Composition, paint, water-resistant substrate, and method for manufacturing the water-resistant substrate

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

[Technical Field] 【0001】 This disclosure relates to a composition for making a substrate water-resistant, a paint containing the composition, a water-resistant substrate obtained by applying the composition, and a method for manufacturing the water-resistant substrate. [Background technology] 【0002】 Conventionally, in the manufacture of various molded products such as laminates for semiconductor substrates, decorative panels, oil filters, and sliding members, impregnated materials made by impregnating cellulose cloth paper with a thermosetting material have been used. Cured products obtained by hardening such impregnated materials have superior strength compared to cellulose cloth paper. 【0003】 Japanese Patent Publication No. 2014-095049 (Patent Document 1) discloses a molded sheet (cellulose fiber-reinforced thermoplastic resin composite molded body) obtained by preparing a persimmon tannin solution by adding trehalose to commercially available odorless persimmon tannin, immersing a fabric (a blend of 65% polyester and 35% cotton yarn) that has been scouring in the persimmon tannin solution, and then thoroughly drying it. Japanese Patent 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 carbohydrates, phenols, and organic acid ammonium salts, and a second container containing a secondary impregnation agent containing drying oils. Japanese Patent Publication No. 2001-081686 (Patent Document 3) discloses a cellulose fiber sheet formed from cellulose fibers and powder or fibers of a weakly alkali-soluble resin. Japanese Patent Publication No. 2003-013391 (Patent Document 4) discloses a paper sheet characterized by having a biodegradable resin layer formed on at least one side of a paper substrate by coating or impregnation with a biodegradable resin. [Prior art documents] [Patent Documents] 【0004】 [Patent Document 1] Japanese Patent Publication No. 2014-095049 [Patent Document 2] Japanese Patent Publication No. 2023-124508 [Patent Document 3] Japanese Patent Publication No. 2001-081686 [Patent Document 4] Japanese Patent Publication No. 2003-013391 [Overview of the project] [Problems that the invention aims to solve] 【0005】 In recent years, the use of cellulose cloth paper has become extremely important from the perspective of SDGs and carbon neutrality. However, cellulose cloth paper has poor water resistance. Therefore, by improving the water resistance of cellulose cloth paper, it is expected to be used in everyday consumables such as paper bags as an alternative to plastic bags, paper plates, paper cups, and paper molded products such as straws. 【0006】 Patent Document 1 describes a method of treating fabric by immersing it in persimmon tannin solution to improve water repellency. However, the cellulose fiber-reinforced thermoplastic resin composite molded article contains a thermoplastic resin, which is a petroleum-derived material, and does not use cellulose fibers alone as the base material. In other words, the cellulose fiber-reinforced thermoplastic resin composite molded article does not take into consideration the improvement of water resistance of cellulose fibers alone. 【0007】 Patent Document 2 describes how to obtain water-resistant cellulose cloth paper by impregnating it with a primary impregnating agent, allowing it to harden, and then impregnating it with a secondary impregnating agent. However, the manufacturing method is complex because it requires two impregnation steps and a heat treatment after impregnation that takes 10 to 60 minutes each, for a total of 20 to 120 minutes. Furthermore, because it uses carbohydrates, the water-resistant cellulose cloth paper produced using the cellulose cloth paper impregnation agent kit becomes brittle and its processability is reduced. 【0008】 Patent Document 3 describes a heating press device that heats cellulose acetate phthalate or casein powder, and then applies 200 kg / cm³ to the sample. 2In a state where a load is applied, a sheet having water resistance and solubility in a weak alkaline aqueous solution is obtained by performing a pressurization treatment for 30 seconds, but there is no description regarding cloth paper. In Patent Document 4, there is a description of impregnating a biodegradable paper sheet with an aqueous solution of a casein resin, but since the purpose is to form a coating film of the casein resin, it cannot be said that the appearance and mechanical properties are the same as those in the case of applying casein, which is a kind of protein. 【0009】 The present disclosure has been made in view of the above circumstances, and an object thereof is to provide a composition, a paint, a water-proofed substrate water-proofed by the composition, and a method for manufacturing the water-proofed substrate, which can more easily impart excellent water resistance to a substrate such as cellulose cloth paper without using petroleum-derived materials. 【Means for Solving the Problems】 【0010】 In order to solve the above problems, the present disclosure is configured as follows. That is, the composition according to the present disclosure contains polyphenols, fats and oils, and casein. The content F of fats and oils with respect to the composition is 2% by mass or more. 【Effects of the Invention】 【0011】 According to the present disclosure, excellent water resistance can be easily imparted to a substrate such as cellulose cloth paper without using petroleum-derived materials. 