Composition, coating, water-resistant base material, and method for producing water-resistant base material

Abstract

Provided are a composition that can impart excellent water resistance to a base material, a coating that contains the composition, and a method for producing a base material that has been made water-resistant. The composition contains polyphenols, fats / oils, and lecithin. The polyphenol is, for example, a tannin. The lecithin is, for example, egg yolk lecithin or soybean lecithin. The composition may also contain acetic acid and can be obtained by emulsifying a mixture of these components. A base material that has been made water-resistant and has excellent water resistance can be obtained by impregnating the base material with the composition and performing drying treatment by 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 blended yarn of 65% polyester and 35% cotton) that has been refined in the persimmon tannin liquid, and then thoroughly drying it.

[0004] JP 2014-095049 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] 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.

[0008] 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, oils and fats, and lecithin.

[0009] According to the present disclosure, excellent water resistance can be imparted to substrates such as cellulose cloth and paper without using petroleum-derived materials.

[0010] FIG. 1 is a diagram showing a method for manufacturing a water-resistant substrate.

[0011] (Configuration 1) A composition according to an embodiment of the present disclosure is a composition for waterproofing a substrate, and includes polyphenols, an oil and fat, and lecithin. The oil and fat may include at least one of an animal oil and fat and a vegetable oil and fat.

[0012] 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.

[0013] (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.

[0014] (Configuration 3) In the composition of Configuration 1 or 2, the composition may satisfy the following formulas (1) and (2): 5<F / L<150 (1) 1.0<F / P<25 (2) In the above formulas (1) and (2), P represents the content (wt%) of polyphenols in the composition, L represents the content (wt%) of lecithin in the composition, and F represents the content (wt%) of fats and oils in the composition. The composition is emulsified by mixing the ingredients. By satisfying the above formula (1), the stability of the emulsion of the composition can be ensured. Furthermore, by satisfying formula (2), the water resistance of the substrate to which the composition is applied can be improved, and the composition can be appropriately applied to the substrate.

[0015] (Configuration 4) In the composition of Configuration 3, F / L in formula (1) is greater than 20. This makes it possible to impart better water resistance.

[0016] (Configuration 5) In the composition of claim 3 or 4, F may be 2 to 50 mass %, L may be 0.05 to 6 mass %, and P may be 0.2 to 4 mass %. This ensures emulsion stability and improves the water resistance of the substrate.

[0017] (Configuration 6) In the composition of any one of Configurations 1 to 5, the polyphenols may be at least one of tannins and flavonoids, thereby further improving water resistance.

[0018] (Configuration 7) In the composition of any one of Configurations 1 to 6, the lecithin may be at least one of egg yolk lecithin and soybean lecithin.

[0019] (Configuration 8) In the composition of any one of Configurations 1 to 7, 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.

[0020] (Configuration 9) In the composition of any one of configurations 1 to 8, the composition may contain egg yolk containing lecithin and acetic acid.

[0021] (Configuration 10) A coating material according to an embodiment of the present disclosure may include the composition of any one of configurations 1 to 9 described above.

[0022] (Configuration 11) A water-resistant substrate according to an embodiment of the present disclosure may be constructed by applying any of the compositions of configurations 1 to 9 to a substrate.

[0023] (Configuration 12) In the water-resistant substrate of Configuration 11, the substrate may be a cellulose cloth paper.

[0024] (Configuration 13) A method for producing a water-resistant substrate according to the present disclosure may include a step of applying to a substrate any of the compositions described above in 1 to 9. This allows a water-resistant substrate with excellent water resistance to be produced in a short period of time.

[0025] (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.

[0026] (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.

[0027] 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.

[0028] The above-described composition may also be emulsified.

[0029] The composition of the present disclosure, the coating material containing the composition, and the water-resistant substrate will be specifically described below.

[0030] [Composition] The composition of the present invention may contain polyphenols, oils and fats, and lecithin (egg yolk lecithin, soybean lecithin, or the like). The composition is applied to a substrate for the purpose of imparting 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] The oil or fat can be either vegetable oil or animal oil. However, vegetable oil is preferred from the viewpoint of economic cost or availability. Furthermore, drying oil is more preferred 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.

