellent water resistance and water repellency in a shorter time.

[0028] (Configuration 15) The method for producing a water-resistant substrate according to Configuration 13 or 14 may include a step of drying the composition applied to the substrate. Here, the composition applied to the substrate may be dried at a temperature of 80° C. or higher and 200° C. or lower for 10 seconds or longer and 10 minutes or shorter.

[0029] The composition may contain a large number of micelles. The large number of micelles may have a volume average particle size of 40 μm or less. Furthermore, the frequency of micelles with a particle size of 65 μm or more may be 10% or less in terms of number. This can improve the stability of the composition.

[0030] The above-described composition may also be emulsified.

[0031] The composition of the present disclosure, the coating material containing the composition, and the water-resistant substrate will be specifically described below.

[0032] [Composition] The composition of the present invention can contain polyphenols, fats and oils, and casein. The composition is applied to a substrate for the purpose of making it water-resistant. Therefore, the composition can be used as a "paint," and the paint can contain the composition. Details of the substrate will be described later.

[0033] The polyphenols may be naturally occurring or synthetically produced as antioxidants. The polyphenols contained in the composition of the present disclosure are preferably flavonoids or tannins.

[0034] Examples of flavonoids include catechins contained in green tea, flavonols such as quercetin contained in onions, isoflavones contained in soybeans, and anthocyanins contained in blueberries. The flavonoids may contain one or more selected from the group consisting of these various flavonoids. Among these, catechins are more preferred.

[0035] Examples of tannins include persimmon tannin (persimmon tannin), cinnamon, tannic acid, mimosa tannin, wattle tannin, quebracho (quebracho) tannin, chestnut tannin, mirabholum tannin, myrobalan tannin, valonia tannin, sumac tannin, Gambia tannin, oak tannin, tara tannin, dividivi tannin, Borneo kacchi tannin, spruce tannin, and hemlock tannin, etc. The tannins may contain one or more types selected from the group consisting of these various tannins.

[0036] As the fat or oil, either animal fat or vegetable fat can be used, but it is preferable to use either animal fat or vegetable fat. Furthermore, vegetable fat is preferred from the viewpoint of environmental load, economic cost, and availability. Furthermore, drying oil is more preferable from the viewpoint of ease of solidification. Drying oil (unsaturated fatty acid) is an oil with an iodine value of 130 or more, and solidifies by oxidation. From the viewpoint of ease of solidification, the iodine value of drying oil is preferably 130 or more, more preferably 150 or more. There is no particular upper limit for the iodine value, but for example, it is preferably 250 or less, more preferably 200 or less. The iodine value can be measured by a method in accordance with JIS K0070.

[0037] Drying oils among vegetable oils include, for example, soybean oil, perilla oil, linseed oil, tung oil, mustard oil, perilla oil, walnut oil, safflower oil, sunflower oil, fish oil (sardine oil), black cumin seed oil, apple oil, grape seed oil, cactus oil, wheat germ oil, pumpkin seed oil, passion fruit seed oil, guava seed oil, borage oil, sissymbrium oil, pine nut oil, camelina oil, cranberry seed oil, lime seed oil, bitter melon oil, hemp oil, and sea buckthorn oil. Examples of suitable drying oils include watercress oil, evening primrose oil, strawberry oil, blackcurrant oil, rosehip oil, raspberry seed oil, Inca inchi oil, kiwi seed oil, calendula seed oil, chia seed oil, pomegranate seed oil, kukui nut oil, black currant seed oil, and borage seed oil, as well as processed oils such as stand linseed oil, boiled poppy oil, sun-bleached poppy oil, boiled linseed oil, and sun-bleached linseed oil. The drying oil may comprise one or more selected from the group consisting of these various drying oils. From the viewpoint of ease of handling, the drying oil is preferably at least one selected from the group consisting of soybean oil, perilla oil, linseed oil, tung oil, mustard oil, shiso oil, walnut oil, safflower oil, and sunflower oil. Perilla oil contains palmitic acid with 16 carbon atoms, oleic acid and linoleic acid with 18 carbon atoms, and arachidic acid with 20 carbon atoms.