【Brief Description of the Drawings】 【0012】 [Figure 1] FIG. 1 is a diagram showing a method for manufacturing a water-proofed substrate. [[ID=…]] 【Modes for Carrying Out the Invention】 【0013】 (Configuration 1) The composition according to an embodiment of the present disclosure is a composition for water-proofing a substrate, and contains polyphenols, fats and oils, and casein. The content of fats and oils with respect to 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. The substrate is, for example, wood, cellulose cloth paper, or a three-dimensional molded article, etc. 【0015】 (Configuration 2) In the composition of Configuration 1, the oil and fat may have an iodine value of 130 to 250. Thereby, solidification can be facilitated. 【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 oil and fat in the composition. The composition is emulsified by mixing the components. 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) Thereby, more excellent water resistance and more excellent paint stability can be ensured. 【0018】 (Configuration 5) In any one of the compositions of Configuration 1 to 4, the composition may satisfy the following formula (5). F / C ≥ 30 (5) In the above formula (5), C represents the content (% by mass) of casein in the composition. Thereby, more excellent water resistance can be imparted. 【0019】 (Configuration 6) In any one of the compositions 1 to 5, the oil content relative to the composition may be 50% by mass or less. This makes it possible to suppress the transfer of oils contained in the water-resistant substrate. 【0020】 (Composition 7) A composition comprising composition 3 or 4, wherein C may be 0.05 to 6% by mass, and P may be 0.2 to 4% by mass. This ensures the stability of the emulsion and improves the water resistance of the substrate. 【0021】 (Composition 8) In any one of the compositions 1 to 7, the polyphenols may be at least one of tannins and flavonoids. This can further improve water resistance. 【0022】 (Composition 9) In any one of compositions 1 to 8, the composition may further contain alcohols. The alcohols may have 2 to 40 carbon atoms in their molecular structure. Furthermore, the alcohols may have fewer than 10 carbon atoms in their molecular structure. 【0023】 (Composition 10) A paint according to the embodiment of this disclosure may include any one of the compositions described above (1 to 9). 【0024】 (Composition 11) A water-resistant substrate according to the embodiment of this disclosure may be constructed by applying any one of the compositions described above (1 to 10) to the substrate. 【0025】 (Composition 12) In the water-resistant substrate of configuration 11, the substrate may be cellulose cloth paper. 【0026】 (Composition 13) The method for manufacturing a water-resistant substrate according to this disclosure may include a step of applying one of the compositions described in components 1 to 9 above to a substrate. This makes it possible to manufacture a water-resistant substrate with excellent water resistance in a short time. 【0027】 (Composition 14) In the method for manufacturing the water-resistant substrate of configuration 13, a step of irradiating the composition applied to the substrate with ultraviolet light may be included. This makes it possible to obtain a water-resistant substrate with excellent water resistance in a short time. Here, the integrated light amount during ultraviolet irradiation is 600 mJ / cm². 2 The following is acceptable. This makes it possible to obtain a water-resistant substrate with excellent water resistance and water repellency in an even shorter time. 【0028】 (Composition 15) In the method for manufacturing the water-resistant substrate of configuration 13 or 14, a step of drying the composition applied to the substrate may be included. Here, the composition applied to the substrate may be dried at a temperature of 80°C to 200°C for 10 seconds to 10 minutes. 【0029】 The above-described composition may contain a large number of micelles. These micelles may have a volume-average particle size of 40 μm or less. Furthermore, the frequency of particles with a particle size of 65 μm or more among the micelles may be 10% or less in numerical terms. This can improve the stability of the composition. 【0030】 Furthermore, the above-mentioned composition may be emulsified. 【0031】 The compositions, coatings containing the compositions, and water-resistant substrates of this disclosure will be described in detail below. 【0032】 [Composition] The composition of the present invention may contain polyphenols, oils and fats, and casein. The composition is applied to a substrate for the purpose of water resistance. Therefore, the composition can be used as a "paint," and the paint may contain the composition. Details of the substrate will be described later. 【0033】 The polyphenols may be naturally derived or synthetic products developed as antioxidants. The polyphenols contained in the compositions of this disclosure are preferably flavonoids or tannins. 【0034】 Flavonoids include, for example, catechins found in green tea, flavonols such as quercetin found in onions, isoflavones found in soybeans, or anthocyanins found in blueberries. The flavonoids may include one selected from this group of various flavonoids, or two or more. Among these, the inclusion of catechins is even more preferable. 