Molding, method for manufacturing the same, method for manufacturing fiber-reinforced plastic product and method for improving antibacterial or antiviral property

Abstract

To provide a molding in which coloration is suppressed, while having antibacterial or antiviral property.SOLUTION: A molding 100 contains a calcium compound 104 and a resin, and has a salt of inositol phosphate 102 and a metal element (silver and zinc) 103 on a surface 101, wherein a carried amount of silver on the surface 101 is 10.0 μg / cm2 or less, and a carried amount of zinc on the surface is 1.0 μg / cm2 or more.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present disclosure relates to a molded body, a method for manufacturing the same, a method for manufacturing a fiber-reinforced plastic product, and a method for improving antibacterial or antiviral properties, etc. [Background technology]

[0002] In recent years, with the increasing trend toward hygiene, plastic products with antibacterial properties have been developed. For example, a method has been proposed in which a material that exhibits antibacterial properties (hereinafter referred to as "antibacterial material") is mixed into a resin to impart antibacterial properties to plastic products.

[0003] For example, Patent Document 1 discloses an antibacterial material characterized in that antibacterial metal particles such as silver microparticles are embedded in a partially exposed and dispersed state on at least a portion of the surface of a substrate such as a plastic product.

[0004] Patent Document 2 discloses a resin bathtub that is manufactured by adding and mixing an antibacterial agent into a resin material in advance, then adding and mixing a filler, and then molding the mixed material.

[0005] Patent Document 3 discloses an antibacterial member in which an antibacterial material is attached to the surface of a substrate, and in which a resin coating film is formed on the surface to which the antibacterial material is attached to such an extent that antibacterial properties remain.

[0006] Fiber reinforced plastic (also known as FRP) is a known plastic material that is strong yet lightweight, rust-resistant, and rot-resistant. Fiber reinforced plastic is a composite material containing fiber materials such as glass fiber and carbon fiber and resin materials (plastics), and demand for it is increasing in the market. For example, fiber reinforced plastic is used not only as components for vehicles and aircraft, but also as parts of everyday items.

[0007] Patent Documents 4 to 6 disclose molded articles of fiber-reinforced plastics or the like that have antibacterial or antiviral properties. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-319109 [Patent Document 2] Japanese Patent Application Publication No. 11-58555 [Patent Document 3] Japanese Patent Application Laid-Open No. 2009-40729 [Patent Document 4] Japanese Patent Publication No. 2022-117428 [Patent Document 5] Japanese Patent Publication No. 2023-081534 [Patent Document 6] International Publication No. 2023 / 100411 Summary of the Invention [Problem to be solved by the invention]

[0009] However, in plastic products in which antibacterial properties are imparted by kneading an antibacterial material into a resin, as in the above-mentioned Patent Documents 1 to 3, the antibacterial material tends to easily peel off or leach out, so the duration of the antibacterial properties is extremely short. Furthermore, once such plastic products lose their antibacterial properties, it is difficult to impart antibacterial properties again, which results in a short product life cycle.

[0010] Furthermore, products that exhibit antibacterial or antiviral properties due to metals or metal ions may exhibit a color derived from the metal or metal ions. In particular, products having antibacterial or antiviral properties are required to suppress coloration derived from metals or metal ions in order to impart a sense of cleanliness and make stains easier to see.

[0011] Therefore, an object of the present invention is to provide a molded article that has antibacterial or antiviral properties and is suppressed from being discolored, and a method for producing the same. [Means for solving the problem]

[0012] A molded article according to one embodiment of the present invention contains a calcium compound and a resin, has a salt of inositol phosphate with silver and zinc on its surface, and has a silver loading on the surface of 10.0 μg / cm 2 and the amount of zinc carried on the surface is 1.0 μg / cm 2 That's all.

[0013] Because this molded article has the above-mentioned configuration, it exhibits excellent antibacterial and / or antiviral properties. The antibacterial or antiviral properties are thought to be due to the salt of inositol phosphate with silver and zinc, and / or the silver ions and zinc ions eluted from the salt. Because the molded article contains a calcium compound, it is presumed that the salt interacts with the calcium compound and is stably retained on the surface of the molded article. Furthermore, because the amount of silver and zinc supported on the surface is within a specific range, surface discoloration due to metal ions is suppressed while maintaining sufficient antibacterial or antiviral properties.

[0014] A method for producing a molded body according to one embodiment of the present invention includes step A1 of applying inositol phosphate to at least a portion of the surface of a molded body of a resin composition containing a calcium compound and a resin, and step A2 of applying silver ions and zinc ions to the surface to which the inositol phosphate has been applied, wherein the color difference between the surface of the molded body after step A2 and the surface of the molded body before step A1 is 3.2 or less, and at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the molded body after step A2 is 2.0 or more, based on the surface of the molded body before step A1.

[0015] According to this manufacturing method, a molded article can be easily manufactured that has sufficient antibacterial or antiviral properties while suppressing surface discoloration caused by metal ions.

[0016] A method for producing a fiber-reinforced plastic product according to one embodiment of the present invention includes step B1 of applying inositol phosphate to the surface of an outer layer of a fiber-reinforced plastic having an outer layer containing a calcium compound and a resin on at least a portion of the surface, and step B2 of applying silver ions and zinc ions to the surface to which the inositol phosphate has been applied, wherein the color difference between the surface of the outer layer after step B2 and the surface of the outer layer before step B1 is 3.2 or less, and at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the outer layer after step B2 is 2.0 or more, relative to the surface of the outer layer before step B1.

[0017] According to this manufacturing method, it is possible to easily manufacture a fiber-reinforced plastic product that has sufficient antibacterial or antiviral properties while suppressing surface discoloration caused by metal ions.

[0018] A method for improving the antibacterial or antiviral properties of a molded article that contains a calcium compound and a resin and has inositol phosphate on its surface, or imparting antibacterial or antiviral properties to the molded article, according to one embodiment of the present invention, includes a step C1 of imparting silver ions and zinc ions to the surface having inositol phosphate, wherein the amount of silver supported on the surface of the molded article after the step C1 is 10.0 μg / cm. 2 or less, and the amount of zinc supported on the surface of the molded body after step C1 is 1.0 μg / cm 2 That's all.

[0019] According to this method, it is possible to extremely simply impart or improve antibacterial or antiviral properties to a molded article that has lost or has reduced antibacterial or antiviral properties, while suppressing surface discoloration derived from metal ions. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide a molded article that has antibacterial or antiviral properties and is suppressed from being discolored, and a method for producing the same. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 2 is a schematic cross-sectional view of the molded body of the present embodiment. [Figure 2] 1 is a schematic cross-sectional view of one aspect of the surface of a molded body of the present embodiment. [Figure 3] 1 is a schematic cross-sectional view of a fiber-reinforced plastic product according to an embodiment of the present invention. [Figure 4] 1 is a schematic cross-sectional view showing one step in an example of a method for producing a molded body according to the present embodiment. [Figure 5] FIG. 4 is a schematic cross-sectional view showing another step in an example of the method for producing a molded body according to the present embodiment. [Figure 6] 1 is a schematic cross-sectional view showing one step in an example of a method for producing a fiber-reinforced plastic product according to the present embodiment. FIG. [Figure 7] FIG. 4 is a schematic cross-sectional view showing another step in an example of the method for producing a fiber-reinforced plastic product of the present embodiment. [Figure 8] FIG. 10 is a schematic cross-sectional view showing yet another step in an example of the method for producing a fiber-reinforced plastic product of the present embodiment. [Figure 9]This figure shows the antibacterial activity of each sample against E. coli. In the figure, for the notations "Ag(X)-FRP," "Zn(Y)-FRP," and "Ag(X) / Zn(Y)-FRP," X represents the concentration (unit: mM) of the silver nitrate aqueous solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate aqueous solution used to prepare the sample. The value shown above each bar is the antibacterial activity value. [Figure 10] This figure shows the antibacterial activity of each sample against S. aureus. In the figure, for the notations "Ag(X)-FRP," "Zn(Y)-FRP," and "Ag(X) / Zn(Y)-FRP," X represents the concentration (unit: mM) of the silver nitrate aqueous solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate aqueous solution used to prepare the sample. The value shown above each bar is the antibacterial activity value. [Figure 11] This figure shows the antiviral activity of each sample. In the figures, for the notations "Ag(X)-FRP," "Zn(Y)-FRP," and "Ag(X) / Zn(Y)-FRP," X represents the concentration (unit: mM) of the silver nitrate aqueous solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate aqueous solution used to prepare the sample. The value shown above each bar graph is the antiviral activity value. [Figure 12] This figure shows the CIE lightness (L*) and color coordinates (a*, b*) of each sample over time in the L*a*b* color system. In the notation "Ag(X)-FRP" and "Ag(X) / Zn(Y)-FRP," X represents the concentration (unit: mM) of the silver nitrate aqueous solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate aqueous solution used to prepare the sample. [Figure 13] This figure shows the color difference of each sample over time. In the figures, for the notations "Ag(X)-FRP," "Zn(Y)-FRP," and "Ag(X) / Zn(Y)-FRP," X represents the concentration (unit: mM) of the silver nitrate aqueous solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate aqueous solution used to prepare the sample. [Figure 14]This figure shows the relationship between the concentrations of silver nitrate and zinc nitrate solutions and the amounts of silver and zinc supported in the outer layer as measured by ICP-AES. In the notations "Ag(X)-FRP," "Zn(Y)-FRP," and "Ag(X) / Zn(Y)-FRP," X represents the concentration (unit: mM) of the silver nitrate solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate solution used to prepare the sample. The values ​​shown above each bar indicate the amount of each metal ion supported. [Figure 15] This figure shows the relative cell proliferation rate of each sample. In the figure, in the notations "Ag(X)-FRP," "Zn(Y)-FRP," and "Ag(X) / Zn(Y)-FRP," X represents the concentration (unit: mM) of the silver nitrate aqueous solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate aqueous solution used to prepare the sample. [Figure 16] This figure shows the relationship between the concentrations of silver nitrate and zinc nitrate solutions and the amounts of silver and zinc supported in the outer layer as measured by ICP-AES. In the notation "Ag(X) / Zn(Y)-FRP" in the figure, X represents the concentration (unit: mM) of the silver nitrate solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate solution used to prepare the sample. The values ​​shown above each bar represent the amount of each metal ion supported. [Figure 17] This figure shows the relationship between the concentrations of silver nitrate and zinc nitrate solutions and the amounts of silver and zinc supported in the outer layer as measured by ICP-AES. In the notation "Ag(X) / Zn(Y)-FRP" in the figure, X represents the concentration (unit: mM) of the silver nitrate solution used to prepare the sample, and Y represents the concentration (unit: mM) of the zinc nitrate solution used to prepare the sample. The values ​​shown above each bar represent the amount of each metal ion supported. DETAILED DESCRIPTION OF THE INVENTION

[0022] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the drawings as necessary, but the present invention is not limited to this, and various modifications are possible without departing from the spirit of the present invention. In the drawings, the same elements are given the same reference numerals, and redundant explanations will be omitted. Furthermore, positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios of the drawings are not limited to those shown in the drawings.