[0035] 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.

[0036] 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 as long as they are drying oils, as they polymerize to a high molecular weight during the heat treatment described below. The fats and oils contained in the composition can include either animal fats and oils or vegetable fats and oils. That is, the composition may include vegetable fats and oils, animal fats, or a mixture of vegetable and animal fats and oils.

[0037] The lecithin is lecithin contained in egg yolk, etc. The egg yolk is that of a chicken egg. However, the egg yolk may be that of a quail, ostrich, or other bird, because these egg yolks also contain egg yolk lecithin, which will be described later. Note that whole eggs may also be used as a material when producing the composition.

[0038] The composition may contain vinegar, which may contain acetic acid as a main component, and preferably has a pH of 2 to 6.

[0039] Mayonnaise is an example of an ingredient containing fats and oils, egg yolk, and vinegar. Mayonnaise is an emulsified food with a high fat content, produced by emulsifying fats and oils with lecithin, a natural emulsifier found in egg yolk. Using mayonnaise as a substitute for fats and oils, egg yolk, and vinegar allows for easier and more cost-effective production of the composition. From a recycling perspective, it is also possible to utilize mayonnaise that is no longer suitable for use as a food product. The mayonnaise used in the production of the composition can be prepared by thoroughly mixing egg yolk, acetic acid, and fats and oils (animal fats or vegetable fats and oils), adding a liquid containing the polyphenols described above (e.g., persimmon tannin paint) to the mayonnaise (fat, egg yolk, and acetic acid), placing the mixture in a sealed container, and emulsifying the mixture by vigorously shaking the sealed container. However, the method for producing the composition is not limited to this. For example, a method is conceivable in which drying oil is added to soybean lecithin, followed by the addition of vinegar or alcohol, etc., followed by dispersion and mixing. That is, the composition is an emulsified mixture containing polyphenols, oils and fats, and lecithin. It is also possible to use commercially available mayonnaise containing salt, the main component of which is sodium chloride.

[0040] Furthermore, the vegetable alcohol is preferably mint oil. Mint oil is an alcohol having 10 to 40 carbon atoms. Thus, even when using an alcohol having 10 to 40 carbon atoms, excellent water resistance can be obtained, particularly when soybean lecithin is used as the lecithin. 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, it is preferable that the alcohol have 10 or less carbon atoms.

[0041] The composition may further contain other components in addition to polyphenols (tannins), oils and fats, egg yolk, and vinegar, 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.

[0042] 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 (lecithin) are dissolved or dispersed in water.

[0043] 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.

[0044] The composition satisfies the following formulas (1) and (2): 5<F / L<150 (1) 1.0<F / P<25 (2) In formulas (1) and (2), P represents the content (% by weight) of polyphenols in the composition, L represents the content (% by weight) of lecithin in the composition, and F represents the content (% by weight) of fats and oils in the composition.

[0045] In formula (1), if the value of F / L is too small or too large, that is, if the amount of fat or oil relative to the amount of lecithin contained in the composition is too small or too large, the emulsion stability of the composition decreases.

[0046] In addition, in formula (1), F / L is preferably greater than 20. This makes it possible to obtain better water resistance.

[0047] In formula (2), if the F / P value is too small, the water resistance of the water-resistant substrate to which the composition is applied decreases. On the other hand, if the F / P value is too large, the viscosity of the composition becomes too high, making it impossible to properly apply the composition to the substrate. Furthermore, because the proportion of oil and fat becomes too high, for example, when cellulose cloth or paper is used as the substrate, it becomes difficult to impregnate the cellulose cloth or paper with the composition. Furthermore, the oil and fat oozes out of the water-resistant cellulose cloth or paper, and when other papers are stacked on top of the water-resistant cellulose cloth or paper and stored, the oil and fat are transferred to the other papers.