[0038] Examples of animal fats and oils include terrestrial animal fats and oils such as beef tallow, lard, mutton fat, and milk fat. Marine animal fats and oils such as fish oil, whale oil, sardine oil, and liver oil can also be used if they are drying oils, as they polymerize and become highly molecular weight during the heat treatment described below. The fats and oils contained in the composition can contain either animal fats and oils or vegetable fats, but it is preferable to contain either animal fats and oils or vegetable fats. That is, the composition may contain vegetable fats and oils, animal fats, or a mixture of vegetable and animal fats and oils. Mineral oil may also be included as the fat and oil.

[0039] The content F of the oil / fat relative to the composition can be 2% by mass or more. This can improve water repellency. Furthermore, the content F of the oil / fat relative to the composition can be less than 50% by mass. This can prevent transfer of the oil / fat to other substrates, particularly substrates arranged below, when multiple substrates coated with the composition are stacked and stored or transported.

[0040] The casein may be isolated casein or a material containing casein. Examples of the material containing casein include milk, milk fermented products, processed milk products, etc. When producing the composition, at least one of milk, milk fermented products, processed milk products, etc. may be used as a material.

[0041] Furthermore, the plant-based alcohol is preferably mint oil. Mint oil is an alcohol having 10 to 40 carbon atoms. Thus, even when an alcohol having 10 to 40 carbon atoms is used, excellent water resistance can be obtained. From the viewpoint of obtaining excellent water resistance, the alcohol preferably has 2 to 40 carbon atoms, and from the viewpoint of improving impregnation into cellulose fabric and paper, the alcohol preferably has 10 or less carbon atoms.

[0042] The composition may further contain other components besides polyphenols (tannins), fats and oils, and casein, as necessary, as long as the effects of the present disclosure are not impaired. The other components are not particularly limited and may be appropriately selected from known components that can be incorporated into compositions. Examples include water, organic solvents, inorganic acid ammonium salts, metal salts, and additives (surfactants, water repellents, antifoaming agents, flame retardants, preservatives, antifungal agents, plasticizers, colorants, thickeners, bulking agents, etc.). These components may be used alone or in combination of two or more. From the viewpoint of improving affinity with the materials of the composition, the organic solvent preferably has an SP value of 10 or more. Using an organic solvent with an SP value of 10 or more can reduce the viscosity of the composition.

[0043] The composition may further contain water to facilitate application or impregnation of the composition onto a substrate. That is, the composition may be a liquid composition in which polyphenols, oils and fats, and an emulsifier (casein) are dissolved or dispersed in water.

[0044] The composition is contained in a container. The material and shape of the container are not particularly limited as long as the container can contain the composition.

[0045] The composition can satisfy the following formulas (1) and (2): 10<F / C<150 (1) 1.0<F / P<70 (2) In formulas (1) and (2) and formulas (3) to (7) described below, P represents the content (% by mass) of polyphenols in the composition, C represents the content (% by mass) of casein in the composition, and F represents the content (% by mass) of fats and oils in the composition.

[0046] In formula (1), if the value of F / C is too small or too large, that is, if the amount of fat or oil relative to the casein contained in the composition is too small or too large, the emulsion stability of the composition decreases.

[0047] In formula (2), if the value of F / P is too small, the water resistance of the water-resistant substrate to which the composition is applied will decrease, whereas if the value of F / P is too large, the viscosity of the composition will be too high, resulting in a decrease in the water resistance of the water-resistant substrate to which the composition is applied.

[0048] Furthermore, it is preferable that the composition satisfy the following formulas (3) and (4): 18.903≦F / C≦76.048 (3) 6.256≦F / P≦48.4 (4) This further improves the stability of the coating material and enables the water resistance of a water-resistant substrate to which the composition is applied to be maintained at a good level.

[0049] As with the above formulas (1) and (2), from the viewpoint of water resistance and proper application, C can be 0.05 to 6 mass %, and P can be 0.2 to 4 mass %. This allows the substrate to which the composition is applied to have excellent water resistance. Furthermore, C is preferably 0.272 to 0.742 mass %, and P is preferably 0.523 to 1.672 mass %. Furthermore, C is more preferably 0.272 to 0.544 mass %, and P is more preferably 0.523 to 1.672 mass %.