[0023] [Molded body] 1 is a schematic cross-sectional view of a molded article of this embodiment. A molded article 100 of this embodiment contains a calcium compound and a resin, and has a salt of inositol phosphate with silver and zinc on a surface 101. Because of this configuration, molded article 100 has at least one of excellent antibacterial and antiviral properties. Furthermore, because it can impart antibacterial properties against bacteria, it can inhibit the formation of biofilms produced by bacterial proliferation. Furthermore, it can also inhibit the proliferation of mold, which uses biofilms as a foothold to attach. Therefore, molded article 100 is further inhibited from attracting dirt, potentially reducing the frequency of maintenance, such as cleaning.

[0024] In this specification, "antibacterial" refers to the property of inhibiting bacterial growth or killing bacteria. Therefore, the molded article of this embodiment may be able to inhibit bacterial growth or kill bacteria on its surface. The antibacterial activity value defined in the examples described below can be used as an index of the antibacterial properties of the molded article. The molded article of this embodiment preferably has an antibacterial activity value of 2.0 or more, more preferably an antibacterial activity value of 2.5 or more.

[0025] In addition, in this specification, "antiviral" refers to the property of reducing the infectivity titer of a virus or suppressing an increase in the infectivity titer of a virus. Therefore, the molded article of this embodiment may be able to suppress the growth of infectious viruses or kill infectious viruses on its surface. As an index of the antiviral properties of the molded article, the antiviral activity value defined in the examples described below can be used. The molded article of this embodiment preferably has an antiviral activity value of 2.0 or more, more preferably an antiviral activity value of 3.0 or more.

[0026] Each component of the molded body 100 will be described in detail below. The molded body of this embodiment has sufficient antibacterial or antiviral properties while suppressing coloration by controlling the amount of silver and zinc carried on the surface within a predetermined range, and by controlling the color difference of the surface of the molded body before and after carrying metal ions, and the antibacterial activity value or antiviral activity value of the molded body within a predetermined range.

[0027] (Calcium compounds and resins) The molded article 100 contains a resin and a calcium compound. The molded article 100 may be one in which a calcium compound is dispersed in a resin (synonymous with a polymer) as a matrix material. The molded article 100 may be a molded article of a resin composition containing a calcium compound and a resin, or may be a cured product of a resin composition containing a calcium compound and a resin. Because the molded article contains a resin, the calcium compound is firmly held in the molded article without easily being released. In this specification, the term "resin" includes not only resin before curing and / or crosslinking, but also cured and / or crosslinked resin.

[0028] Resins contained in the molded body 100 include, but are not limited to, thermoplastic resins and thermosetting resins. From the viewpoint of improving the strength of the molded body 100, it is preferable that the molded body 100 contains a thermosetting resin. Examples of thermosetting resins that can be contained in the molded body 100 include unsaturated polyester resins, phenolic resins, polyamide resins, epoxy resins, vinyl ester resins, polyimide resins, urea resins, and melamine resins. Examples of thermoplastic resins that can be contained in the molded body 100 include acrylic resin, acrylonitrile butadiene styrene (ABS) resin, polyethylene resin, polycarbonate resin, polyamide resin, and polypropylene resin.

[0029] The molded body 100 preferably contains any one of an unsaturated polyester resin, a vinyl ester resin, and a mixed resin of an unsaturated polyester resin and a vinyl ester resin. This embodiment tends to increase the strength of the molded body and more reliably prevent calcium compounds from being released from the molded body. The mixing ratio of each resin in the mixed resin is not particularly limited. The above resins may be used alone or in combination of two or more.

[0030] The calcium compound that can be contained in the molded body 100 is not particularly limited as long as it is a compound containing calcium element. The molded body 100 can contain various calcium compounds. From the viewpoint of further strengthening the interaction between the inositol phosphate and the calcium compound on the surface of the molded body 100, the calcium compound is preferably calcium ions (more specifically, Ca 2+ From the same viewpoint, the calcium compound is more preferably an inorganic salt of calcium.

[0031] Examples of inorganic salts of calcium that can be contained in the molded body 100 include calcium phosphate, calcium hydrogen phosphate, calcium sulfate, calcium carbonate, calcium oxide, and calcium silicate. Examples of calcium phosphate include tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, and hydroxyapatite (Ca 10(PO4)6(OH)2). Examples of calcium hydrogen phosphate include calcium monohydrogen phosphate and calcium dihydrogen phosphate. Examples of organic salts of calcium include calcium acetate.

[0032] The calcium compound may be the above-mentioned compound in which part of the calcium element has been substituted with magnesium element.

[0033] Preferred embodiments of the calcium compound include calcium carbonate, calcium sulfate, calcium oxide, and hydroxyapatite. This embodiment further strengthens the interaction between the inositol phosphate and the calcium compound on the surface of the molded body 100. From the same viewpoint, more preferred embodiments of the calcium compound include calcium carbonate and hydroxyapatite. The calcium compound is more preferably calcium carbonate.

[0034] The molded body 100 may contain one type of the calcium compounds listed above alone, or may contain two or more types in combination.

[0035] The calcium compound may be contained as particles. The particle size of the calcium compound particles is not particularly limited, but is preferably equal to or less than the average thickness of the molded body 100, more preferably equal to or less than one-fifth of the average thickness of the molded body, and even more preferably equal to or less than one-tenth of the average thickness of the molded body. More specifically, the particle size of the calcium compound particles is preferably 1 μm or more and 400 μm or less, more preferably 5 μm or more and 200 μm or less, and even more preferably 10 μm or more and 100 μm or less. The particle size of the calcium compound particles may be 10 μm or more and 50 μm or less.

[0036] The particle size of the calcium compound particles is determined by calculating the circle-equivalent diameters of three or more calcium compound particles in an image of a cross section of a molded body 100, as shown in FIG. 2, observed with a scanning electron microscope (SEM) and then calculating the average value. The above particle size calculation method preferably involves arithmetic averaging of the circle-equivalent diameters of ten or more calcium compound particles. In this embodiment, when calcium compound fine particles with a particle size of approximately several μm are used to produce a molded body, the calcium compound fine particles typically tend to aggregate to form aggregate particles with a particle size of approximately 10 to 100 μm. In such cases, the calcium compound particles observed with SEM are such aggregates, and the average particle size of the aggregates is used as the particle size of the calcium compound. However, the above description is not intended to exclude from this embodiment a case where the calcium compound fine particles are dispersed within the molded body without forming aggregates. To confirm that the calcium compound observed with SEM is an aggregate of calcium compound fine particles, the calcium compound can be observed with a transmission electron microscope (TEM), for example.

[0037] The average thickness of the molded body is determined by measuring the thickness of the molded body at three or more points in an image of a cross section of the molded body as shown in Figure 1 observed with an optical microscope or the like, and calculating the arithmetic mean. More specifically, the average thickness of the molded body is determined as follows. First, the molded body is cut in a direction approximately parallel to its thickness direction, and the exposed cross section is observed from a direction approximately perpendicular to the cross section. A scanning electron microscope (SEM), a transmission electron microscope (TEM), or an optical microscope can be used for the observation. In the obtained observation image, the thickness of the molded body is measured at three or more locations, preferably five locations, and more preferably ten locations. The arithmetic mean of the obtained values ​​is calculated, and this value is defined as the average thickness of the molded body.

[0038] The molded body 100 may contain, as components other than the calcium compound and resin, conventionally known fillers (excluding calcium compounds), curing agents for curing resins, and additives such as paints, etc. Examples of such fillers include oxides such as titanium oxide and silicon dioxide.

[0039] The resin and calcium compound contents in the molded body 100 are not particularly limited. The calcium compound may be contained in an amount of 20% by mass or more and 60% by mass or less, or may be contained in an amount of 30% by mass or more and 60% by mass or less, based on the total mass of the molded body. The resin may be contained in an amount of 5.0% by mass or more and 60% by mass or less, or 10% by mass or more and 50% by mass or less, based on the entire molded body. The filler other than the calcium compound may be contained in an amount of 0% by mass or more and 10% by mass or less, or 1.0% by mass or more and 8.0% by mass or less, based on the entire molded body.

[0040] (Surface of molded body) The molded body 100 has, on its surface 101, a salt of inositol phosphate with silver and zinc.

[0041] Inositol phosphate refers to inositol (1,2,3,4,5,6-cyclohexanehexaol) in which one or more of the six hydroxyl groups have been substituted with a phosphate group (-OP(=O)(OH)2). Specific examples of inositol phosphate include inositol monophosphate, inositol diphosphate, inositol triphosphate, inositol tetraphosphate, inositol pentaphosphate, and inositol hexaphosphate (compounds in which one, two, three, four, five, and six hydroxyl groups of inositol have been substituted with phosphate, respectively). Inositol phosphate has many OH groups (OH groups directly bonded to the cyclohexane ring and OH groups in the phosphate group) and can therefore coordinate to metal atoms or metal ions at multiple coordination sites.

[0042] Therefore, in this specification, the expression "having a salt of inositol phosphate with silver and zinc" refers not only to the case where a species in which both silver and zinc are coordinated to one inositol phosphate is present on the surface 101, but also to the case where both a species in which silver is coordinated to one or more inositol phosphates and a species in which zinc is coordinated to one or more inositol phosphates are present on the surface 101. Thus, the molded article 100 may have, on the surface 101, a species in which both silver and zinc are coordinated to one inositol phosphate, or may have, on the surface 101, both a species in which silver is coordinated to one or more inositol phosphates and a species in which zinc is coordinated to one or more inositol phosphates.