[0048] As with the above formulas (1) and (2), from the viewpoints of water resistance and appropriate application, F can be 2 to 50 mass %, L can be 0.05 to 6 mass %, and P can be 0.2 to 4 mass %, thereby enabling a substrate coated with the composition to have excellent water resistance.

[0049] 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 micelles is the 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 the particle size calculated by the following formula, where di is the radius of the particle and ni is the number of particles: Σ(di ４ ×ni) / Σ(di 3 ×ni)

[0050] [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.

[0051] 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.

[0052] 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:

[0053] 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.

[0054] [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.

[0055] 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.

[0056] [Ultraviolet Irradiation Step S2] In the ultraviolet irradiation step (S2), after the composition is applied to the substrate, ultraviolet light is irradiated onto the composition applied to the substrate. 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 by the lamp light, thereby irradiating ultraviolet light onto the composition applied to the substrate. 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.

[0057] 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.

[0058] 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.

[0059] [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%.

[0060] 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.

[0061] 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.

[0062] In this way, a water-resistant substrate having excellent water resistance can be 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.

[0063] 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.

[0064] The composition, paint, and water-resistant substrate, as well as the method for producing a water-resistant substrate, according to the present disclosure, can contribute to the achievement of Goal 7 "Affordable and clean energy" and Goal 12 "Responsible consumption and production" of the Sustainable Development Goals (SDGs) advocated by the United Nations.

[0065] 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.

[0066] 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.

[0067] (Materials used) Polyphenols: Persimmon tannin paint (Mitsuru Kakishibu) manufactured by Mimasu Kasshichi Shoten Co., Ltd. Mayonnaise: Contains 7 ml (6.5%) of vinegar, 20 g (18.7%) of one egg yolk, and 80 ml (72.7%) of vegetable oil. The mayonnaise was made as follows. First, the above ingredients were returned to room temperature, and half of the vegetable oil was added little by little to the egg yolk containing lecithin while mixing to make it cloudy, and then vinegar was added and mixed. Finally, the remaining half of the vegetable oil was added little by little while mixing to obtain mayonnaise. Organic solvent: 2-propanol manufactured by Wako Pure Chemical Industries, Ltd. Drying oil: Linseed oil manufactured by Ohta Oil Co., Ltd., perilla oil manufactured by Ohta Oil Co., Ltd.

[0068] In Table 1 below, P is the content (% by mass) of polyphenols relative to the composition, F is the content (% by mass) of fats and oils relative to the composition, and L is the content (% by mass) of lecithin relative to the composition. P was calculated assuming that the persimmon tannin paint contains 4.18% by mass of polyphenols. F is calculated in Table 1 below assuming that the fats and oils contained in mayonnaise generally contain 72.7% fats and oils, and is the sum of linseed oil (F1) and perilla oil (F2) contained in this mayonnaise. L is calculated assuming that the mayonnaise lecithin (egg yolk lecithin) (L1) generally contains 0.71% fats and oils, and is the sum of soybean lecithin (L2) contained in this mayonnaise lecithin (L1). In addition, soybean lecithin (L2), linseed oil (F1), perilla oil (F2), 2-propanol, etc. were calculated as having a concentration of 100%. Furthermore, in Tables 1 and 2, 2-propanol (C3) and peppermint oil (C10) indicate the number of carbon atoms in each.

[0069]

[0070]

[0071] [Preparation of Compositions] (Examples 1 to 10 and 13 to 23) Persimmon tannin paint (polyphenols), mayonnaise, soybean lecithin, 2-propanol (organic solvent, having three carbon atoms) or drying oil were placed in a sealed container in the weight parts shown in Table 1 and dispersed and mixed by vigorously shaking for about 1 minute to prepare liquid compositions. In Examples 1 to 4, 7, 9, and 10, the ratio of mayonnaise to persimmon tannin paint is as shown in Tables 1 and 2. In Examples 1 to 3, 5 to 6, 8 to 10, and 13 to 23, the ratio of 2-propanol:IPA (organic solvent) to persimmon tannin paint was 75 to 100%.