[0050] The composition can satisfy the following formula (5): F / C≧30 (5) This allows a water-resistant substrate coated with the composition to have better water resistance. That is, it is more preferable that 30≦F / C<150 and 1.0<F / P<70, and it is even more preferable that 30≦F / C≦76.048 and the above formula (2) satisfies 6.256≦F / P≦48.4.

[0051] It is most preferable that the composition satisfies the following formulas (6) and (7): 37.077≦F / C≦76.048 (6) 12.47≦F / P≦48.4 (7) This ensures good paint stability and allows the water-resistant substrate coated with the composition to maintain extremely high water resistance.

[0052] The composition contains a large number of micelles. The large number of micelles have a volume-average particle size of 40 μm or less. This stabilizes the emulsion. From this perspective, the volume-average particle size of the micelles is preferably 40 μm or less, more preferably 20 μm or less. The lower limit of the volume-average particle size of the micelles is not particularly limited, but is preferably 0.1 μm or more. The volume-average particle size of the micelles is measured by light scattering using a "HORIBA LA-920 (manufactured by HORIBA, Ltd.)" (laser diffraction / scattering particle distribution analyzer). The concentration of the liquid to be measured is adjusted so that the light transmittance does not exceed the measurement limit. Furthermore, the frequency of micelles with particle sizes of 65 μm or more is 10% or less, calculated as numbers. That is, the number of micelles with particle sizes of 65 μm or more is preferably 10% or less, more preferably 2% or less, and more preferably 0.1% or less, of the total number of micelles. This improves the stability of the composition. That is, it makes the composition easier to manage. The particle size of the micelles is a value obtained by integrating the frequency percentage of particles of 65 μm or more from a particle size histogram measured by a light scattering method. Here, the volume average particle size is calculated by dividing the particle radius by d ｉ , the number of particles is n ｉ When the particle size is calculated by the following formula: Σ(d ｉ ４ ×n ｉ ) / Σ(d ｉ ３ ×n ｉ )

[0053] [Method for producing water-resistant substrate] Next, a method for producing a water-resistant substrate according to the present disclosure will be specifically described with reference to Fig. 1. The water-resistant substrate according to the present disclosure can be produced by applying the above-described composition to a substrate.

[0054] The substrate may include not only a paper sheet such as cellulose cloth paper or cardboard, but also an injection-molded body made of pulp, wooden furniture, etc. In other words, in the present disclosure, the substrate is not limited to a sheet but also includes a three-dimensional object, and also includes not only intermediate parts used as materials for manufacturing a finished product, but also the finished product.

[0055] Cellulose cloth paper is a cloth paper whose main component is cellulose fiber. Cloth paper is a general term for paper and cloth. Examples of cloth include nonwoven fabric, woven fabric, and felt. The cellulose cloth paper is not particularly limited and can be appropriately selected depending on the application of the waterproof substrate. However, the cellulose cloth paper is preferably paper. Examples of paper include filter paper, kraft paper, and processed base paper. The basis weight of cellulose cloth paper is 30 g / m ２ It is preferable that the thickness is 50 g / m or more. ２ More preferably, it is 500 g / m or more. ２ It is preferable that the thickness is 300 g / m or less. ２ Preferably, it is:

[0056] As shown in FIG. 1, the method for producing cellulose cloth paper can include a coating step S1, an ultraviolet irradiation step S2, and a drying step S3.

[0057] [Coating Step S1] First, the composition is applied to the substrate. The method for applying the composition to the substrate may be any known method, and is not particularly limited. Examples include a method of applying the composition using a brush or the like, a method of immersing the substrate in the composition and applying it, and a method of spraying the composition onto the substrate using a spray or the like. The composition may be diluted with water or the like to facilitate application to the substrate. Depending on the material of the substrate, the composition may form a coating on the surface of the substrate. Alternatively, when cellulose cloth paper is used as the substrate, for example, the composition may be applied so that the entire cellulose cloth paper is impregnated with the composition, or only a portion of the cellulose cloth paper, for example, near the surface, may be impregnated with the composition.