[0043] The molded article 100 contains a calcium compound and a resin, and has a salt of inositol phosphate with silver and zinc on its surface 101, thereby exhibiting excellent antibacterial or antiviral properties. It is believed that this antibacterial or antiviral property is derived from the salt of inositol phosphate with silver and zinc held on the surface 101 and / or metal ions eluted from the salt. Furthermore, in the molded article of this embodiment, a strong chemical interaction between inositol phosphate and the calcium compound on the surface 101 is believed to partially suppress elution of the salt of inositol phosphate with silver and zinc. This tends to result in the antibacterial or antiviral properties of the molded article of this embodiment remaining effective for a long period of time. The factors that enable the molded article of this embodiment to exhibit antibacterial or antiviral properties and to maintain the antibacterial or antiviral properties for a long period of time are not limited to those described above. Furthermore, the above description does not in any way limit the duration of the antibacterial or antiviral properties of the molded article of this embodiment.

[0044] The molded body 100 only needs to have a salt of inositol phosphate with silver and zinc present on the surface 101. The form of the salt on the surface 101 is not particularly limited, and a schematic cross-sectional view of one form is shown in FIG.

[0045] In FIG. 2, molded body 100 contains calcium compound 104 such that at least a portion of calcium compound 104 is exposed on surface 101. Inositol phosphate has the property of coordinating with calcium element (calcium metal and / or calcium ion), and therefore inositol phosphate 102 is coordinated to the exposed calcium compound 104 on surface 101. Inositol phosphate also has the property of coordinating with silver and zinc, and has a coordination site other than the coordination site coordinated to calcium compound 104. Therefore, metal element 103 (silver and / or zinc) is further coordinated to inositol phosphate 102 coordinated to calcium compound 104. Note that in FIG. 2, inositol phosphate 102 and metal element 103 form a salt, and the salt can also be considered to be supported on calcium compound 104.

[0046] Thus, in one aspect of the molded article of the present embodiment, on the surface 101, the metal element 103 is held by the calcium compound 104 via the inositol phosphate 102.

[0047] As described above, since the salt of inositol phosphate with silver and zinc is retained on the surface 101 of the molded body 100, the dissociation constant of the salt of inositol phosphate with silver and zinc, or the metal ion, falls within a suitable range, and as a result, it is presumed that the molded body 100 can exhibit sufficient antibacterial or antiviral properties for a long period of time.

[0048] However, although the presence of a salt of inositol phosphate with silver and zinc on surface 101 can be easily detected by surface analysis or the like, it is not necessarily easy to detect that the salt of inositol phosphate with silver and zinc is present in the manner shown in Figure 2. From this perspective, the salt of inositol phosphate with silver and zinc does not necessarily have to be present on surface 101 in the manner shown in Figure 2. For example, silver and zinc may be directly supported on surface 101, and such silver and zinc may interact with inositol phosphate.

[0049] The inositol phosphate contained in the molded body 100 is not particularly limited, and may be inositol monophosphate, inositol diphosphate, inositol triphosphate, inositol tetraphosphate, inositol pentaphosphate, or inositol hexaphosphate.

[0050] The inositol phosphate preferably has 3 to 6 phosphate groups. According to this embodiment, the interaction between the inositol phosphate and the calcium compound and / or the metal element (silver and zinc) is strengthened, which tends to further improve the antibacterial or antiviral properties of the molded body 100. That is, the inositol phosphate is preferably one or more selected from the group consisting of inositol triphosphate, inositol tetraphosphate, inositol pentaphosphate, and inositol hexaphosphate. From the same viewpoint, the inositol phosphate more preferably has 4 to 6 phosphate groups, even more preferably has 5 to 6 phosphate groups, and particularly preferably has 6 phosphate groups.

[0051] The three-dimensional structure of inositol to which the phosphate group in inositol phosphate is bonded is not particularly limited, and examples thereof include myo-inositol, scyllo-inositol, muco-inositol, chiro-inositol, neo-inositol, allo-inositol, epi-inositol, and cis-inositol. The inositol phosphate is preferably inositol phosphate derived from myo-inositol (i.e., inositol phosphate in which at least one hydroxyl group of myo-inositol is substituted with a phosphate group). According to this embodiment, the balance between the interaction between the inositol phosphate and the calcium compound and the interaction between the inositol phosphate and the silver and zinc is further improved, which tends to further improve the antibacterial or antiviral properties of the molded article 100.

[0052] Preferred embodiments of inositol phosphates include myo-inositol having 3 to 6 phosphate groups bound thereto (3 to 6 of the hydroxyl groups of myo-inositol are phosphorylated; the same applies hereinafter in this paragraph), more preferably myo-inositol having 4 to 6 phosphate groups bound thereto, even more preferably myo-inositol having 5 to 6 phosphate groups bound thereto, and even more preferably myo-inositol having 6 phosphate groups bound thereto. Another preferred embodiment of the inositol phosphate is inositol hexaphosphate, particularly phytic acid (myo-inositol-1,2,3,4,5,6-hexaphosphate).

[0053] The molded body 100 may contain one type of the above inositol phosphate alone, or may contain two or more types in combination.

[0054] On the surface 101, silver and zinc form a salt with inositol phosphate. As described above, it is believed that the salt and / or metal ions eluted from the salt cause the molded body 100 to exhibit antibacterial or antiviral properties. The fact that the surface 101 has a salt of inositol phosphate with silver and zinc can also be said to mean that the surface 101 has inositol phosphate ions, silver ions, and zinc ions.

[0055] The amount of silver carried on the surface 101 is 10.0 μg / cm 2 or less, preferably 0.1 to 10.0 μg / cm 2 and more preferably 0.3 to 9.0 μg / cm 2 and more preferably 0.5 to 8.0 μg / cm 2 and even more preferably 0.8 to 7.0 μg / cm 2 and even more preferably 1.0 to 5.0 μg / cm 2 and particularly preferably 1.1 to 3.0 μg / cm 2 The silver loading is 2.5 μg / cm in this range. 2 Below, 2.0μg / cm2 or less, or 1.5 μg / cm 2 It may be the following:

[0056] The amount of zinc supported on the surface 101 is 1.0 μg / cm 2 or more, preferably 1.0 μg / cm 2 ~500mg / cm 2 and more preferably 5.0 μg / cm 2 ~300mg / cm 2 and more preferably 8.0 μg / cm 2 ~100mg / cm 2 and even more preferably 10 μg / cm 2 ~80mg / cm 2 and even more preferably 12 μg / cm 2 ~50mg / cm 2 and particularly preferably 13 μg / cm 2 ~5.0mg / cm 2 or 15 μg / cm 2 ~500μg / cm 2 The zinc loading is 10 mg / cm in this range. 2 Below 1.0mg / cm 2 Below, 100μg / cm 2 Below, 80μg / cm 2 Below, 50μg / cm 2 Below, 40μg / cm 2 Below 30μg / cm 2 or less, or 35 μg / cm 2 It may be the following:

[0057] The ratio of the amount of supported silver and zinc on the surface 101 is not particularly limited, but the molar ratio of the amount of supported zinc to the amount of supported silver (Zn / Ag) is, for example, 3 to 10,000, preferably 4 to 5,000, and more preferably 5 to 1,000, or 6 to 500. The molar ratio of the amount of supported zinc to the amount of supported silver (Zn / Ag) may be 300 or less, 200 or less, 100 or less, 50 or less, 20 or less, or 10 or less.

[0058] When the amount of silver carried on the surface 101 is equal to or less than the upper limit, coloration of the molded body tends to be suppressed. Furthermore, when the amount of silver carried is equal to or more than the lower limit, the antibacterial or antiviral properties of the molded body are further improved.

[0059] When the amount of zinc supported on the surface 101 is equal to or less than the above upper limit, the amount of silver supported indirectly increases, and the antibacterial or antiviral properties of the molded article tend to be further improved. This is thought to be because when silver and zinc are supported on the surface 101, silver and zinc compete with each other for coordination with inositol phosphate. Furthermore, when the amount of zinc supported is equal to or greater than the above lower limit, the antibacterial or antiviral properties of the molded article tend to be further improved and discoloration of the molded article tends to be suppressed. This is thought to be because the support of zinc provides the antibacterial or antiviral properties derived from zinc as well as the whitening effect derived from zinc.

[0060] In this way, in the molded body of this embodiment, by setting the amount of silver supported to a predetermined amount or less, discoloration due to silver is suppressed, and by setting the amount of zinc supported to a predetermined amount or more, antibacterial or antiviral properties derived from zinc are exhibited, and discoloration is further suppressed by the whitening effect derived from zinc.

[0061] The supported amounts of silver and zinc can be measured by washing the surface of the molded body with an acid (e.g., a strong acid such as nitric acid) and measuring the resulting washings using an inductively coupled plasma atomic emission spectroscopy (ICP-AES). More specifically, the methods described in the Examples can be mentioned. Alternatively, the amounts can be measured by surface analysis techniques such as EDS (energy dispersive X-ray spectroscopy), AES (Auger electron spectroscopy), and XPS (X-ray photoelectron spectroscopy).

[0062] (Physical properties and effects of molded products) The molded body 100 has antibacterial or antiviral properties while being suppressed from discoloration. As described above, when attempting to improve the antibacterial or antiviral properties, particularly by supporting silver, discoloration may occur on the surface of the molded body. Therefore, in order to impart antibacterial or antiviral properties to the molded body 100 while suppressing discoloration, it is preferable to strike a balance between the antibacterial or antiviral properties and the suppression of discoloration by setting them within an appropriate range.

[0063] The color difference between surface 101 of molded body 100 and the surface of a reference molded body having the same configuration as molded body 100 except that it does not have a salt of inositol phosphate with silver and zinc on its surface is preferably 3.2 or less. The color difference is preferably 0 to 3.2, more preferably 0.5 to 3.0, even more preferably 0.7 to 2.8, and even more preferably 0.8 to 2.0. The color difference may be measured immediately after producing molded body 100 and the reference molded body, or may be measured one day, one week, two weeks, or three weeks later.

[0064] The above color difference is L * a * b * It is a color difference in a color system, and may be measured in accordance with Japanese Industrial Standards (JIS Z 8723:2000 and JIS Z 8781-4:2013). Specifically, it may be measured by the method described in the examples.