[0072] In Examples 11 and 12, 2-propanol was not added, and instead, peppermint oil was placed in a sealed container as the alcohol, and the mixture was dispersed and mixed in the same manner as described above to prepare a composition. The peppermint oil has 10 to 40 carbon atoms.

[0073] [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%.

[0074] [Preparation of Samples] In Examples 1 to 23, the compositions were applied to a cellulose cloth paper substrate (JK Wiper (registered trademark) 150S (manufactured by Nippon Paper Crecia Co., Ltd.)), and the composition was impregnated into 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.

[0075] (Comparative Examples 1 to 6) Basis weight approximately 50g / m ２ Kraft paper (unbleached, matte on both sides) (manufactured by Hokuetsu Corporation) was cut into a 15 cm x 15 cm square and its mass was measured. This kraft paper alone was used as the sample for Comparative Example 1.

[0076] In Comparative Examples 2 to 4, persimmon tannin paint containing polyphenols (Comparative Example 2), mayonnaise (Comparative Example 3), a mixture of mayonnaise and an organic solvent (Comparative Example 4), and egg yolk (Comparative Example 6) were each impregnated into JK Wiper 150S (manufactured by Nippon Paper Crecia Co., Ltd.) in the formulations shown in Tables 1 and 2, and the paper was impregnated tightly onto both sides of kraft paper. Heat treatment was then performed under the heat treatment conditions shown in Table 2, and samples impregnated with each component were obtained.

[0077] In Comparative Example 5, a persimmon tannin paint containing polyphenols was impregnated into JK Wiper 150S (manufactured by Nippon Paper Crecia Co., Ltd.) as a base with the formulation shown in Tables 1 and 2, and impregnated tightly onto both sides of kraft paper, followed by heat treatment under the heat treatment conditions shown in Table 2, to obtain a sample impregnated with the persimmon tannin paint. Subsequently, drying oil and organic solvent were impregnated in the same manner as the top layer, and heat treatment was again performed under the heat treatment conditions shown in Table 2, to obtain a sample impregnated with the drying oil and organic solvent.

[0078] The mass of each sample was measured, and the solid application amount of the composition impregnated into the kraft paper was calculated from the measured mass using the following formula: Composition (g) = B - A Here, "A" represents the mass (g) of the kraft paper before impregnation, and "B" represents the mass (g) of the sample impregnated with the composition after heat treatment. Note that in Comparative Example 2, the solid application amount of the composition was negative because a large amount of water contained in the kraft paper had evaporated before the composition was applied.

[0079] [Evaluation of Water Absorption] The water absorption of the prepared samples was evaluated using the following procedure. The mass of each prepared sample measuring 150 mm x 150 mm was measured. A Pax Naturon (registered trademark) kitchen sponge manufactured by Taiyo Yushi Co., Ltd. was cut with a cutter to 6 cm x 10.5 cm x 3 cm, and after fully absorbing water, it was placed on the center of the sample surface and left for 60 minutes. After 60 minutes, the sponge was removed, and the water was wiped off with a white Kimtowel folded in four (manufactured by Nippon Paper Crecia Co., Ltd.). Subsequently, water droplets remaining on the sample surface were wiped off with another Kimtowel to ensure that no water droplets remained on the sample surface. The mass of the wiped sample was measured, and the difference in mass before and after placing the sponge was taken as the water absorption. The results are shown in Table 1. The lower the water absorption, the better the water resistance of the sample.

[0080] [Evaluation of Oil Transfer] The state of oil transfer of the prepared samples was evaluated as follows: First, the sample was sandwiched between two sheets of kraft paper made of virgin pulp, a 10 cm square metal plate was placed on top of the two sheets, and a weight was further placed on top of the metal plate. ２ The sandwiched kraft paper was then visually inspected to see if oil had seeped into it and formed stains, and if stains had formed on the kraft paper, the oil transfer was evaluated as "present."

[0081] [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."

