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

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

[Technical Field]

[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. [Background technology]

[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 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 fabric (a blend of 65% polyester and 35% cotton) that has been refined in the persimmon tannin liquid, and then thoroughly drying it. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-095049 Summary of the Invention

[0005] In recent years, the use of cellulose cloth and paper has become increasingly important from the perspectives of 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 fiber-reinforced thermoplastic resin composite molding contains a thermoplastic resin, which is a petroleum-derived material, and is not based solely on cellulose fiber. In other words, the cellulose fiber-reinforced thermoplastic resin composite molding does not take into consideration the improvement of water resistance of cellulose fiber 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. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a diagram showing a method for producing a water-resistant substrate. DETAILED DESCRIPTION OF THE INVENTION

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

[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 the first or second aspect, 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 %, thereby ensuring the stability of the emulsion and improving the water resistance of the substrate.

[0017] (Configuration 6) In any of the compositions 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 any of the compositions 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 Aspects 1 to 7, the composition may further contain 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) The coating material according to an embodiment of the present disclosure may contain any of the compositions 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 waterproof substrate of configuration 11, the substrate may be a cellulose cloth paper.

[0024] (Configuration 13) The 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 1 to 9 described above, thereby enabling 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 the thirteenth aspect 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 cumulative 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 can contain polyphenols, oils and fats, and lecithin (egg yolk lecithin, soybean lecithin, etc.). The composition is applied to a substrate for the purpose of making it water-resistant. Therefore, the composition can be used as a "paint," and the paint can contain the composition. Details of the substrate will be described later.

[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, myraborum 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 fats and oils can be either vegetable fats or animal fats and oils. However, vegetable fats are preferred from the viewpoint of economic cost and 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 more, and solidify by oxidation. From the viewpoint of ease of solidification, the iodine value of drying oils 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 contain 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 the perspective of recycling, 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., and then dispersing and mixing the mixture. 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, the alcohol preferably has 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, to the extent that 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. The viscosity of the composition can be reduced by using an organic solvent with an SP value of 10 or more.

[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 (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.

[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 difficult to properly apply the composition to the substrate. Furthermore, if the oil content 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 will ooze out of the water-resistant cellulose cloth or paper, and if other papers are stacked on top of the water-resistant cellulose cloth or paper when stored, the oil and fat will be 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 set to 2 to 50 mass %, L can be set to 0.05 to 6 mass %, and P can be set to 0.2 to 4 mass %, thereby allowing the substrate to which the composition is applied 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 a particle size of 65 μm or more is 10% or less in terms of number. That is, the number of micelles with a particle size 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 and makes it easier to manage the composition. The particle size of micelles is the sum of the percentage of particles 65 μm or larger in size from a particle size histogram measured by light scattering. Here, the volume-average particle size is the particle size calculated by the following formula, where di is the particle radius 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 Figure 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. There are no particular limitations on the cellulose cloth paper, and it 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 better to have more than 50g / m 2 More preferably, it is 500 g / m or more. 2 It is better to have less than 300g / m 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 process 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 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 a 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, the prepreg preferably contains 10% or more of water in the composition. Furthermore, after the composition is applied to the substrate, the aforementioned oil or fat may be further applied to the substrate.

[0056] [Ultraviolet irradiation process S2] In the ultraviolet irradiation step (S2), after the composition is applied to the substrate, ultraviolet rays are 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. Generally, 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 the composition applied to the substrate with ultraviolet rays. At this time, the irradiation time, i.e., the amount of ultraviolet irradiation, can be adjusted by the moving speed of the workpiece. The ultraviolet 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 intensity of ultraviolet light are not particularly limited, but the cumulative light amount is 600 mJ / cm 2 It is best to keep it below 500mJ / cm 2 It is preferable to use a dose of 400 mJ / cm or more. 2 It is more preferable that the integrated light amount is equal to or less than the upper limit mentioned above. 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. In addition, the integrated light amount is 100 mJ / cm 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 process 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. 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. In the present disclosure, a dry composition refers to a composition whose water content is 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 manufacturing a water-resistant substrate, according to the present disclosure, can contribute to achieving Goal 7 "Affordable and clean energy" and Goal 12 "Responsible consumption and production" of the Sustainable Development Goals (SDGs) advocated by the United Nations.