[0065] The molded body 100 is preferably such that, with respect to a reference molded body having the same configuration as the molded body 100 except that it does not have a salt of inositol phosphate with silver and zinc on its surface, at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface 101 of the molded body 100 is 2.0 or more, and at least two of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses are 2.0 or more. It is more preferable that at least three of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses (for example, at least the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, and the antiviral activity value against non-enveloped viruses) are 2.0 or higher, and it is even more preferable that all of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses are 2.0 or higher. The activity value may preferably be 2.5 or higher, 3.0 or higher, 3.5 or higher, or 4.0 or higher. There is no particular upper limit to the activity value, but the activity value may be, for example, 10 or lower, or 8 or lower.

[0066] The antibacterial activity value and antiviral activity value may be measured in accordance with the Japanese Industrial Standards (JIS Z 2801:2010) and the International Standards (ISO 21702), respectively. Specifically, they may be measured by the method described in the Examples. In this specification, the Gram-negative bacterium may be, but is not limited to, E. coli. The Gram-positive bacterium may be, but is not limited to, S. aureus. The non-enveloped virus may be, but is not limited to, Feline calicivirus. The enveloped virus may be, but is not limited to, Influenza A virus.

[0067] Furthermore, in this specification, the phrase "the antibacterial activity value of the surface of a molded article against gram-negative bacteria is 2.0 or more" means that the antibacterial activity value measured using any bacteria known as gram-negative bacteria is 2.0 or more, and does not necessarily mean that the antibacterial activity value against all bacteria known as gram-negative bacteria is 2.0 or more. The same applies to expressions such as "the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses are 2.0 or more."

[0068] In addition to the advantageous effects of the molded body of this embodiment compared to conventional antibacterial plastic products such as zeolite-containing plastic products, metal microparticle-containing plastic products, and coated antibacterial plastic products, in addition to those described in Patent Documents 4 to 6, there is also the point that coloring is suppressed while the molded body has antibacterial or antiviral properties.

[0069] Furthermore, since the molded article of this embodiment does not simply have metal ions on its surface but also has salts of inositol phosphate with silver and zinc, it may be possible to achieve not only excellent antibacterial or antiviral properties but also sufficiently low cytotoxicity. More specifically, the molded article of this embodiment preferably has a relative cell proliferation rate M, as defined in the examples described below, of 70% or more, and more preferably 80% or more.

[0070] (Shape of molded body) The shape of the molded article of this embodiment is not particularly limited, and may be plate-like, spherical, cylindrical, or columnar, or may be a three-dimensional shape including a flat surface having irregularities. Furthermore, the molded article of this embodiment may be a final product itself, or may be one of the components that constitute the final product.

[0071] The molded article of this embodiment may be a combination of two or more different materials, like the fiber-reinforced plastic product of this embodiment described below. When the molded article of this embodiment is a combination of two or more different materials, it is sufficient that at least one of the materials contains a calcium compound and a resin and has a salt of inositol phosphate, silver, and zinc on its surface. Furthermore, in such a case, the surface having the salt of inositol phosphate, silver, and zinc does not necessarily have to be exposed on the surface of the molded article. For example, when the molded article is hollow, the inner surface of a component constituting the hollow portion of the molded article (i.e., the portion corresponding to the interior of the molded article) may have the salt of inositol phosphate, silver, and zinc.

[0072] The molded article of this embodiment does not need to have the salt of inositol phosphate, silver, and zinc on the entire surface of the molded article. As shown in Figures 1 and 2, the molded article of this embodiment may have the salt of inositol phosphate, silver, and zinc on only a portion of its surface. That is, the molded article of this embodiment has the salt of inositol phosphate, silver, and zinc on at least a portion of its surface. The proportion of the surface of the molded body that has the salt of inositol phosphate and silver and zinc is not particularly limited, and it is sufficient that the salt of inositol phosphate and silver and zinc is present in the part that should be particularly imparted with antibacterial or antiviral properties.

[0073] (Use of molded body) The molded article of this embodiment can be used in various applications, and is particularly preferably used in applications requiring antibacterial or antiviral properties. In one aspect, the molded article of this embodiment is used as an antibacterial or antiviral product or component. The molded article of this embodiment is suitable for use, for example, in interior components of vehicles, aircraft, buildings, and the like that may be frequently touched by multiple people, as well as in bathtubs and sanitary products that require high levels of hygiene. Examples of applications of the molded article of this embodiment include bathtubs, sanitary products, play equipment, vases, champagne coolers, portable toilet boxes, washing machine tubs, stationery, automobile steering wheels, door handles, food court trays and tables, station and park benches, and interior components of vehicles, aircraft, and buildings.

[0074] [Fiber reinforced plastic products] One aspect of the molded article of this embodiment is a fiber-reinforced plastic product. In this specification, this aspect is referred to as the "fiber-reinforced plastic product of this embodiment." FIG. 3 is a schematic cross-sectional view of the fiber-reinforced plastic product of this embodiment. The fiber-reinforced plastic product 200 of this embodiment includes a fiber-reinforced plastic layer 210 and an outer layer 220 provided on the fiber-reinforced plastic layer 210. The outer layer 220 is a layer containing a calcium compound and a resin. Furthermore, the outer layer 220 has, on its surface 221, a salt of inositol phosphate with silver and zinc (not shown in FIG. 3). Due to this configuration, the fiber-reinforced plastic product 200 has antibacterial or antiviral properties. Therefore, the fiber-reinforced plastic product of this embodiment can inhibit bacterial growth or kill bacteria on its surface, particularly on the surface of the outer layer.

[0075] Each component of the fiber-reinforced plastic product 200 will be described in detail below, but explanations that overlap with those of the molded product 100 will be omitted. The fiber-reinforced plastic product 200 is characterized in that it is composed of two members, one of which is fiber-reinforced plastic, and the other of which is specified as a member that contains a resin and a calcium compound and has a predetermined salt on its surface, compared to the molded product 100.

[0076] (fiber reinforced plastic layer) The fiber reinforced plastic layer 210 includes a fiber material and a resin, and therefore the fiber reinforced plastic product 200 has excellent mechanical properties such as high strength and high elastic modulus, while being lightweight and resistant to rust and decay.

[0077] The fiber material contained in the fiber-reinforced plastic layer is not particularly limited as long as it is a fibrous material, and examples thereof include aramid fiber, natural fiber, metal fiber, glass fiber, and carbon fiber. The fiber material contained in the fiber-reinforced plastic layer 210 is preferably glass fiber or carbon fiber, and more preferably glass fiber. Fiber-reinforced plastics containing glass fiber are called GFRP, and fiber-reinforced plastics containing carbon fiber are called CFRP. The fiber-reinforced plastic layer 210 may contain one type of the above-mentioned fiber material alone or two or more types in combination.

[0078] Resins contained in the fiber reinforced plastic layer include, but are not limited to, thermoplastic resins and thermosetting resins. From the viewpoint of improving the strength of the fiber reinforced plastic product 200, it is preferable that the fiber reinforced plastic layer contains a thermosetting resin. Examples of thermosetting resins that can be contained in the fiber reinforced plastic layer include unsaturated polyester resins, phenolic resins, polyamide resins, epoxy resins, vinyl ester resins, polyimide resins, urea resins, and melamine resins. Examples of thermoplastic resins that can be contained in the fiber reinforced plastic layer include polyamide resins and polypropylene resins. The above resins may be used alone or in combination of two or more.

[0079] The fiber reinforced plastic layer 210 may contain, as components other than the fiber material and resin, conventionally known fillers (not fiber materials), curing agents for curing the resin, and additives such as paints. The shape and thickness of the fiber reinforced plastic layer 210 are not particularly limited and can be adjusted appropriately depending on the application of the fiber reinforced plastic product.

[0080] (outer layer) 3, in the fiber-reinforced plastic product 200, the outer layer 220 is provided on the fiber-reinforced plastic layer 210. That is, in the fiber-reinforced plastic product 200, at least a portion of the surface of the fiber-reinforced plastic layer 210 is covered with the outer layer 220, and the outer layer 220 is exposed in the direction opposite to the fiber-reinforced plastic layer 210. The outer layer 220 contains a calcium compound and a resin, and has salts of inositol phosphate with silver and zinc on a surface 221 thereof.

[0081] The outer layer 220 may have a configuration similar to that of the molded body 100 . Furthermore, surface 221 of outer layer 220 may have the same configuration as surface 101 of molded body 100. That is, as shown in Fig. 2, surface 221 may have calcium compounds 104 exposed on the surface, inositol phosphate 102 held on the calcium compounds, and metal elements (silver and zinc) 103 coordinated with the inositol phosphate.

[0082] Examples and preferred embodiments of the calcium compound contained in the outer layer are the same as those of the calcium compound contained in the molded body 100.

[0083] The outer layer 220 may contain one or more of the above calcium compounds. The amount of calcium compound contained in the outer layer 220 is not particularly limited. The calcium compound may be contained in an amount of, for example, 20% by mass to 60% by mass, or 30% by mass to 60% by mass, based on the entire outer layer.

[0084] The particle size of the calcium compound in the outer layer 220 is not particularly limited, but is preferably equal to or smaller than the average thickness of the outer layer, more preferably equal to or smaller than one-fifth of the average thickness of the outer layer, and even more preferably equal to or smaller than one-tenth of the average thickness of the outer layer. More specifically, the particle size of the calcium compound is preferably from 1 μm to 400 μm, more preferably from 5 μm to 200 μm, and even more preferably from 10 μm to 100 μm. The particle size of the calcium compound may be from 10 μm to 50 μm. The method for measuring the particle size of the calcium compound is the same as described above.

[0085] Resins contained in the outer layer 220 include, but are not limited to, thermoplastic resins and thermosetting resins. From the viewpoint of improving the strength of the fiber-reinforced plastic product 200, it is preferable that the outer layer contains a thermosetting resin. Examples of thermosetting resins that can be included in the outer layer include unsaturated polyester resins, phenolic resins, polyamide resins, epoxy resins, vinyl ester resins, polyimide resins, urea resins, and melamine resins. Examples of thermoplastic resins that can be included in the outer layer include polyamide resins and polypropylene resins.

[0086] The outer layer 220 preferably contains any one of an unsaturated polyester resin, a vinyl ester resin, and a mixed resin of an unsaturated polyester resin and a vinyl ester resin. This embodiment tends to increase the strength of the outer layer and more reliably prevent calcium compounds from being released from the outer layer. The mixing ratio of each resin in the mixed resin is not particularly limited.

[0087] There are no particular limitations on the resin content in the outer layer 220. In the outer layer, the resin content may be adjusted as appropriate so that the calcium compound content falls within the above range.