[0082] [Evaluation of Appearance of Water-Resistant Cellulose Fabric Paper (Water-Resistant Paper)] The samples were evaluated as "uneven" if color unevenness due to the impregnated composition was clearly visible, and as "uniform" if not.

[0083] [Evaluation of Water Repellency] The water repellency of the prepared samples was tested based on the old JIS standard (JIS P8137), and samples rated as R9 or R10 in the standard were rated as "A", and other samples were rated as "B".

[0084] The water absorption of Examples 1 to 3, which were coated with a composition containing persimmon tannin paint (polyphenols), mayonnaise (oil, egg yolk, and vinegar), and an organic solvent, and Example 4, which was coated with a composition containing persimmon tannin paint and mayonnaise, was lower than that of Comparative Example 1, which was coated with only kraft paper, confirming improved water resistance. Similarly, improved water resistance was confirmed in Example 5, which was coated with a composition lacking persimmon tannin paint, soybean lecithin, an organic solvent, and a drying oil. The water absorption of Comparative Examples 2 to 5, which were coated with a composition lacking either persimmon tannin paint (polyphenols), mayonnaise (egg yolk lecithin), soybean lecithin, or a drying oil, was lower than that of Comparative Example 1 but higher than that of Examples 1 to 6. In Comparative Example 5, the persimmon tannin paint and the drying oil separated, requiring the composition to be applied twice: once to apply the persimmon tannin paint and once to apply the drying oil. This suggests that lecithin prevents the composition from separating. Furthermore, the water absorption amount of Comparative Example 6, which contained only egg yolk as a composition, was approximately the same as that of Comparative Example 1. From the above, it was confirmed that the water absorption amount of cellulose cloth and paper can be significantly reduced by using a composition containing polyphenols contained in persimmon tannin paint and either egg yolk lecithin or soybean lecithin and fats and oils.

[0085] Furthermore, comparing Examples 1 to 3, the longer the drying time, the lower the amount of water absorption. However, even in Examples 3 to 6, which had relatively short drying times, the amount of water absorption was still significantly lower than in the comparative examples. That is, the evaluation of Examples 1 to 3 confirmed that it was possible to produce water-resistant cellulose fabric paper with excellent water resistance while shortening the production period. Furthermore, comparing Examples 1 to 23, when the F / L value exceeded 20, the amount of water absorption tended to decrease significantly. In other words, the water resistance tended to improve significantly. Therefore, in formula (1), it was found that better water resistance could be obtained when F / L was greater than 20.

[0086] Furthermore, in Examples 1 to 23, the above-mentioned "oil transfer," "stability of the coating (composition)," and "appearance of the waterproof paper (water-resistant cellulose cloth paper)" were evaluated.

[0087] As a result, in the "oil transfer" test, oil transfer was "yes" in Examples 10 and 23, while oil transfer was "no" in the other Examples. In other words, Examples 10 and 23 contained relatively high amounts of oil and fat components such as mayonnaise or perilla oil. This suggests that the L / P value became too large, increasing the viscosity and preventing proper impregnation of the composition, resulting in oil transfer. Therefore, it was confirmed that the L / P value in formula (2) should be less than 25. While dilution with water may be considered to properly impregnate the composition, it is believed that this would reduce water repellency due to a decrease in the polyphenol content P.

[0088] Next, the "paint stability" was evaluated. As a result, Examples 17, 18, 21, and 22 were rated "B," while the other Examples were rated "A." In Examples 18, 21, and 22, the F / L value was too small, i.e., the lecithin content was too low, which is thought to be why the paint stability was rated "B." In addition, in Example 17, the F / L value was too large, i.e., the lecithin content was too high, which is thought to be why the paint stability was rated "B." Therefore, it was confirmed that, from the perspective of ensuring paint stability, it is best for the F / L value to be greater than 5 and less than 150. In other words, it was found that the paint stability can be ensured by the composition satisfying formula (1) "5 < F / L < 150."