[0058] When cellulose cloth paper is used as the substrate, the composition may be applied to the cellulose cloth paper to impregnate it, and then the cellulose cloth paper impregnated with the composition may be dried in advance before the ultraviolet irradiation step S2 described below or before the heat treatment in the drying step S3 described below to form a prepreg. In this case, it is desirable that the prepreg contains 10% or more of water in the composition. Furthermore, after applying the composition to the substrate, the above-mentioned oil or fat may be further applied to the substrate.

[0059] [Ultraviolet Irradiation Step S2] In the ultraviolet irradiation step (S2), after the composition is applied to the substrate, the composition applied to the substrate is irradiated with ultraviolet light. The ultraviolet irradiation method is not particularly limited and can be carried out by a known method. In general, an ultraviolet lamp is installed on a production line, and the substrate, which is the workpiece, passes through an area irradiated with the lamp light, thereby irradiating the composition applied to the substrate with ultraviolet light. At this time, the irradiation time, i.e., the amount of ultraviolet light irradiation, can be adjusted by the moving speed of the workpiece. The ultraviolet light irradiation may be performed once or in multiple steps.

[0060] The ultraviolet irradiation lamp that irradiates the composition applied to the substrate with ultraviolet rays is not particularly limited, and examples thereof include an LED lamp, a mercury lamp, a metal halide lamp, a xenon lamp, and a black light lamp.

[0061] The irradiation time and illuminance of ultraviolet light are not particularly limited, but the cumulative light amount is 600 mJ / cm ２ It is preferable to set it to 500 mJ / cm or less. ２ It is preferable that the dose is 400 mJ / cm or more. ２ If the integrated light amount is equal to or less than the upper limit mentioned above, the water resistance of the cellulose cloth paper can be improved. ２ Furthermore, it is preferable that the ultraviolet light source contains a wavelength of 350 nm or less, and more preferably contains a wavelength of 300 nm or less.

[0062] [Drying Step S3] The drying step S3 is performed to remove solvents such as water and to adjust the curing conditions. Drying can be performed by known methods. For example, in the case of a roll-to-roll mass production line, a temperature-controlled drying facility can be installed on the line, and the substrate can be continuously dried by passing it through the drying facility. In this case, the drying time is determined by the length and conveying speed of the drying facility. Drying conditions can be appropriately set within a range that does not completely cure the composition. Note that, for example, when a sheet such as cellulose cloth paper is used as the substrate, several to several tens of substrate compositions coated with the composition may be stacked before curing by heat treatment. Furthermore, several to several tens of substrates coated with the composition may be stacked and molded into any shape before curing by heat treatment. Note that, in the present disclosure, a dry composition refers to a composition having a water content of less than 10%.

[0063] In the drying step S3, the composition applied to the substrate is then heat-treated. The heat treatment can be performed by a known method, such as heat pressing or annealing. The heat treatment may be performed, for example, by heating at a temperature of 80 to 200°C for 10 seconds to 10 minutes, or by drying the composition applied to the substrate in a hot air drying oven at 80 to 200°C. Alternatively, the heat treatment may be performed in a batch-type constant temperature bath or safe vent dryer.

[0064] The order of the ultraviolet irradiation step S2 and the drying step S3 can be reversed. That is, the ultraviolet irradiation step S2 may be performed after the drying step S3. From the viewpoint of further improving water resistance, it is preferable to perform the ultraviolet irradiation step S2, but sufficient water resistance can be obtained even if the ultraviolet irradiation step S2 is omitted.

[0065] In this way, a water-resistant substrate having excellent water resistance can be easily obtained. The water-resistant substrate has better water resistance than the substrate before the composition is applied. Furthermore, according to the above-mentioned method, a water-resistant substrate having excellent water resistance and water repellency can be obtained in a shorter time.

[0066] The use of the waterproof substrate is not particularly limited, and the waterproof substrate can be used as a material for various products such as bags, plates, cups, straws, tableware, laminates such as semiconductor substrates, decorative sheets, oil filters, sliding members, core materials, rollers, boxes, desks, chairs, and shelves.