[0088] The outer layer 220 may contain, in addition to the calcium compound and resin, conventionally known fillers (excluding calcium compounds), curing agents for curing the resin, and additives such as paints. Examples of such fillers include oxides such as titanium oxide and silicon dioxide. The outer layer 220 may contain a fibrous material, but preferably does not contain one.

[0089] The filler other than the calcium compound in the outer layer 220 may be contained in an amount of 0% by mass to 10% by mass, or 1.0% by mass to 8.0% by mass, based on the entire outer layer 220.

[0090] The average thickness of the outer layer 220 is not particularly limited and can be changed as appropriate depending on the application of the fiber-reinforced plastic product 200, the required mechanical strength, etc. The average thickness of the outer layer is preferably 0.1 mm or more and 5.0 mm or less. According to this embodiment, the fiber-reinforced plastic product 200 tends to have even better antibacterial or antiviral properties and higher strength. The average thickness of the outer layer may be 0.2 mm or more, or 0.3 mm or more, or may be 3.0 mm or less, or 2.0 mm or less. The average thickness of the outer layer may be a value within a range obtained by arbitrarily selecting the above lower limit and upper limit values.

[0091] The average thickness of the outer layer is determined by measuring the thickness of the outer layer 220 at three or more points in an image of a cross section of the outer layer 220 as shown in Figure 3 observed with an optical microscope or the like, and calculating the arithmetic mean. More specifically, the average thickness of the outer layer is determined as follows. First, the fiber-reinforced plastic product is cut in a direction substantially parallel to its thickness direction, and the exposed cross section is observed from a direction substantially perpendicular to the cross section. A scanning electron microscope (SEM), a transmission electron microscope (TEM), or an optical microscope can be used for the observation. In the obtained observation image, the thickness of the outer layer, which is a layer containing a resin and a calcium compound, is measured at three or more locations, preferably five locations, and more preferably ten locations. The arithmetic mean of the obtained values ​​is calculated, and this value is defined as the average thickness of the outer layer.

[0092] 3, the outer layer 220 is provided on only one side of the fiber-reinforced plastic product 200, but in another embodiment, the outer layer may cover the entire surface of the fiber-reinforced plastic product. There are no particular restrictions on the proportion of the surface area of ​​the fiber-reinforced plastic product that is occupied by the outer layer, and the outer layer can be provided on a portion that should be particularly imparted with antibacterial or antiviral properties. Also, in FIG. 3, the fiber reinforced plastic product 200 has a two-layer structure of a fiber reinforced plastic layer 210 and an outer layer 220, but in other embodiments, the fiber reinforced plastic product may include other layers.

[0093] (Fiber reinforced plastic product shape) The shape of the fiber reinforced plastic product of this embodiment is not particularly limited, and may be plate-like, spherical, cylindrical, or columnar, or may be a three-dimensional shape including a flat surface with irregularities.

[0094] (Applications of fiber reinforced plastic products) The fiber-reinforced plastic product of this embodiment can be used in a variety of applications, but is preferably used for components requiring antibacterial or antiviral properties. For example, it is suitable for use in interior components of vehicles, aircraft, buildings, and the like that may be frequently touched by multiple people, as well as bathtubs and sanitary products that require high levels of hygiene. Examples of applications of the fiber-reinforced plastic product of this embodiment include bathtubs, sanitary products, playground equipment, vases, champagne coolers, portable toilet boxes, washing machine tubs, stationery, automobile steering wheels, doorknobs, food court trays and tables, station and park benches, and interior components of vehicles, aircraft, and buildings.

[0095] [Method of manufacturing molded body] The method for producing the molded article of this embodiment is not particularly limited, and for example, the method for producing the molded article of this embodiment described in detail below can be used.

[0096] The method for producing a molded article of this embodiment includes: (1) a step of adding inositol phosphate to at least a portion of the surface of a molded article of a resin composition containing a calcium compound and a resin (hereinafter referred to as "step A1"); and (2) a step of adding silver ions and zinc ions to the surface to which the inositol phosphate obtained in step A1 has been added (hereinafter referred to as "step A2").

[0097] In the method for producing a molded article of this embodiment, the color difference between the surface of the molded article after step A2 and the surface of the molded article before step A1 is 3.2 or less, and at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the molded article after step A2 is 2.0 or more, based on the surface of the molded article before step A1. This makes it possible to easily produce a molded article that has antibacterial or antiviral properties and is suppressed from coloring.

[0098] Each step will be described below. For convenience, the step of molding a resin composition containing a calcium compound and a resin (hereinafter referred to as "step A0") will also be described, but the method for producing a molded article of this embodiment does not necessarily have to include step A0. For example, instead of step A0, a molded article of a commercially available resin composition containing a calcium compound and a resin may be prepared.

[0099] (Process A0) First, a resin composition containing a calcium compound and a resin is molded. More specifically, step A0 may be carried out as follows. First, the calcium compound and optionally other additives are added to the resin described above to obtain a resin composition. The resin composition is molded by an appropriate method to obtain a molded article of the resin composition. The molded article of the resin composition may be a cured product of the resin composition.

[0100] The resin composition can be molded by various known methods depending on the desired shape of the molded product and the type of resin used, such as injection molding, blow molding, extrusion molding, casting, vacuum molding, compression molding, press molding, and hand layup.

[0101] (Process A1) Next, inositol phosphate is applied to at least a portion of the surface of the molded article obtained in step A0. That is, step A1 is a step of applying inositol phosphate 102 to surface 111 of molded article 110 of a resin composition, as shown in Fig. 4. As the inositol phosphate, the one described above may be applied.

[0102] Examples of methods for applying inositol phosphate to the surface 111 of the molded product 110 include coating or spraying the surface of the molded product 110 with a solution containing inositol phosphate and / or a salt thereof; and contacting the surface of the molded product 110 with a solution containing inositol phosphate and / or a salt thereof for a certain period of time. Examples of methods for contacting the surface of the molded product 110 with a solution containing inositol phosphate and / or a salt thereof for a certain period of time include immersing the molded product 110 in a solution containing inositol phosphate and / or a salt thereof. Step A1 preferably includes a step of contacting the surface 111 with a solution containing inositol phosphate and / or a salt thereof for a certain period of time, and more preferably includes a step of immersing the molded product 110 in a solution containing inositol phosphate and / or a salt thereof. The solution used in the above methods may be a solution containing inositol phosphate.

[0103] The solution containing inositol phosphate may be an aqueous solution of inositol phosphate. Furthermore, the solution containing a salt of inositol phosphate may be an aqueous solution containing any salt of inositol phosphate. The concentration of inositol phosphate in the solution is not particularly limited, but may be, for example, 100 mg / dm 3 It may be more than 500 mg / dm 3 It may be more than 800 mg / dm3 or more, or 8000 mg / dm 3 It may be less than 6000 mg / dm 3 It may be less than 4000 mg / dm 3 It may be less than 2000 mg / dm 3 The concentration of inositol phosphate may be set to a value within a range obtained by arbitrarily selecting the above lower and upper limits. Examples of salts of inositol phosphate include sodium salts and potassium salts of inositol phosphate.

[0104] The pH of the solution containing inositol phosphate is not particularly limited, and may be 3.0 or higher, 4.0 or higher, 5.0 or higher, or 6.0 or higher, or 12.0 or lower, 11.0 or lower, 10.0 or lower, 9.0 or lower, or 8.0 or lower. The pH of the solution may be set to a value within a range obtained by arbitrarily selecting the above-mentioned lower and upper limits.

[0105] In the step of contacting surface 111 with a solution containing inositol phosphate and / or a salt thereof for a certain period of time, or in the step of immersing molded body 110 in a solution containing inositol phosphate and / or a salt thereof, the contact time or immersion time is not particularly limited and may be 5 hours or more, 10 hours or more, 15 hours or more, or 20 hours or more, or 60 hours or less, 50 hours or less, 40 hours or less, or 30 hours or less. The contact time or immersion time may be a value within a range obtained by arbitrarily selecting the above lower limit and upper limit.

[0106] (Process A2) Next, silver ions and zinc ions are applied to the surface 111 of the molded product 110 containing inositol phosphate obtained in step A1. That is, step A2 is a step of applying metal elements 103 (silver and zinc) to the surface 111 of the molded product 110 containing inositol phosphate 102, as shown in Fig. 5. By step A2, the molded product 100 of this embodiment is produced.

[0107] In the method for producing a molded article of this embodiment, the conditions for steps A1 and A2 are controlled so that the color difference between the surface of the molded article after step A2 and the surface of the molded article before step A1 is 3.2 or less. The color difference is preferably 0 to 3.2, more preferably 0.5 to 3.0, even more preferably 0.7 to 2.8, and still more preferably 0.8 to 2.0. The color difference may be measured immediately after step A2, or one day, one week, two weeks, or three weeks after step A2.

[0108] The above color difference is L * a * b * It is a color difference in a color system, and may be measured in accordance with Japanese Industrial Standards (JIS Z 8723:2000 and JIS Z 8781-4:2013). Specifically, it may be measured by the method described in the examples.

[0109] Furthermore, in the method for manufacturing a molded body of this embodiment, the conditions for steps A1 and A2 are controlled so that, based on the surface of the molded body before step A1, at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the molded body after step A2 is 2.0 or higher. Here, it is more preferable that at least two of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses are 2.0 or higher, and it is more preferable that at least three of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses (e.g., at least the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, and the antiviral activity value against non-enveloped viruses) are 2.0 or higher, and it is even more preferable that all of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses are 2.0 or higher. The activity values ​​may preferably be 2.5 or higher, 3.0 or higher, 3.5 or higher, or 4.0 or higher. The upper limit of the activity value is not particularly limited, but the activity value may be, for example, not more than 10, or not more than 8. The activity value may be measured immediately after step A2.

[0110] The antibacterial activity value and antiviral activity value may be measured in accordance with the Japanese Industrial Standards (JIS Z 2801:2010) and the International Standards (ISO 21702), respectively. Specifically, they may be measured by the methods described in the Examples.

[0111] In order to control the color difference and activity value within the above ranges, the amount of inositol phosphate applied to the surface 111 of the molded body 110 in step A1 and / or the amount of silver ions and zinc ions applied to the surface 111 of the molded body 110 in step A2 may be appropriately adjusted. The preferred conditions for step A1 are as described above. Regarding step A2, for example, when the amount of silver supported on the surface of the molded body after step A2 is 10.0 μg / cm 2 The zinc loading is 1.0 μg / cm or less. 2 It is preferable to set the conditions so that the above-mentioned conditions are satisfied. It is more preferable that the amounts of silver and zinc supported on the surface of the molded body after step A2 are each within the ranges described in the section (Surface of molded body).