[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. [Example]

[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 components contained in the compositions of each example and comparative example, and Table 2 shows the % by mass of the components contained in the compositions of 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: Mimasu Kashiwa Shoten's persimmon tannin paint Mayonnaise: Contains vinegar: 7ml (6.5%), 1 egg yolk: 20g (18.7%), vegetable oil: 80ml (72.7%). The mayonnaise was prepared as follows: First, the above ingredients were returned to room temperature, and half of the vegetable oil was gradually added to the egg yolk containing lecithin while mixing until the mixture became cloudy. Then, vinegar was added and mixed. Finally, the remaining half of the vegetable oil was gradually added and mixed to obtain the 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), and 2-propanol were calculated as having a concentration of 100%. Furthermore, in Tables 1 and 2, the numbers of carbon atoms in 2-propanol (C3) and peppermint oil (C10) indicate the respective numbers of carbon atoms.

[0069] [Table 1]

[0070] [Table 2]

[0071] [Preparation of Composition] (Examples 1 to 10 and 13 to 23) Persimmon tannin paint (polyphenols), mayonnaise, soybean lecithin, 2-propanol (organic solvent, containing 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 a liquid composition. 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] Examples 11 and 12 In Examples 11 and 12, 2-propanol was not added, and mint 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 the composition. The mint oil has 10 to 40 carbon atoms.

[0073] [Particle size measurement of composition] The particle size distribution of the micelles in the composition was measured using the light scattering method with the aforementioned 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] [Sample preparation] In Examples 1 to 23, the composition was applied to a substrate of cellulose cloth paper (JK Wiper (registered trademark) 150S (manufactured by Nippon Paper Crecia Co., Ltd.)), impregnated tightly onto both sides of kraft paper, and heat-treated under the heat-treatment conditions shown in Table 2 to obtain samples impregnated with the composition.

[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 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 to obtain samples impregnated with each component.

[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) = BA Here, "A" indicates the mass (g) of the kraft paper before impregnation, and "B" indicates the mass (g) of the sample impregnated with the composition after heat treatment. Note that in Comparative Example 2, the solid composition application amount was negative because the amount of water contained in the kraft paper that had evaporated was large even before the composition was applied.

[0079] [Evaluation of water absorption] The water absorption of the prepared samples was evaluated by the following procedure. The mass of each sample, measuring 150 mm x 150 mm, was measured. A Pax Naturon (registered trademark) kitchen sponge manufactured by Taiyo Yushi was cut into a size of 6 cm x 10.5 cm x 3 cm using a cutter. 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.). Any remaining water droplets on the sample surface were then 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 prepared samples were evaluated for the state of oil transfer as follows. First, the sample was sandwiched between two sheets of kraft paper made of virgin pulp, and a 10 cm square metal plate was placed on top of it. A weight was then placed on top of that, and the sample was then placed at a 10 cm 2 The sandwiched kraft paper was then visually inspected to see if oil had soaked into it and formed stains. 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, after preparing the compositions, they were left as is for 24 hours. If the composition separated into two layers or precipitated after that, it was deemed unstable and rated "C." If the apparent viscosity increased without clear separation such as precipitation and the viscosity decreased upon further stirring, it was rated "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 "A."

[0082] [Evaluation of the appearance of water-resistant cellulose cloth paper (water-resistant paper)] The prepared samples were evaluated as "uneven" if color unevenness due to the impregnated composition was clearly visible, and as "uniform" if not.

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

[0084] The water absorption amounts of Examples 1 to 3, in which a composition containing persimmon tannin paint (polyphenols), mayonnaise (oil, egg yolk, and vinegar), and an organic solvent was applied, and Example 4, in which a composition containing persimmon tannin paint and mayonnaise was applied, were lower than that of Comparative Example 1, in which only kraft paper was used, confirming improved water resistance. Similarly, improved water resistance was confirmed in Example 5, in which a persimmon tannin paint, soybean lecithin, an organic solvent, and a drying oil were applied. The water absorption amounts of Comparative Examples 2 to 5, in which a composition lacking either persimmon tannin paint (polyphenols), mayonnaise (egg yolk lecithin), soybean lecithin, or a drying oil was applied, were lower than those of Comparative Example 1 but higher than those of Examples 1 to 6. In Comparative Example 5, the persimmon tannin paint and the drying oil separated, so the composition had 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 a relatively short drying time, 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 if the F / L value 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. That is, Examples 10 and 23 have a relatively high content of oil and fat components such as mayonnaise or perilla oil. That is, F It is believed that the value of / P became too large, the viscosity increased, and the composition could not be properly impregnated, resulting in the transfer of oil. F It was confirmed that it is better to set the value of / P to be smaller than 25. Note that diluting the composition with water may be considered to properly impregnate the composition, but this is thought to result in a decrease in the content P of polyphenols, which would result in a decrease in water repellency.