【0035】 Examples of tannins include persimmon tannin, cinnamon, tannic acid, mimosa tannin, wattle tannin, quebracho tannin, chestnut tannin, miraborum tannin, myrobalan tannin, baronia tannin, sumac tannin, gambian tannin, oak tannin, tara tannin, zibichibi tannin, borneo katch tannin, spruce tannin, and hemlock tannin. The tannins may include one or more selected from this group of various tannins. 【0036】 The oils and fats used can be either animal oils or vegetable oils, but it is preferable to use either one. Furthermore, vegetable oils are preferred from the viewpoint of environmental impact, economic cost, or availability. Furthermore, drying oils are more preferred from the viewpoint of ease of solidification. Drying oils (unsaturated fatty acids) are oils with an iodine value of 130 or higher and solidify by oxidation. From the viewpoint of ease of solidification, the iodine value of drying oils is preferably 130 or higher, and more preferably 150 or higher. There is no particular upper limit for the iodine value, but for example, it is preferably 250 or less, and more preferably 200 or less. The iodine value can be measured by a method in accordance with JIS K0070. 【0037】 Among vegetable oils, drying oils include, for example, soybean oil, perilla oil, linseed oil, tung oil, poppy oil, shiso 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, sisylin oil, pine nut oil, camelina oil, cranberry seed oil, lime seed oil, bitter melon oil, hemp oil, sea buckthorn oil, and sea buckthorn oil. Examples of drying oils include kusoon 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, blackcurrant seed oil, borage seed oil, etc., and 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 include one selected from the group consisting of these various drying oils, or two or more. From the viewpoint of ease of handling, at least one drying oil selected from the group consisting of soybean oil, perilla oil, linseed oil, tung oil, poppy seed oil, shiso oil, walnut oil, safflower oil, and sunflower oil is preferred. Perilla oil contains palmitic acid, which has 16 carbon atoms; oleic acid and linoleic acid, which have 18 carbon atoms; and arachidic acid, which has 20 carbon atoms. 【0038】 Animal fats and oils include, for example, land-based animal fats and oils such as beef tallow, pork tallow, mutton tallow, and milk fat. Aquatic 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 to a high molecular weight during the heat treatment described later. The fats and oils contained in the composition may include either animal fats and oils or vegetable fats, but it is preferable to include either animal fats and oils or vegetable fats. That is, the composition may contain vegetable fats and oils, or animal fats and oils, or a mixture of vegetable fats and animal fats. Mineral oil may also be included as a fat or oil. 【0039】 The content F of the oil and fat in the composition can be 2% by mass or more. This can improve water repellency. Alternatively, the content F of the oil and fat in the composition can be less than 50% by mass. This can suppress oil and fat transfer, that is, when multiple substrates coated with the composition are stacked and stored or transported, the oil and fat will not transfer to other substrates, especially those placed lower down. 【0040】 Casein may be used as an isolated form of casein, or as a material containing casein. Examples of material containing casein include milk, fermented milk products, or processed milk products. When manufacturing the composition, at least one of milk, fermented milk products, and processed milk products may be used as a material. 【0041】 Furthermore, peppermint oil is preferred among plant-derived alcohols. Peppermint oil is an alcohol having 10 to 40 carbon atoms. Thus, even when using alcohols having 10 to 40 carbon atoms, excellent water resistance can be obtained. From the viewpoint of obtaining excellent water resistance, it is preferable that the alcohols have 2 to 40 carbon atoms, and from the viewpoint of improving impregnation into cellulose cloth paper, it is preferable that they have 10 or fewer carbon atoms. 【0042】 The composition may further contain other components besides polyphenols (tannins), oils and fats, and casein, as necessary, to the extent that it does not impair the effects of the present disclosure. These other components are not particularly limited and can be appropriately selected from known components that can be incorporated into the composition. Examples include water, organic solvents, inorganic ammonium salts, metal salts, and additives (surfactants, water repellents, defoamers, flame retardants, preservatives, fungicides, plasticizers, colorants, thickeners, fillers, etc.). These components may be used individually or in combination of two or more. From the viewpoint of improving affinity with the composition's materials, the organic solvent is preferably of an SP value of 10 or higher. Using an organic solvent with an SP value of 10 or higher can reduce the viscosity of the composition. 【0043】 The composition may further contain water to facilitate application or impregnation to a substrate. That is, the composition may be a liquid composition in which polyphenols, oils and fats, and emulsifiers (casein) are dissolved or dispersed in water. 【0044】 The composition is contained in a container. The container only needs to be capable of containing the composition, and its material, shape, etc., are not particularly limited. 【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), (2), and formulas (3) to (7) described later, P represents the content of polyphenols in the composition (mass%), C represents the content of casein in the composition (mass%), and F represents the content of oils and fats in the composition (mass%). 