[0112] Methods for applying metal ions such as silver ions and zinc ions to the surface of the molded body 110 include, for example, a method of coating or spraying a solution containing metal ions onto the surface of the molded body 110; and a method of bringing the surface of the molded body 110 into contact with the solution containing metal ions for a certain period of time. A method of bringing the surface of the molded body 110 into contact with the solution containing metal ions for a certain period of time includes, for example, a method of immersing the molded body 110 in the solution containing metal ions. Step A2 preferably includes a step of bringing the surface 111 into contact with the solution containing metal ions for a certain period of time, and more preferably includes a step of immersing the molded body 110 in the solution containing metal ions.

[0113] The solution containing metal ions may be an aqueous solution of an inorganic salt containing the metal ions. The anion in the inorganic salt is not particularly limited, and examples thereof include nitrate ions, sulfate ions, and carbonate ions.

[0114] The concentration of the metal ions in the solution is not particularly limited, but may be, for example, 0.1 mM (mM stands for "mmol / dm 3". The same applies hereinafter.) or more, 1.0 mM or more, or 3.0 mM or more, or 1.0 M or less, 500 mM or less, 200 mM or less, 100 mM or less, or 50 mM or less. The metal ion concentration may be a value within a range obtained by arbitrarily selecting the above lower limit and upper limit values.

[0115] From the viewpoint of more reliably controlling the color difference and activity value within the above ranges, when step A2 includes a step of contacting the surface of the molded body obtained in step A1 with a solution containing silver ions and zinc ions, it is preferred that the silver ion concentration in the solution is 0.4 to 50 mM or 0.8 to 30 mM, and the zinc ion concentration in the solution is 10 mM or more, or 50 mM or more.

[0116] The concentration of silver ions in the solution is preferably 0.5 to 40 mM, more preferably 0.9 to 25 mM, and even more preferably 1.0 to 20 mM, and may be 1.5 to 15 mM, 1.8 to 10 mM, or 2.0 to 8.0 mM.

[0117] The concentration of zinc ions in the solution is preferably 20 mM to 1.2 M, more preferably 50 mM to 1.0 M, and even more preferably 60 mM to 800 mM, and may be 80 to 500 mM, 90 to 300 mM, or 100 to 200 mM.

[0118] The ratio of the concentrations of silver ions and zinc ions in the solution is not particularly limited, but the molar concentration ratio of zinc ions to silver ions (Zn 2+ / Ag + ) is, for example, 3 to 10,000, preferably 4 to 5,000, and more preferably 5 to 1,000, or 6 to 500. The molar concentration ratio of zinc ions to silver ions (Zn 2+ / Ag + ) may be 300 or less, 200 or less, 100 or less, 50 or less, 30 or less, or 10 or less.

[0119] It is more preferable that the concentrations of silver ions and zinc ions in the solution satisfy the following relational expressions (A) and (B), where the concentration of zinc ions is x (mM) and the concentration of silver ions is y (mM). (A) y≧0.042x+0.2 (B) y≦0.080x+0.4

[0120] By satisfying the above formula (A), a fiber-reinforced plastic product with sufficiently high antibacterial properties can be obtained. Furthermore, by satisfying the above formula (B), a fiber-reinforced plastic product with sufficiently suppressed coloration can be obtained. Furthermore, in the above formulas (A) and (B), the ranges of x and y may be the ranges described above as the preferred ranges for the concentrations of zinc ions and silver ions, respectively.

[0121] In the step of contacting surface 111 with a solution containing metal ions for a certain period of time, or in the step of immersing molded body 110 in a solution containing metal ions, the contact time or immersion time is not particularly limited and may be 1 minute or more, 5 minutes or more, 10 minutes or more, or 1 hour or less, 45 minutes or less, or 30 minutes or less. The contact time or immersion time may be a value within a range obtained by arbitrarily selecting the above lower limit and upper limit.

[0122] (Other processes) The method for producing a molded body of this embodiment may include steps other than steps A0, A1, and A2. For example, it may include a cleaning step and / or a drying step between steps A0 and A1, between steps A1 and A2, and / or after step A2.

[0123] [Method of manufacturing fiber-reinforced plastic products] The method for producing the fiber-reinforced plastic product of this embodiment is not particularly limited, and for example, the method for producing the fiber-reinforced plastic product of this embodiment described in detail below can be used.

[0124] The method for producing a fiber-reinforced plastic product of this embodiment includes: (1) a step of applying inositol phosphate to the surface of an outer layer of a fiber-reinforced plastic having an outer layer containing a calcium compound and a resin on at least a portion of the surface (hereinafter referred to as "step B1"); and (2) a step of applying silver ions and zinc ions to the surface to which the inositol phosphate obtained in step B1 has been applied (hereinafter referred to as "step B2").

[0125] In the method for producing a fiber-reinforced plastic product of this embodiment, the color difference between the surface of the outer layer after step B2 and the surface of the outer layer before step B1 is 3.2 or less, and at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the outer layer after step B2 is 2.0 or more, based on the surface of the outer layer before step B1. This makes it possible to easily produce a fiber-reinforced plastic product that has antibacterial or antiviral properties and is suppressed from coloring.

[0126] Each step will be described below. For convenience, the step of producing a fiber-reinforced plastic having an outer layer containing a calcium compound and a resin on at least a portion of its surface (hereinafter referred to as "step B0") will also be described, but the method for producing a fiber-reinforced plastic product of this embodiment does not necessarily have to include step B0. For example, instead of step B0, a commercially available fiber-reinforced plastic having an outer layer containing a calcium compound and a resin on at least a portion of its surface may be prepared.

[0127] (Process B0) First, a fiber-reinforced plastic is manufactured having an outer layer containing a calcium compound and a resin on at least a portion of its surface. FIG. 6 is a diagram showing an embodiment of step B0. Step B0 may include, as shown in FIG. 6(A), forming an outer layer 220 on a mold 310 for molding a fiber-reinforced plastic product into a desired shape, and then forming a fiber-reinforced plastic layer 210 on the outer layer 220, thereby manufacturing a fiber-reinforced plastic 300 having an outer layer containing a calcium compound and a resin on at least a portion of its surface. Alternatively, step B0 may include, as shown in FIG. 6(B), forming a fiber-reinforced plastic layer 210 on a mold 310, and then forming an outer layer 220 on the fiber-reinforced plastic layer 210, thereby manufacturing a fiber-reinforced plastic 300 having an outer layer containing a calcium compound and a resin on at least a portion of its surface.

[0128] Step B0 may further include a step of forming a new outer layer 220 on the exposed surface of the fiber-reinforced plastic layer 210 after the step of producing the fiber-reinforced plastic 300 having an outer layer containing a calcium compound and a resin on at least a part of the surface.

[0129] The outer layer 220 can be formed, for example, by applying a composition prepared by mixing a resin, a calcium compound, and, if necessary, a curing agent in an appropriate ratio, followed by drying and curing. Alternatively, the outer layer 220 may be formed by adding a calcium compound to a solution containing a thermoplastic resin and applying the solution. The resin and calcium compound may be any of those listed above. It is preferable to adjust the blending amounts of the resin and calcium compound so that the contents of the resin and calcium compound fall within the above-mentioned ranges.

[0130] The fiber reinforced plastic layer 210 may be formed by a conventionally known method, for example, by hand lay-up molding or machine molding.

[0131] (Process B1) Next, inositol phosphate is applied to the surface of the outer layer 220 of the fiber-reinforced plastic obtained in step B0. That is, step B1 is a step of applying inositol phosphate 102 to the surface 221 of the outer layer 220 of the fiber-reinforced plastic 300, as shown in Fig. 7 . Step B1 may be carried out in the same manner as step A1, except that the target to which inositol phosphate is applied is changed from surface 111 of molded body 110 of a resin composition to surface 221 of outer layer 220 of fiber-reinforced plastic 300.

[0132] (Process B2) Next, silver ions and zinc ions are applied to the surface 221 of the outer layer 220 containing inositol phosphate obtained in step B1. That is, step B2 is a step of applying metal elements 103 (silver ions and zinc ions) to the surface 221 of the outer layer 220 of a fiber-reinforced plastic 300 containing inositol phosphate 102, as shown in Fig. 8. A fiber-reinforced plastic product 200 is produced by step B2. Step B2 may be carried out in the same manner as step A2, except that the target to which metal ions are applied is changed from surface 111 of molded body 110 of a resin composition to surface 221 of outer layer 220 of fiber reinforced plastic 300.

[0133] (Other processes) The method for manufacturing a fiber-reinforced plastic product of this embodiment may include steps other than steps B0, B1, and B2, and may include, for example, a cleaning step and / or a drying step between steps B0 and B1, between steps B1 and B2, and / or after step B2.

[0134] [Improving / imparting antibacterial or antiviral properties of molded products] As described above, it is believed that the molded article and fiber-reinforced plastic product of this embodiment exhibit antibacterial or antiviral properties mainly due to the salt of inositol phosphate and metal ions (silver ions and zinc ions) and / or the metal ions eluted from the salt. Therefore, it is believed that the molded article and fiber-reinforced plastic product of this embodiment will have a reduced antibacterial or antiviral property if metal ions are eluted during long-term use.

[0135] Even in such cases, the method of the present embodiment for improving the antibacterial or antiviral properties of a molded body or imparting antibacterial or antiviral properties to a molded body (hereinafter simply referred to as the "method of the present embodiment for improving / imparting antibacterial or antiviral properties") can improve the antibacterial or antiviral properties of molded bodies and fiber-reinforced plastic products with reduced antibacterial or antiviral properties.

[0136] In other words, the method for improving / imparting antibacterial or antiviral properties of this embodiment is a method for improving the antibacterial or antiviral properties of a molded article that contains a calcium compound and a resin and has inositol phosphate on its surface, or for imparting antibacterial or antiviral properties to the molded article, and includes a step of imparting silver ions and zinc ions to the surface of the molded article having inositol phosphate (hereinafter referred to as "step C1"). According to this method, it is possible to easily impart excellent antibacterial or antiviral properties to a molded article that does not contain silver or zinc, or to easily improve the antibacterial or antiviral properties of a molded article that has an insufficient amount of silver or zinc supported thereon.