[0089] Next, the "appearance of the waterproof paper" was evaluated. As a result, Examples 11, 12, 14, 18, 21, and 22 were "uneven," while in the other Examples, color unevenness due to the composition was not visually observed. In Example 11, "peppermint oil" was used as the organic solvent instead of 2-propanol. Although sufficient water resistance was obtained in Example 11, it is believed that the "appearance of the waterproof paper" became uneven due to the increased viscosity. Furthermore, in Example 12, although impregnation was easier than in Example 11 due to dilution with water twice, the "appearance of the waterproof paper" became uneven. Note that when 2-propanol was used, excellent water resistance was obtained even when diluted with water four times. In Example 14, the relatively low content of 2-propanol increased the viscosity, and the low oil content caused the paint to impregnate the kraft paper poorly, which is believed to have resulted in the "appearance of the waterproof paper" becoming uneven. In addition, it is believed that the viscosity increased due to the excessive lecithin content in Examples 18, 21, and 22, resulting in a non-uniform "appearance of waterproof paper." Therefore, it is believed that the contents of 2-propanol, peppermint oil, and lecithin affect the "appearance of waterproof paper."

[0090] Next, the "water repellency" was evaluated. As a result, excellent water repellency was obtained in all of Examples 1 to 23. That is, in all of Examples 1 to 23, the F / P value was greater than 1.0. Thus, taking into account the evaluation of "oil transfer" described above, it was found that satisfying formula (2) "1.0<F / P<25" improved water repellency and allowed the composition to be appropriately impregnated into the cellulose fabric / paper.

[0091] 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.

[0092] The lecithin content L can be determined by the following method. First, a 2:1 mixture of chloroform and methanol is added to 1.2 g of a composition sample to obtain a mixed solution. Next, the mixed solution is centrifuged, and 100 ml of the 2:1 mixture of chloroform and methanol is added to the precipitate, mixed thoroughly, and centrifuged. 20 ml of the 2:1 mixture of chloroform and methanol is added to the solid fraction, and centrifuged again. 93 ml of 0.99% potassium chloride solution is added to the entire upper layer obtained by this centrifugation, and the mixture is left overnight. The mixture is then dehydrated and filtered, and the solvent is removed by evaporation. 50 ml of chloroform is added, mixed, and 5 ml is taken. After removing the solvent, 0.5 g of magnesium nitrate is added, and the mixture is decomposed at 550 °C for 16 hours. 5 ml of 6 mol / L hydrochloric acid solution is added, and 50 ml of constant volume water is added, mixed uniformly, and 20 ml is taken. After neutralizing the solution, 5 ml of a molybdenum blue coloring reagent, 1 ml of a 5% ascorbic acid solution, and 50 ml of water are added to develop color, and the absorbance is measured at a wavelength of 710 nm for quantification.

[0093] 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, comprising polyphenols, an oil or fat, and lecithin, wherein the composition satisfies the following formulas (1) and (2). 5 < F / L < 150 (1) 1.0 < F / P < 25 (2) In the above formulas (1) and (2), F represents the content (% by weight) of the oil or fat with respect to the composition, L represents the content (% by weight) of the lecithin with respect to the composition, and P represents the content (% by weight) of the polyphenols with respect to the composition.

2. The composition according to claim 1, wherein the oil or fat has an iodine value of 130 to 250.

3. The composition according to claim 1, wherein in formula (1), F / L is greater than 20.

4. The composition according to claim 1, wherein F is 2 to 50% by mass, L is 0.05 to 6% by mass, and P is 0.2 to 4% by mass.

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

6. The composition according to claim 1, wherein the lecithin is at least one of egg yolk lecithin and soybean lecithin.

7. The composition according to claim 1, wherein the composition further contains alcohols, and the alcohols have 2 to 40 carbon atoms in their molecular structure.

8. The composition according to claim 1, wherein the composition contains egg yolk containing the lecithin and acetic acid.

9. A composition for making a substrate water-resistant, comprising polyphenols, an oil or fat, and lecithin, wherein the composition contains egg yolk containing the lecithin and acetic acid.

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. The water-resistant substrate according to claim 11, wherein the substrate is cellulose paper.

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

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

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