【0046】 In formula (1), if the F / C value is too small or too large, that is, if the amount of oil or fat relative to the casein in the composition is too little or too much, the stability of the emulsion of the composition decreases. 【0047】 In equation (2), if the F / P value is too small, the water resistance of the water-resistant substrate to which the composition is applied will decrease. On the other hand, if the F / P value is too large, the viscosity of the composition will become too high, and the water resistance of the water-resistant substrate to which the composition is applied will decrease. 【0048】 Furthermore, the composition preferably satisfies 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 paint and maintains good water resistance of the water-resistant substrate to which the composition is applied. 【0049】 Similar to the above formulas (1) and (2), from the viewpoints of water resistance and proper coating, etc., C can be 0.05 to 6% by mass, and P can be 0.2 to 4% by mass. Thereby, the substrate coated with the composition can obtain excellent water resistance. Also, C is preferably 0.272 to 0.742% by mass, and P is preferably 0.523 to 1.672% by mass. Further, C is more preferably 0.272 to 0.544% by mass, and P is more preferably 0.523 to 1.672% by mass. 【0050】 The composition can satisfy the following formula (5). F / C ≧ 30 (5) Thereby, the water-resistant substrate coated with the composition can obtain 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) is 6.256 ≦ F / P ≦ 48.4. 【0051】 Also, 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) Thereby, the stability of the paint is good, and the water resistance of the water-resistant substrate coated with the composition can be maintained at an extremely high level. 【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. Thereby, the emulsion can be stabilized. From such a viewpoint, 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 the light scattering method using "HORIBA LA-920 (manufactured by Horiba, Ltd.)" (laser diffraction / scattering type particle size distribution measuring device). At this time, the concentration of the liquid to be measured is measured by adjusting it to a level where the light transmittance does not exceed the measurement limit. Also, the particle size frequency of 65 μm or more in the whole micelles is 10% or less in terms of number conversion. That is, the number of micelles having a particle size of 65 μm or more is preferably 10% or less in the whole micelles, preferably 2% or less, and more preferably 0.1% or less. Thereby, the stability of the composition is improved. That is, the management of the composition becomes easy. Note that the particle size of the micelles is a value obtained by integrating the frequency % of particles of 65 μm or more from the histogram of the particle size measured by the light scattering method. Here, the volume average particle size is the radius of the particle d i , the number of the particles is n i , and it is the particle size obtained by the following formula. Σ(d i 4 ×n i ) / Σ(d i 3 ×n i ) 【0053】 [Manufacturing method of water-resistant substrate Next, the manufacturing method of the water-resistant substrate according to the present disclosure will be specifically described using FIG. 1. The water-resistant substrate of the present disclosure can be manufactured by applying the above-described composition to a substrate. 【0054】 The base material may include not only paper sheets such as cellulose cloth or corrugated cardboard, but also molded articles injection-molded from pulp, wooden furniture, etc. In other words, in this disclosure, the base material is not limited to sheets but includes three-dimensional objects, and it includes not only intermediate parts as materials for manufacturing finished products, but also finished products. 【0055】 Cellulose cloth paper is a type of cloth paper whose main component is cellulose fibers. "Cloth paper" is a general term encompassing both paper and cloth. Examples of cloth include nonwoven fabrics, woven fabrics, and felt. Cellulose cloth paper is not particularly limited and can be appropriately selected depending on the application of the water-resistant substrate. However, it is preferable that the cellulose cloth paper be paper. Examples of paper include filter paper, kraft paper, and processed base paper. The basis weight of cellulose cloth paper is 30 g / m². 2 The above is good, 50g / m 2 It is more preferable that the amount be greater than or equal to 500g / m². 2 The following is preferable: 300g / m 2 The following is preferable: 【0056】 As shown in Figure 1, the method for manufacturing cellulose cloth paper may include a coating step S1, an ultraviolet irradiation step S2, and a drying step S3. 【0057】 [Coating process S1] First, the above-mentioned composition is applied to the above-mentioned substrate. The method of applying the composition to the substrate can be any known method and is not particularly limited. For example, methods include applying the composition using a brush, applying the composition by immersing the substrate in the composition, or applying the composition by spraying it onto the substrate using a sprayer. 