[0067] The composition, paint, and water-resistant substrate, as well as the method for manufacturing a water-resistant substrate, according to the present disclosure, can contribute to achieving Goal 7 "Affordable and clean energy" and Goal 12 "Responsible consumption and production" of the Sustainable Development Goals (SDGs) advocated by the United Nations.

[0068] Although the embodiments have been described above, the present disclosure is not limited to the above-described embodiments, and various modifications are possible without departing from the spirit of the present disclosure.

[0069] In the tables below, "composition (parts)" indicates parts by mass, and "composition (%)" indicates % by mass. Table 1 shows the parts by mass of the composition contained in the composition in each example and comparative example, and Table 2 shows the mass % of the composition contained in the composition in each example and comparative example and the test results. Note that the present disclosure is not limited by the following description of the examples.

[0070] (Materials used) Polyphenols: Persimmon tannin paint (Mitsuru Kakishibu) manufactured by Mimasu Kasshichi Shoten Co., Ltd. Milk: Rich and delicious milk manufactured by Ezaki Glico Co., Ltd. (Examples 1 to 5, Example 16, Comparative Examples 1 to 5), milk rich in calcium and iron manufactured by Ezaki Glico Co., Ltd. (Examples 6 to 15) Organic solvents: 2-propanol manufactured by Wako Pure Chemical Industries, Ltd., ethanol (95) manufactured by Wako Pure Chemical Industries, Ltd., peppermint oil P manufactured by Kenei Pharmaceutical Drying oil: Linseed oil manufactured by Ohta Oil Co., Ltd., perilla oil manufactured by Ohta Oil Co., Ltd. Soybean lecithin: Soybean lecithin (granules) manufactured by Marugo Corporation

[0071] In Table 1 below, P is the content (mass%) of polyphenols in the composition, F is the content (mass%) of fats and oils in the composition, and C is the content (mass%) of casein in the composition. P was calculated assuming that the persimmon tannin paint contains 4.18 mass% of polyphenols. F is the content (mass%) of fats and oils contained in milk in Table 1 below. ｍ ) per 200 mL (Examples 1 to 5, Comparative Examples 1 to 5) and 2.3 g per 200 mL (Examples 6 to 15). ｄ ) is added together. C was calculated by calculating the total protein content (mass%) in milk, based on the total protein content in milk being 6.8 g per 200 mL (Examples 1 to 5, Comparative Examples 1 to 5) and 3.3 g per 200 mL (Examples 6 to 15), and assuming that casein generally accounts for 80% of the total protein content (mass%) in the obtained milk. In addition, when perilla oil or flaxseed oil (F ｄ ), and 2-propanol, etc. were calculated assuming a concentration of 100%.

[0072]

[0073]

[0074] [Preparation of Compositions] (Examples 1 to 4 and 6 to 13) Persimmon tannin paint (polyphenols), perilla oil, milk, 2-propanol (organic solvent, having three carbon atoms), and drying oil were placed in a sealed container in the weight parts shown in Table 1, and the mixture was dispersed and mixed by vigorously shaking for about 1 minute to prepare a liquid composition. In Examples 1 to 4 and 6 to 13, the ratio of milk to persimmon tannin paint is as shown in Tables 1 and 2. In Examples 1 to 4 and 6 to 13, the ratio of 2-propanol:IPA (organic solvent) to persimmon tannin paint was 50%.

[0075] Example 5 In Example 5, the composition of Example 1 and 250 parts by weight of water were sealed in a sealed container, and dispersed and mixed in the same manner as above to prepare a composition.

[0076] (Examples 14 and 15) In Example 14, ethanol was placed in a sealed container as the alcohol without adding 2-propanol, and the mixture was dispersed and mixed in the same manner as described above to prepare a composition. In Example 15, 2-propanol and ethanol were placed in a sealed container in the weight parts shown in Table 1, and the mixture was dispersed and mixed in the same manner as described above to prepare a composition. Note that ethanol has two carbon atoms.