[0137] In the method for improving / imparting antibacterial or antiviral properties of this embodiment, the amount of silver carried on the surface of the molded article after step C1 is 10.0 μg / cm 2 or less, and the amount of zinc supported on the surface of the molded body after step C1 is 1.0 μg / cm 2 Step C1 is carried out under the above conditions.

[0138] In the method for improving / imparting antibacterial or antiviral properties of this embodiment, the target for improving or imparting antibacterial or antiviral properties is a molded article containing a calcium compound and a resin, which has inositol phosphate on its surface. The molded article may or may not be a fiber-reinforced plastic. Silver and zinc may or may not be supported on the surface of the molded article.

[0139] In one aspect of the method for improving / imparting antibacterial or antiviral properties of the present embodiment, the molded article to which silver ions and zinc ions are imparted is the molded article of the present embodiment that has lost its antibacterial or antiviral properties, i.e., the molded article of the present embodiment from which silver and zinc have eluted from the surface. According to this aspect, the antibacterial or antiviral properties of the molded article of the present embodiment that has lost its antibacterial or antiviral properties can be restored.

[0140] In one aspect of the method for improving / imparting antibacterial or antiviral properties of the present embodiment, a molded article to which silver ions and zinc ions are imparted includes a fiber-reinforced plastic layer and an outer layer provided on the fiber-reinforced plastic layer, the outer layer containing a calcium compound and a resin and having inositol phosphate on its surface. According to this aspect, antibacterial or antiviral properties can be imparted to the fiber-reinforced plastic or the antibacterial or antiviral properties of the fiber-reinforced plastic can be improved.

[0141] The step of providing metal ions to the surface of the molded body can be the same as step A2 or B2 in the method for producing a molded body of the present embodiment. For example, the surface of the molded body may be brought into contact with a solution containing silver ions and zinc ions at concentrations within the above-mentioned ranges. The method for improving / imparting antibacterial or antiviral properties of this embodiment may include a step of imparting inositol phosphate to the surface of the molded body, such as step A1 or B1 in the method for producing a molded body of this embodiment, before the step of imparting the metal ions.

[0142] The conditions for step C1 may be controlled so that the color difference between the surface of the molded article after step C1 and the surface of the molded article before step C1 is 3.2 or less. The color difference is preferably 0 to 3.2, more preferably 0.5 to 3.0, even more preferably 0.7 to 2.8, and still more preferably 0.8 to 2.0. The color difference may be measured immediately after step C1, or one day, one week, two weeks, or three weeks after step C1.

[0143] Furthermore, the conditions for step C1 may be controlled so that, based on the surface of the molded body before step C1, at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the molded body after step C1 is 2.0 or higher. Here, it is more preferable that at least two of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses are 2.0 or higher, and it is more preferable that at least three of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses (e.g., at least the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, and the antiviral activity value against non-enveloped viruses) are 2.0 or higher, and it is even more preferable that all of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses are 2.0 or higher. The activity values ​​may preferably be 2.5 or higher, 3.0 or higher, 3.5 or higher, or 4.0 or higher. The upper limit of the activity value is not particularly limited, but the activity value may be, for example, not more than 10, or not more than 8. The activity value may be measured immediately after step C1.

[0144] [Note] The present disclosure includes the following embodiments. [1] Contains a calcium compound and a resin, having a salt of inositol phosphate with silver and zinc on its surface; The amount of silver carried on the surface is 10.0 μg / cm 2 is as follows: The amount of zinc carried on the surface is 1.0 μg / cm 2 That's all. Molded body. [2] A reference molded body having the same structure as the molded body except that it does not have a salt of inositol phosphate with silver and zinc on its surface was used as a standard. The color difference between the surface of the molded body and the surface of the reference molded body is 3.2 or less. [1] The molded article according to the present invention. [3] A reference molded body having the same structure as the molded body except that it does not have a salt of inositol phosphate with silver and zinc on its surface was used as a standard. At least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the molded body is 2.0 or more. [1] or [2]. [4] The resin includes any one of an unsaturated polyester resin, a vinyl ester resin, and a mixed resin of an unsaturated polyester resin and a vinyl ester resin. The molded article according to any one of [1] to [3]. [5] The calcium compound includes calcium carbonate. The molded article according to any one of [1] to [4]. [6] The number of phosphate groups contained in the inositol phosphate is 3 or more and 6 or less. The molded article according to any one of [1] to [5]. [7] The inositol phosphate is phytic acid. [6] The molded article according to [6]. [8] The molded body includes a fiber-reinforced plastic layer and an outer layer provided on the fiber-reinforced plastic layer, the outer layer contains the calcium compound and the resin, and has on its surface salts of inositol phosphate with silver and zinc; The molded article according to any one of [1] to [7]. [9] The average thickness of the outer layer is 0.1 mm or more and 5.0 mm or less. [8] The molded article according to [8].

[10] Bathtubs, sanitary products, play equipment, flower vases, champagne coolers, portable toilet boxes, washing machine tubs, stationery, car steering wheels, door handles, food court trays or tables, station or park benches, or interior components of vehicles, aircraft or buildings. The molded article according to any one of [1] to [9].

[11] A step A1 of providing inositol phosphate to at least a portion of the surface of a molded article of a resin composition containing a calcium compound and a resin; A step A2 of applying silver ions and zinc ions to the surface to which the inositol phosphate has been applied; Including, a color difference between the surface of the molded body after the step A2 and the surface of the molded body before the step A1 is 3.2 or less; With respect to the surface of the molded body before step A1 as a reference, at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the molded body after step A2 is 2.0 or more. A method for manufacturing a molded body.

[12] The amount of silver supported on the surface of the molded body after step A2 is 10.0 μg / cm 2 is as follows: The amount of zinc supported on the surface of the molded body after step A2 is 1.0 μg / cm 2 That's all.

[11] The manufacturing method described in

[11] .

[13] The step A2 is a step of contacting the surface of the molded body obtained in the step A1 with a solution containing silver ions and zinc ions, The silver ion concentration of the solution is 0.8 to 30 mM, The concentration of zinc ions in the solution is 50 mM or more.

[11] or

[12] .

[14] When the concentration of zinc ions in the solution is x (mM) and the concentration of silver ions in the solution is y (mM), the following formulas (A) and (B) are satisfied: (A) y≧0.042x+0.2 (B) y≦0.080x+0.4 The manufacturing method according to any one of

[11] to

[13] .

[15] A step B1 of applying inositol phosphate to a surface of an outer layer of a fiber-reinforced plastic having an outer layer containing a calcium compound and a resin on at least a part of the surface of the outer layer; Step B2 of applying silver ions and zinc ions to the surface to which the inositol phosphate has been applied; Including, a color difference between the surface of the outer layer after step B2 and the surface of the outer layer before step B1 is 3.2 or less; With respect to the surface of the outer layer before step B1 as a reference, at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the outer layer after step B2 is 2.0 or more. A method for manufacturing fiber-reinforced plastic products.

[16] A method for improving antibacterial or antiviral properties of a molded article containing a calcium compound and a resin and having inositol phosphate on its surface, or imparting antibacterial or antiviral properties to the molded article, comprising: a step C1 of providing silver ions and zinc ions to the surface having inositol phosphate; The amount of silver supported on the surface of the molded body after step C1 is 10.0 μg / cm 2 is as follows: The amount of zinc supported on the surface of the molded body after the step C1 is 1.0 μg / cm 2 That's all. method.

[17] the molded article has lost its antibacterial or antiviral properties, Restoring the antibacterial or antiviral properties of the molded body,

[16] The method described in

[16] .

[18] The molded body includes a fiber-reinforced plastic layer and an outer layer provided on the fiber-reinforced plastic layer, The outer layer contains a calcium compound and a resin and has inositol phosphate on its surface. The method according to

[16] or

[17] . [Example]

[0145] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0146] [Manufacturing of fiber-reinforced plastics] A fiber-reinforced plastic was produced as follows. First, a fiber-reinforced plastic was fabricated by hand lay-up molding. The fiber-reinforced plastic consisted of a fiber-reinforced plastic layer containing glass fiber and unsaturated polyester resin, and an outer layer formed on the fiber-reinforced plastic layer and containing calcium carbonate and unsaturated polyester resin. The calcium carbonate content in the outer layer was 50 mass% of the entire outer layer. The average thickness of the outer layer measured by the above method was 0.3 mm. Commercially available calcium carbonate microparticles with a particle size of approximately 2.2 μm were used to form the outer layer. SEM observation of the cross section of the outer layer revealed that the calcium carbonate microparticles formed aggregates, with the particle size of the aggregate particles being 15 μm.

[0147] Next, an aqueous solution of inositol phosphate (phytic acid) at pH 7.3 (phytic acid concentration: 1000 mg / dm 3 The fiber-reinforced plastic was immersed in a solution of 100% ammonium nitrate at 37°C for 24 hours, thereby adding inositol phosphate to the outer layer of the fiber-reinforced plastic. The plastic was then washed with pure water. Energy dispersive X-ray spectroscopy (EDX) confirmed that inositol phosphate had been added to the outer layer of the fiber-reinforced plastic.

[0148] Next, the fiber-reinforced plastic to which inositol phosphate had been added was immersed in an aqueous silver nitrate solution, an aqueous zinc nitrate solution, or a mixture thereof at room temperature for 15 minutes to add silver ions, zinc ions, or silver ions and zinc ions to the outer layer of the fiber-reinforced plastic. The concentrations of the aqueous silver nitrate solution and the aqueous zinc nitrate solution were as described below. The fiber-reinforced plastic was washed with pure water and dried to obtain a fiber-reinforced plastic containing inositol phosphate and silver ions, zinc ions, or silver ions and zinc ions.

[0149] [Evaluation of antibacterial properties of fiber-reinforced plastics] (Test Example 1) The antibacterial properties of the fiber-reinforced plastics obtained above were evaluated in accordance with the Japanese Industrial Standard (JIS Z 2801:2010). The samples used were: a sample in which silver ions were immobilized using a 5 mM silver nitrate aqueous solution; a sample in which zinc ions were immobilized using a 100 mM zinc nitrate aqueous solution; a sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 1 mM silver nitrate and 500 mM zinc nitrate; and a sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate. A fiber-reinforced plastic to which inositol phosphate and silver ions had not been added was used as a control sample.