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 film on the surface of the substrate, or, for example, when cellulose cloth paper is used as the substrate, the composition may be applied to impregnate the entire cellulose cloth paper, or only a part of the cellulose cloth paper, for example, near the surface, may be impregnated. 【0058】 Furthermore, when cellulose cloth paper is used as the base material, the cellulose cloth paper may be coated with the composition and impregnated, and then pre-dried before the ultraviolet irradiation step S2 described later, or before the heat treatment in the drying step S3 described later, to form a prepreg. In this case, it is desirable that the prepreg contains 10% or more water in the composition. Alternatively, after coating the base material with the composition, the aforementioned oils and fats may be applied to the base material as well. 【0059】 [Ultraviolet irradiation process S2] In the ultraviolet irradiation step (S2), after applying the composition to the substrate, the composition applied to the substrate is irradiated with ultraviolet light. The method of ultraviolet irradiation is not particularly limited and can be carried out by known methods. Generally, an ultraviolet lamp is installed on the production line, and the substrate, which is the workpiece, passes through the area illuminated by the lamp, thereby irradiating the composition applied to the substrate with ultraviolet light. At this time, the irradiation time, i.e., the amount of ultraviolet irradiation, can be adjusted by the speed at which the workpiece moves. The ultraviolet irradiation may be performed once or in multiple stages. 【0060】 The ultraviolet irradiation lamp used to irradiate the composition coated on the substrate with ultraviolet light is not particularly limited and may include LED lamps, mercury lamps, metal halide lamps, xenon lamps, and black light lamps. 【0061】 While there are no specific limitations on the duration or intensity of UV exposure, the cumulative light intensity is 600 mJ / cm². 2 The following is a good rule of thumb: 500 mJ / cm² 2 Preferably, it should be 400 mJ / cm² or higher. 2 It is more preferable to keep the values ​​above the above limit. If the cumulative light intensity is below the above upper limit, the water resistance of the cellulose cloth can be improved. The cumulative light intensity should be 100 mJ / cm². 2 The above is preferable. Furthermore, the ultraviolet light source preferably includes wavelengths of 350 nm or less, and more preferably includes wavelengths of 300 nm or less. 【0062】 [Drying process S3] Drying step S3 is performed to remove solvents such as water and to adjust the curing conditions. Drying can be carried out by known methods. For example, in the case of a roll-to-roll mass production line, temperature-controlled drying equipment can be installed on the line, and the substrate can be continuously dried by passing it through the drying equipment. In this case, the drying time is determined by the length of the drying equipment and the conveying speed. The drying conditions can be set appropriately within a range in which the composition does not completely harden. For example, if a sheet body such as cellulose cloth paper is used as the substrate, several to tens of sheets of the substrate composition coated with the composition may be stacked before curing by heat treatment. Alternatively, several to tens of sheets of the substrate coated with the composition may be stacked and molded into any shape before curing by heat treatment. In this disclosure, a dry state of the composition means that the water content of the composition is less than 10%. 【0063】 As drying step S3, the composition applied to the substrate is then subjected to heat treatment. The heat treatment can be carried out by known methods, such as hot pressing and annealing. The heat treatment may be carried out 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, or by heat treatment in a batch system using a constant temperature bath or a safe vent dryer. 【0064】 The order in which the UV irradiation step S2 and the drying step S3 are performed can be reversed. That is, the UV irradiation step S2 may be performed after the drying step S3. Furthermore, while it is preferable to perform the UV irradiation step S2 from the viewpoint of further improving water resistance, sufficient water resistance can be obtained even if the UV irradiation step S2 is omitted. 【0065】 In this way, a water-resistant substrate with excellent water resistance can be easily obtained. The water-resistant substrate has superior water resistance compared to the substrate before the composition is applied. Furthermore, according to the method described above, a water-resistant substrate with excellent water resistance and water repellency can be obtained in a shorter time. 【0066】 The applications of water-resistant substrates are not particularly limited. For example, water-resistant substrates can be used as materials for various products such as bags, plates, cups, straws, tableware, laminates for semiconductor substrates, decorative panels, oil filters, sliding members, core materials, rollers, boxes, desks, chairs, and shelves. 【0067】 Furthermore, the composition, paint, and water-resistant substrate described herein, as well as the method for manufacturing the water-resistant substrate, can contribute to Goal 7, "Affordable and Clean Energy," and Goal 12, "Responsible Consumption and Production," of the United Nations Sustainable Development Goals (SDGs). 