[0077] Example 16 In Example 16, the composition of Example 6 and 1.5 parts by mass of soybean lecithin were sealed in a sealed container and dispersed and mixed in the same manner as above to prepare a composition.

[0078] In Comparative Example 1, perilla oil was not added, and the persimmon tannin paint, milk, and 2-propanol were sealed in a sealed container in the weight parts shown in Table 1, and the mixture was dispersed and mixed in the same manner as described above to prepare a composition. That is, the composition was prepared so that the F shown in Table 2 was less than 2% by mass.

[0079] In Comparative Example 2, milk, 2-propanol, and perilla oil were placed in a sealed container in the weight parts shown in Table 1 without adding the persimmon tannin paint, and the mixture was dispersed and mixed in the same manner as described above to prepare a composition. That is, the composition of Comparative Example 2 did not contain polyphenols (P).

[0080] In Comparative Example 3, perilla oil and 2-propanol were not added, and the persimmon tannin paint and milk were sealed in a sealed container in the weight parts shown in Table 1, and the mixture was dispersed and mixed in the same manner as above to prepare a composition. That is, the composition was prepared so that the F shown in Table 2 was less than 2 mass%.

[0081] In Comparative Example 4, milk and perilla oil were placed in a sealed container in the weight parts shown in Table 1 without adding persimmon tannin paint or 2-propanol, and the mixture was dispersed and mixed in the same manner as described above to prepare a composition. That is, the composition of Comparative Example 4 does not contain polyphenols (P).

[0082] In Comparative Example 5, a composition was prepared by adding persimmon tannin paint and perilla oil in the weight parts shown in Table 1 to a sealed container without adding milk or 2-propanol, and dispersing and mixing in the same manner as described above. That is, the composition of Comparative Example 5 does not contain casein (C).

[0083] In preparing the compositions of the Examples and Comparative Examples, the compositions could be easily prepared, especially when casein contained in milk was used. This is because casein is stably dispersed in the water in milk in the form of micelles. Thus, the compositions could be prepared in a short time, especially when milk was used.

[0084] [Measurement of particle size of composition] The particle size distribution of the micelles in the composition was measured by light scattering using the above-mentioned "HORIBA LA-920 (manufactured by Horiba, Ltd.)." The results showed that the volume-average particle size of the micelles immediately after preparation was 40 μm or less, and the components separated over time. After dispersion and mixing, the proportion of particles 65 μm or larger was 10% or less, improving the stability of the composition. Here, the average particle size refers to the particle size (volume-average particle size) at which the cumulative number of particles in the particle size distribution reaches 50%.

[0085] [Preparation of Samples] In Examples 1 to 16 and Comparative Examples 1 to 5, the compositions were applied to a substrate of cellulose cloth paper (JK Wiper (registered trademark) 150S (manufactured by Nippon Paper Crecia Co., Ltd.)) measuring 150 mm x 150 mm, and the composition was impregnated onto both sides of kraft paper without leaving any gaps. Heat treatment was then performed under the heat treatment conditions shown in Table 2 to obtain samples impregnated with the compositions.

[0086] [Evaluation of Paint Stability] The stability of the compositions (paints) was evaluated as follows. First, the compositions were prepared and left as they were for 24 hours. If the composition separated into two layers or precipitated, it was deemed unstable and rated as "C." If the composition did not separate clearly (e.g., precipitate) but the apparent viscosity increased and the viscosity decreased when stirred again, it was rated as "B." If the composition remained uniformly dispersed without separating into two layers, i.e., remained in an emulsion state, it was deemed stable and rated as "A."

[0087] [Evaluation of Water Repellency] The water repellency of the prepared samples was tested based on the old JIS standard (JIS P8137), and the water repellency of the samples was evaluated according to this standard.