[0088] Next, the "stability of the paint" was evaluated. As a result, the evaluation was "B" in Examples 17, 18, 21, and 22, and "A" in the other examples. In Examples 18, 21, and 22, the F / L value was too small, that is, the lecithin content was too low, so the stability of the paint was evaluated as "B". Also, in Example 17, the F / L value was too large, that is, the lecithin content was too high, so the stability of the paint was evaluated as "B". Therefore, from the viewpoint of ensuring the stability of the paint, it was confirmed that the F / L value should be greater than 5 and less than 150. That is, it was found that the composition can ensure the stability of the paint by satisfying the formula (1) "5 < F / L < 150".

[0089] Next, the "appearance of the water-resistant paper" was evaluated. As a result, it was "non-uniform" in Examples 11, 12, 14, 18, 21, and 22, and no color unevenness due to the composition was visually observed in the other examples. In Example 11, "peppermint oil" was used as the organic solvent instead of 2-propanol. In Example 11, although sufficient water resistance could be obtained, the "appearance of the water-resistant paper" became non-uniform because the viscosity increased. Also, in Example 12, although it became easier to penetrate compared to Example 11 by diluting twice with water, the "appearance of the water-resistant paper" was non-uniform. When 2-propanol was used, excellent water resistance could be obtained even when diluted four times with water. In Example 14, the viscosity increased because the content of 2-propanol was relatively low, and the "appearance of the water-resistant paper" became non-uniform because the invasiveness of the paint into the kraft paper was low due to the small amount of oil component. Also, in Examples 18, 21, and 22, the viscosity increased because the lecithin content was too high, and the "appearance of the water-resistant paper" became non-uniform. Therefore, the contents of 2-propanol, peppermint oil, and lecithin are considered to affect the "appearance of the water-resistant paper".

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

[0091] Here, the content P of polyphenols can be determined as follows. First, 550% ethanol is added to 0.2 to 0.6 g of the composition sample, followed by ultrasonic irradiation and centrifugation. Then, it is filtered to obtain a test solution. Also, 1 ml of a catechin standard solution is prepared. For the catechin standard solution, 0.5 ml of Folin-Ciacalteu reagent and 5 ml of 0.4 mol / L aqueous sodium carbonate solution are added, and after leaving it standing for 25 minutes in an environment at 30°C, the content P of polyphenols is specified by measuring at a wavelength of 660 nm using an ultraviolet-visible spectrophotometer. The catechin standard solution is a standard sample composed of (+)-catechin dissolved and diluted 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.

[0092] The lecithin content (L) can be determined using the following method. First, a 2:1 mixture of chloroform and methanol is added to 1.2 g of a sample of the composition 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 this, 5 ml of molybdenum blue coloring reagent, 1 ml of 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 with a molecular structure without CH groups, 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 waterproofing a substrate, comprising: Contains polyphenols, fats and oils, and lecithin, 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 (wt%) of the fat or oil in the composition, L represents the content (wt%) of the lecithin in the composition, and P represents the content (wt%) of the polyphenols in the composition.

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

3. 10. The composition of claim 1, A composition wherein, in formula (1), F / L is greater than 20.

4. 10. The composition of claim 1, The F content is 2 to 50 mass %, The L is 0.05 to 6 mass %, The composition, wherein the P is 0.2 to 4 mass%.

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

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

7. 10. The composition of claim 1, The composition further comprises an alcohol, The composition, wherein the alcohols have 2 to 40 carbon atoms in their molecular structure.

8. 10. The composition of claim 1, The composition comprises egg yolk containing the lecithin and acetic acid.

9. A composition for waterproofing a substrate, comprising: Contains polyphenols, fats and oils, and lecithin, The composition comprises 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, The substrate is a water-resistant substrate that is a cellulose cloth paper.

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

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

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

Images