【0068】 Although embodiments have been described above, this disclosure is not limited to the embodiments described above, and various modifications are possible without departing from the spirit of the disclosure. [Examples] 【0069】 In the tables below, "Composition (parts)" refers to parts by mass, and "Composition (%)" refers to mass percent. Table 1 shows the parts by mass of the composition contained in each example and comparative example, and Table 2 shows the mass percent of the composition contained in each example and comparative example, as well as the test results. The disclosure is not limited by the following descriptions of the examples. 【0070】 (Materials used) Polyphenols: Persimmon tannin paint manufactured by Mimasu Yoshishichi Shoten Co., Ltd. (Mimasu Persimmon Tannin) Milk: Rich and delicious milk manufactured by Ezaki Glico Co., Ltd. (Examples 1-5, Example 16, Comparative Examples 1-5), Milk with high calcium and iron content manufactured by Ezaki Glico Co., Ltd. (Examples 6-15) 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 Ken-ei Pharmaceutical Co., Ltd. Drying oils: Linseed oil manufactured by Ota Oil Co., Ltd., Perilla oil manufactured by Ota Oil Co., Ltd. Soy lecithin: Soy lecithin (granules) manufactured by Marugo Corporation. 【0071】 In Table 1 below, P represents the polyphenol content (mass%) of the composition, F represents the fat and oil content (mass%) of the composition, and C represents the casein content (mass%) of the composition. P was calculated assuming that persimmon tannin paint contains 4.18 mass% polyphenols. F is calculated in Table 1 below assuming that the fat and oil content (F) of milk is the casein content. m The amount of ) was calculated assuming that it was 8.5g per 200mL (Examples 1-5, Comparative Examples 1-5) and 2.3g per 200mL (Examples 6-15), and the fats and oils contained in this milk were perilla oil or flaxseed oil (F d ) is added. C is calculated by determining the total protein content (mass%) in milk from the fact that the total protein content in milk is 6.8g per 200mL (Examples 1-5, Comparative Examples 1-5) and 3.3g per 200mL (Examples 6-15), and then assuming that casein generally accounts for 80% of the total protein content (mass%) in the milk. In addition, perilla oil or flaxseed oil (F d ), and 2-propanol, etc., were calculated at a concentration of 100%. 【0072】 [Table 1] 【0073】 [Table 2] 【0074】 [Preparation of composition] (Examples 1-4 and 6-13) Persimmon tannin paint (polyphenols), perilla oil, milk, 2-propanol (organic solvent, having 3 carbon atoms), and drying oil were sealed in a container in the parts by weight shown in Table 1, and dispersed and mixed by shaking vigorously for about 1 minute to prepare a liquid composition. In Examples 1-4 and 6-13, the ratio of milk to persimmon tannin paint is as shown in Tables 1 and 2. Also, in Examples 1-4 and 6-13, the ratio of 2-propanol:IPA (organic solvent) to persimmon tannin paint is 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 described above to prepare the composition. 【0076】 (Examples 14 and 15) In Example 14, ethanol was sealed in a sealed container as the alcohol without adding 2-propanol, and the composition was prepared by dispersing and mixing it in the same manner as described above. In Example 15, 2-propanol and ethanol were each sealed in a sealed container in the parts by weight shown in Table 1, and the composition was prepared by dispersing and mixing them in the same manner as described above. 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 soy lecithin were sealed in a sealed container and dispersed and mixed in the same manner as described above to prepare the composition. 【0078】 (Comparative Example 1) In Comparative Example 1, without adding perilla oil, persimmon tannin paint, milk, and 2-propanol were sealed in a sealed container in the parts by weight shown in Table 1, and the composition was prepared by dispersing and mixing them in the same manner as described above. That is, the composition was prepared so that F shown in Table 2 was less than 2% by mass. 【0079】 (Comparative Example 2) In Comparative Example 2, without adding persimmon tannin paint, milk, 2-propanol, and perilla oil were sealed in a sealed container in the parts by weight shown in Table 1, and the composition was prepared by dispersing and mixing them in the same manner as described above. In other words, the composition of Comparative Example 2 does not contain polyphenols (P). 【0080】 (Comparative Example 3) In Comparative Example 3, without adding perilla oil and 2-propanol, the persimmon tannin paint and milk were sealed in a sealed container in the parts by weight shown in Table 1, and the composition was prepared by dispersing and mixing them in the same manner as described above. That is, the composition was prepared so that F shown in Table 2 was less than 2% by mass. 【0081】 (Comparative Example 4) In Comparative Example 4, without adding persimmon tannin paint and 2-propanol, milk and perilla oil were sealed in a sealed container in the parts by weight shown in Table 1, and the composition was prepared by dispersing and mixing them in the same manner as described above. In other words, the composition of Comparative Example 4 does not contain polyphenols (P). 【0082】 (Comparative Example 5) In Comparative Example 5, without adding milk and 2-propanol, the persimmon tannin paint and perilla oil were sealed in a sealed container in the parts by weight shown in Table 1, and the composition was prepared by dispersing and mixing them in the same manner as described above. In other words, the composition of Comparative Example 5 does not contain casein (C). 