[0088] Comparing Examples 1 to 16 with Comparative Examples 1 to 5, excellent water repellency was achieved when polyphenols, fats and oils, and casein were included and the fat content F was 2% by mass or more. That is, Comparative Examples 1 and 3, in which the fat content F was less than 2% by mass, and Comparative Examples 2 and 4, which did not contain polyphenols, were evaluated as "R0" for water repellency, and excellent water repellency was not achieved. Thus, it was confirmed that sufficient water repellency could be achieved for a water-resistant substrate containing polyphenols, casein, and fats and oils, and in which the fat content F relative to the composition was 2% by mass or more. In Comparative Example 5, which did not contain casein, the paint was unstable, and water repellency could not be evaluated. From this, it is believed that casein is necessary to stabilize the paint.

[0089] Furthermore, in Examples 1 to 16, the above-mentioned "stability of the coating material (composition)" and "water repellency" were evaluated.

[0090] First, the "paint stability" was evaluated. As a result, Examples 6, 7, 11, and 12 were rated "B," while the other Examples were rated "A." In Example 11, the F / C value was too small, i.e., the casein content was too low, which is thought to be the reason for the "B" rating. In Examples 6, 7, and 12, the F / C value was too large, i.e., the casein content was too high, which is thought to be the reason for the "B" rating. In Example 12, the F / P value was too large, i.e., the perilla oil content was too high, which is thought to be the reason for the "B" rating. In Example 12, the viscosity was too high compared to the compositions of Examples 6 and 7, which is thought to be the reason for the inferior paint stability. Therefore, it was confirmed that, from the perspective of ensuring paint stability, the F / C value should be greater than 10 and less than 150, and the F / P value should be greater than 1.0 and less than 70. That is, it was found that the stability of the paint can be ensured by the composition satisfying the formula (1) "10<F / C<70" and the formula (2) "1.0<F / P<70." Furthermore, although alcohols other than 2-propanol were used in Examples 14 and 15, they were rated "A," which confirmed that the paint was stable even when alcohols other than 2-propanol were used.

[0091] Next, "water repellency" was evaluated. As a result, among Examples 1 to 16, Examples 2 to 4, 8, and 13, in which the F / C value was less than 30, were rated as "R8" or less in water repellency, while the other Examples, in which the F / C value was 30 or more, were rated as "R9" or more, which is a high water repellency. From this, it can be seen that if the F / C value is 30 or more, that is, by satisfying formula (3) "F / C≧30", water repellency can be further improved. Furthermore, by satisfying the above formulas (1), (2), and (3), better paint stability and water repellency can be obtained.

[0092] In addition, for all paints except Comparative Example 5, the number of applications was limited to one, and the heat treatment time was shortened to one minute. Furthermore, in Example 16, the "paint stability" was rated "A" and the "water repellency" was rated "R10," indicating that excellent paint stability and water repellency were achieved even when trace amounts of both lecithin and casein were included. In other words, excellent paint stability and water repellency were achieved even when the paint contained a small amount of lecithin that did not affect the mixing of the paint. Based on these results, the present invention provides a composition, a paint, a water-resistant substrate made water-resistant by the composition, and a method for producing a water-resistant substrate, which can more easily impart excellent water resistance to substrates such as cellulose cloth and paper.

[0093] The polyphenol content P can be determined as follows. First, 550% ethanol is added to 0.2 to 0.6 g of a composition sample, followed by ultrasonic irradiation and centrifugation. The mixture is then filtered to prepare a test solution. Also, 1 ml of a catechin standard solution is prepared. 0.5 ml of Folin-Ciacalteu reagent and 5 ml of 0.4 mol / L sodium carbonate aqueous solution are added to the catechin standard solution, and the mixture is left to stand for 25 minutes at 30°C. The polyphenol content P is then determined by measuring at a wavelength of 660 nm using a UV-visible spectrophotometer. The catechin standard solution is prepared by dissolving and diluting a standard sample consisting of (+)-catechin in water. More specifically, 10 mg of (+)-catechin is weighed and placed in a 10 mL volumetric flask. The solution is then diluted to 10 mL with methanol to prepare a 1000 ppm standard sample. 400 μL of purified water is added to this standard sample to prepare a 100 ppm catechin standard solution.