【0083】 Furthermore, in preparing the compositions for each example and comparative example, the compositions could be easily prepared, particularly 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, when milk was used in particular, the compositions could be prepared in a short time. 【0084】 [Measuring particle size of the composition] Using the aforementioned "HORIBA LA-920 (manufactured by HORIBA, Ltd.)" light scattering method, the particle size distribution of the micelles in the composition was measured. 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, indicating improved stability of the composition. Here, the average particle size refers to the particle size at 50% of the cumulative value of the number of particles in the particle size distribution (volume-average particle size). 【0085】 [Sample preparation] In Examples 1-16 and Comparative Examples 1-5, the composition was applied to a cellulose cloth paper substrate measuring 150 mm x 150 mm (JK Wiper® 150S (manufactured by Nippon Paper Crecia Co., Ltd.)), impregnating both sides of the kraft paper without any gaps. Heat treatment was then performed under the heat treatment conditions shown in Table 2 to obtain samples impregnated with the composition. 【0086】 [Evaluation of paint stability] The stability of the composition (paint) was evaluated as follows: First, the composition was prepared and left to stand for 24 hours. After that, if the composition separated into two layers or precipitate formed, it was evaluated as unstable and given a rating of "C". If there was no clear separation such as precipitation, but the apparent viscosity increased and decreased again after stirring, it was evaluated as "B". If it remained uniformly dispersed without separating into two layers, i.e., maintained an emulsion state, it was evaluated as stable and given a rating of "A". 【0087】 [Evaluation of water repellency] The water repellency of the prepared samples was tested according to the old JIS standard (JIS P8137), and the water repellency of the samples was evaluated according to that standard. 【0088】 Comparing Examples 1-16 with Comparative Examples 1-5, excellent water repellency was obtained when polyphenols, oils and fats, and casein were included, and the oil content F was 2% by mass or more. In other words, Comparative Examples 1 and 3, where the oil 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 could not be obtained. Thus, it was confirmed that if polyphenols, casein, and oils and fats are included, and the oil content F relative to the composition is 2% by mass or more, the water-resistant substrate can obtain sufficient water repellency. In Comparative Example 5, which did not contain casein, the paint was unstable, and water repellency could not be evaluated. From this, it is considered that casein is necessary to stabilize the paint. 【0089】 Furthermore, the "stability of the paint (composition)" and "water repellency" described above were evaluated in Examples 1 to 16. 【0090】 First, the "stability of the paint" was evaluated. As a result, in Examples 6, 7, 11, and 12, the evaluation was "B", while in the other examples, the evaluation was "A". In Example 11, since the F / C value was too small, that is, the content of casein was too low, the stability of the paint was considered to be rated "B". Also, in Examples 6, 7, and 12, since the F / C value was too large, that is, the content of casein was too high, the stability of the paint was considered to be rated "B". In Example 12, since the F / P value was too large, that is, the content of sesame oil was too high, the stability of the paint was considered to be rated "B". In Example 12, it is considered that the stability of the paint was inferior because the viscosity became too high compared to the compositions of Examples 6 and 7. Therefore, from the viewpoint of ensuring the stability of the paint, it was confirmed that 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 composition can ensure the stability of the paint by satisfying the formula (1) "10 < F / C < 70" and the formula (2) "1.0 < F / P < 70". Also, in Examples 14 and 15, alcohols other than 2-propanol were used, but since the evaluation was "A", it was confirmed that the paint is stable even when alcohols other than 2-propanol are used. 【0091】 Next, the "water repellency" was evaluated. As a result, in Examples 1 to 16, in Examples 2 to 4, 8, and 13 where the F / C value was less than 30, the evaluation of water repellency was "R8" or less. On the other hand, in the other examples where the F / C value was 30 or more, the evaluation of water repellency was high, "R9" or more. From this, it was possible to further improve the water repellency by having the F / C value be 30 or more, that is, by satisfying the formula (3) "F / C ≥ 30". Furthermore, by satisfying the above formulas (1), (2), and (3), more excellent paint stability and water repellency could be obtained. 【0092】 Furthermore, with the exception of Comparative Example 5, the number of coatings was reduced to one, and the heat treatment time was shortened to one minute for all coatings. In addition, in Example 16, the "stability of the coating" was rated as "A" and the "water repellency" was rated as "R10," indicating that excellent coating stability and water repellency could be obtained even when containing trace amounts of both lecithin and casein. In other words, excellent coating stability and water repellency could be obtained even when containing an amount of lecithin that does not affect the mixing of the coatings. From these results, the present invention provides a composition, a coating, a water-resistant substrate made water-resistant by the composition, and a method for manufacturing a water-resistant substrate, which can more easily impart excellent water resistance to substrates such as cellulose cloth paper. 