[0094] Additionally, methods for measuring the casein content C include methods using antibodies, such as ELISA. These are methods for detecting specific proteins. When determining the casein content C in a paint using ELISA, a sample can be prepared from the paint as follows: The paint is diluted with a buffer solution so that the alcohol concentration in the paint is 1% by mass or less. When diluting the paint, a buffer solution is added until the pH of the sample is around 7. The type of buffer solution is not particularly limited as long as it can bring the sample pH to around 7; however, a buffer solution with a pH of 3 to 11, more preferably 4 to 10, and even more preferably 5 to 9 can be used. Specifically, phosphate buffer solutions such as PBS, glycine buffer solutions, Tris buffer solutions, borate buffer solutions, citrate buffer solutions, Good's buffer solutions, etc. can be used. The concentration of the buffer solution is not particularly limited as long as it can bring the sample pH to around 7; however, a concentration of 0.1 to 200 mM is preferred, and a concentration of 1 to 150 mM is more preferred. In the present invention, the buffer solution concentration refers to the concentration (mM) of the buffer agent contained in the buffer solution. Furthermore, a sample with a pH of around 7 refers to a pH of 7.2 to 7.4. The sample is preferably diluted to a casein concentration of 10 to 1000 μg / L. If the casein concentration of the sample needs to be 1 / 1000 or less of that of the paint, stepwise dilution is preferred.

[0095] Furthermore, when using milk, the casein content C can be determined, for example, by determining the total protein amount using a simple method of measuring the total nitrogen content, and then confirming that 80% by mass of the protein determined by LC-MS is casein. Measurement can also be performed by separating proteins using various LCs.

[0096] The fat and oil content F can be determined by the following method. First, a solvent having a molecular structure without a CH group, such as carbon tetrachloride or trichlorotrifluoroethane, is added to a sample of the composition to separate the oil component from non-oil components such as water. Then, a calibration curve is created from the absorbance of the infrared spectrum using an OCB mixed standard substance, and the fat and oil content F is quantified by comparing the absorbance of the sample with the calibration curve.

Claims

1. A composition for making a substrate water-resistant, It contains polyphenols, oils and fats, and casein. A composition in which the content F of the oil and fat in the composition is 2% by mass or more.

2. The composition according to claim 1, The aforementioned oil and fat composition has an iodine value of 130 to 250.

3. The composition according to claim 1, The aforementioned composition is a composition that satisfies the following formulas (1) and (2). 10<F / C<150 (1) 1.0<F / P<70 (2) In formulas (1) and (2) above, C represents the mass %) of the casein in the composition, and P represents the mass %) of the polyphenols in the composition.

4. The composition according to claim 1, The aforementioned composition is a composition that satisfies the following formulas (3) and (4). 18.903 ≤ F / C ≤ 76.048 (3) 6.256 ≤ F / P ≤ 48.4 (4)

5. The composition according to claim 1, The aforementioned composition is a composition that satisfies the following formula (5). F / C ≥ 30 (5) In formula (5) above, C represents the mass %) of the casein in the composition.

6. The composition according to claim 1, A composition in which the content F of the oil and fat in the composition is 50% by mass or less.

7. The composition according to claim 3, The aforementioned C is 0.05 to 6% by mass, The composition wherein P is 0.2 to 4% by mass.

8. The composition according to claim 1, The composition wherein the polyphenols are at least one of tannins and flavonoids.

9. The composition according to claim 1, The composition further comprises alcohols, The alcohols are compositions having 2 to 40 carbon atoms in their molecular structure.

10. A paint comprising the composition according to any one of claims 1 to 9.

11. A water-resistant substrate obtained by applying the composition according to any one of claims 1 to 9 to the substrate.

12. A water-resistant substrate according to claim 11, The aforementioned substrate is a water-resistant substrate, which is a cellulose cloth paper.

13. A method for manufacturing a water-resistant substrate, A method for producing a water-resistant substrate, comprising the step of applying a composition according to any one of claims 1 to 9 to a substrate.

14. A method for producing a water-resistant substrate according to claim 13, A method for producing a water-resistant substrate, comprising the step of irradiating the composition applied to the substrate with ultraviolet light.

15. A method for producing a water-resistant substrate according to claim 13, A method for producing a water-resistant substrate, comprising the step of drying the composition applied to the substrate.