【0093】 Here, the polyphenol content P can be determined as follows. First, 550% ethanol is added to 0.2-0.6 g of the composition sample, and then it is irradiated with ultrasound and centrifuged. After that, it is filtered to obtain the test solution. Also, 1 ml of catechin standard solution is prepared. To the catechin standard solution, 0.5 ml of Folin-Ciacalteu reagent and 5 ml of 0.4 mol / L sodium carbonate aqueous solution are added, and after standing at 30°C for 25 minutes, the polyphenol content P is determined by measuring at a wavelength of 660 nm using a UV-Vis 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. Then, it is made up to 10 mL with methanol to obtain 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】 Furthermore, methods for measuring the casein content C include antibody-based methods such as ELISA. These are methods for detecting specific proteins. When determining the casein content C in paint using the ELISA method, a sample can be prepared from the paint as follows: Dilute the paint with a buffer solution so that the alcohol concentration in the paint is 1% by mass or less. When diluting the paint, add buffer solution until the pH of the sample is around 7. The type of buffer solution is not particularly limited as long as the pH of the sample is around 7, but preferably a pH of 3 to 11, more preferably a pH of 4 to 10, and even more preferably a pH of 5 to 9 can be used. Specifically, phosphate buffers such as PBS, glycine buffers, Tris buffers, borate buffers, citrate buffers, Good's buffers, etc., can be used. The concentration of the buffer solution is not particularly limited as long as the pH of the sample is around 7, but for example, it is preferably 0.1 to 200 mM, and more preferably 1 to 150 mM. In this invention, the concentration of the buffer solution refers to the concentration (mM) of the buffering agent contained in the buffer solution. Furthermore, a sample pH of around 7 refers to a pH of 7.2 to 7.4. It is preferable to dilute the sample to a casein concentration of 10 to 1000 μg / L. If it is necessary to reduce the casein concentration of the sample to less than 1 / 1000 of the paint concentration, serial dilution is preferable. 【0095】 Furthermore, the casein content C can be determined, especially when using milk, by first measuring the total nitrogen content to determine the total protein content and then confirming that 80% of the protein determined by LC-MS is casein. It is also possible to separate and measure the protein using various LC methods. 【0096】 Furthermore, the oil and fat content F can be determined by the following method. First, a solvent with a molecular structure without CH groups, such as carbon tetrachloride or trichlorotrifluoroethane, is added to the composition sample to separate the oil component from other components such as water. Then, a calibration curve is created from the absorbance of the infrared spectroscopic spectrum using an OCB mixed standard substance, and the oil and fat content F is quantified by comparing the absorbance of the calibration curve with that of the sample.

Claims

[Claim 1] A composition for making a substrate water-resistant, It contains tannins, drying oils, and casein found in milk. A composition in which the content F of the drying oil in the composition is 2% by mass or more. [Claim 2] The composition according to claim 1, The drying oil is a composition having an iodine value of 130 to 250. [Claim 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 casein contained in the milk relative to the composition, and P represents the mass %) of tannin relative to the composition. [Claim 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) [Claim 5] The composition according to claim 1, The composition is a composition that satisfies the following formula (5). F / C ≥ 30 (5) In formula (5) above, C represents the mass %) of casein contained in the milk relative to the composition. [Claim 6] The composition according to claim 1, A composition in which the content F of the drying oil in the composition is 50% by mass or less. [Claim 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. [Claim 8] 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. [Claim 9] A paint comprising the composition according to any one of claims 1 to 8. [Claim 10] A water-resistant substrate obtained by applying the composition according to any one of claims 1 to 8 to the substrate. [Claim 11] A water-resistant substrate according to claim 10, The aforementioned substrate is a water-resistant substrate, which is a cellulose cloth paper. [Claim 12] 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 8 to a substrate. [Claim 13] A method for producing a water-resistant substrate according to claim 12, A method for producing a water-resistant substrate, comprising the step of irradiating the composition applied to the substrate with ultraviolet light. [Claim 14] A method for producing a water-resistant substrate according to claim 12, A method for producing a water-resistant substrate, comprising the step of drying the composition applied to the substrate.

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