[0150] The specific procedure for evaluating antibacterial properties is as follows. A bacterial solution containing Gram-negative bacteria (E. coli) pre-cultured in LB medium was inoculated at a density of 5 x 10 5 The bacterial solution was prepared so that the concentration was CFU / mL. The prepared bacterial solution was seeded on the sample and then covered with a film. The bacterial solution on the sample was cultured at 37°C for 24 hours and then washed away. The resulting washings were diluted, and the diluted washings were cultured in LB medium at 37°C for 24 to 48 hours, after which the number of colonies was counted. The viable bacterial count was calculated from the number of colonies that appeared.

[0151] The antibacterial activity value was calculated using the following formula: The antibacterial activity value is a value that indicates the antibacterial properties of an antibacterial material, and if the value is 2.0 or higher, it can be determined that the material has sufficient antibacterial properties. Antibacterial activity value = log (number of viable bacteria after incubation of non-antibacterial treated sample) - log (number of viable bacteria after incubation of antibacterial treated sample)

[0152] The viable cell counts and antibacterial activity values ​​for each sample are shown in Figure 9. The sample in which silver ions were immobilized using a 5 mM silver nitrate aqueous solution, the sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 1 mM silver nitrate and 500 mM zinc nitrate, and the sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate all had antibacterial activity values ​​of 2 or higher, demonstrating sufficient antibacterial properties. The sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 1 mM silver nitrate and 500 mM zinc nitrate had an antibacterial activity value of 2.28.

[0153] (Test Example 2) The antibacterial properties were evaluated in the same manner as in Test Example 1, except that gram-positive bacteria (Staphylococcus aureus (S. aureus)) were used instead of Escherichia coli (E. coli) as the bacteria.

[0154] The viable cell count and antibacterial activity value of each sample are shown in Figure 10. The sample in which silver ions were immobilized using a 5 mM silver nitrate aqueous solution and the sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate had an antibacterial activity value of 2 or more, indicating that they had sufficient antibacterial properties.

[0155] [Evaluation of antiviral properties of fiber-reinforced plastics] The antiviral properties of the fiber-reinforced plastics obtained above were evaluated in accordance with the international standard (ISO 21702). The samples used were those in which silver ions were immobilized using a 5 mM silver nitrate aqueous solution, those in which zinc ions were immobilized using a 100 mM zinc nitrate aqueous solution, and those in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate. A fiber-reinforced plastic without inositol phosphate or silver ions was used as a control sample. Each sample was sterilized with EOG before testing, and three samples were used. A non-enveloped virus (feline calicivirus) was used as the test virus, and CRFK cells were used as the host cells.

[0156] The specific evaluation procedure is as follows: Infectivity titer is 2.5 x 10 7 PFU / cm 3 400 mL of the virus solution prepared to achieve a concentration of 1000 μg / ml was inoculated onto each sample and allowed to stand at 25.0°C for 24 hours. The virus solution on the sample was then washed off and inoculated onto pre-cultured host cells. The cells were then cultured for the specified time and fixed in semi-solid medium. The medium was stained with crystal violet, and the number of plaques was counted.

[0157] The logarithmic value of the infectivity titer per unit area was calculated from the number of plaques, and the antiviral activity value was calculated using the following formula. Antiviral activity value = log (viral infectivity per unit area after incubation of non-antiviral treated sample) - log (viral infectivity per unit area after incubation of antiviral treated sample)

[0158] The number of plaques and antiviral activity values ​​for each sample are shown in Figure 11. According to the Japanese Industrial Standards (JIS L 1922:2016, Annex G), an antiviral activity value of 2 or more but less than 3 is considered to have an "antiviral effect," and an antiviral activity value of 3 or more is considered to have a "sufficient antiviral effect." Therefore, it was found that the sample in which silver ions were immobilized using a 5 mM silver nitrate aqueous solution, and the sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate, had excellent antiviral properties.

[0159] [Evaluation of color change in fiber-reinforced plastics] The color change of the fiber-reinforced plastic obtained above was evaluated in accordance with Japanese Industrial Standards (JIS Z 8723:2000 and JIS Z 8781-4:2013). The samples used were: a sample in which silver ions were immobilized using a 5 mM silver nitrate aqueous solution; a sample in which zinc ions were immobilized using a 100 mM zinc nitrate aqueous solution; a sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 1 mM silver nitrate and 500 mM zinc nitrate; and a sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate. A fiber-reinforced plastic to which inositol phosphate and silver ions had not been added was used as a control sample.

[0160] The specific procedure for evaluating the color change is as follows. Using a color analyzer color difference meter (color meter; Satotec TES-3250), first perform white calibration using the attached calibration sheet, then measure the L of each sample. * a * b * CIE lightness (L * ), and color coordinates (a * ,b * The CIE lightness (L) of a sample in which silver ions were fixed using a 5 mM silver nitrate aqueous solution and a sample in which silver ions and zinc ions were fixed using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate was measured over time. * ), and color coordinates (a * ,b * ) over time is shown in Figure 12. Figure 12 shows that the change in color coordinate over time is suppressed in the sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate, compared to the sample in which silver ions were immobilized using a 5 mM silver nitrate aqueous solution.

[0161] In addition, L obtained from the following formula * a * b * The color difference in the color system was calculated.

number

[0162] The change in color difference for each sample is shown in Figure 13. A color difference of 3.2 or less is considered to be above the Class A tolerance, and is a color difference level that is barely noticeable in a color comparison. As shown in Figure 13, the sample in which zinc ions were immobilized using a 100 mM zinc nitrate aqueous solution and the sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate had a color difference of 2 or less even after three weeks, indicating that there was almost no color change. Furthermore, for the sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 1 mM silver nitrate and 500 mM zinc nitrate, the color difference ΔE * ab was 0.564.

[0163] [Measurement of metal element loading in fiber-reinforced plastics] The amounts of silver and zinc supported on the surface of the outer layer of the fiber reinforced plastic obtained above were measured using an inductively coupled plasma atomic emission spectrometer (ICP-AES). Specifically, the surface of each sample was washed with 70% nitric acid, and the resulting washings were measured by ICP-AES. The ICP-AES measurement was performed using the calibration curve method. The instrument used was the SPS-7800 manufactured by Hitachi High-Tech Science Corporation.

[0164] The amounts of silver and zinc supported, measured by ICP-AES, for a sample in which silver ions were immobilized using a 5 mM silver nitrate aqueous solution, a sample in which zinc ions were immobilized using a 100 mM zinc nitrate aqueous solution, and a sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate are shown in Figure 14. Similarly, a sample in which silver ions were immobilized using a 0.5 mM silver nitrate aqueous solution was also measured, and the amount of silver ions supported was 3.2 μg / cm. 2 It was.

[0165] [Evaluation of cytotoxicity of fiber-reinforced plastics] Next, the cytotoxicity of the above fiber-reinforced plastics was evaluated. The cells evaluated were mouse connective tissue-derived fibroblasts (L929 cells) (passage number: p = 3 or later), and the culture medium was Eagle's minimum essential medium supplemented with 10% fetal bovine serum and 100 U / cm 3 Penicillin, and 100 μg / cm 3 The medium was supplemented with streptomycin, and the cell culture environment was 37°C in a 5% CO2 atmosphere.

[0166] The samples used were a sample in which zinc ions were immobilized using a 100 mM zinc nitrate aqueous solution, and a sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate, as described above. A control sample was a fiber-reinforced plastic to which inositol phosphate and silver ions had not been added.

[0167] The above samples were seeded with cultured L929 cells at a seeding density of 6.0 × 10 4 cells / cm 3 After 1 or 4 days of culture, the number of cells in each sample was measured using an Automated Cell Counter (TC20) manufactured by BIO-RAD.

[0168] For each sample, the relative cell proliferation rate M was calculated using the following formula.

number

[0169] The relative cell proliferation rate for each sample is shown in Figure 15. The relative cell proliferation rate was 70% or higher for the sample in which zinc ions were immobilized using an aqueous solution containing 100 mM zinc nitrate, and the sample in which silver ions and zinc ions were immobilized using an aqueous solution containing 5 mM silver nitrate and 100 mM zinc nitrate. These samples were determined to be non-cytotoxic in accordance with the "Criteria for colony formation assay using extraction method" in "Yakushokuki-hatsu 0301-20, March 1, 2012, Basic Concepts for Biological Safety Assessment Required for Medical Device Marketing Approval Applications, Part 1: Cytotoxicity Testing."

[0170] [Adjusting the amount of supported metal elements] (Effect on antibacterial properties) In accordance with the Japanese Industrial Standards (JIS Z 2801:2010), the antibacterial properties of fiber-reinforced plastics obtained by the same method as described in "Manufacturing of fiber-reinforced plastics" were evaluated. In the above manufacturing method, multiple samples were prepared by varying the concentrations of the silver nitrate aqueous solution and the zinc nitrate aqueous solution, and the antibacterial properties were evaluated. The antibacterial properties were evaluated using the method described in "Evaluation of the antibacterial properties of fiber-reinforced plastics," and gram-negative bacteria (E. coli) were used.

[0171] The relationship between the concentrations of the silver nitrate and zinc nitrate solutions used and the calculated antibacterial activity values ​​is shown in the table below. Note that R stands for antibacterial activity value. In the table, cells without values ​​were not used for the experiment.

[0172] [Table 1]

[0173] (Effect on color change) In accordance with the Japanese Industrial Standards (JIS Z 2801:2010), the color change of fiber-reinforced plastics obtained by the same method as described in [Manufacturing of fiber-reinforced plastics] was evaluated. In addition, multiple samples were prepared by varying the concentrations of the silver nitrate aqueous solution and the zinc nitrate aqueous solution in the above manufacturing method, and color change was evaluated. The color change was evaluated using the method described in [Evaluation of color change of fiber-reinforced plastics].

[0174] Concentration of silver nitrate and zinc nitrate solutions used and color difference ΔE 28 days after preparation * ab The relationship between the values ​​is shown in the table below. In the table, cells with no value indicated were not subjected to the experiment.

[0175] [Table 2]

[0176] These results demonstrate that all samples have high antibacterial properties or high resistance to color change. In particular, the sample prepared using a 5 mM silver nitrate aqueous solution and a 100 mM zinc nitrate aqueous solution, and the sample prepared using a 20 mM silver nitrate aqueous solution and a 300 mM zinc nitrate aqueous solution, exhibited an excellent balance of high antibacterial properties and high resistance to color change.

[0177] (Measurement of supported amount of metal element) Using the fiber reinforced plastic obtained above as a sample, the amounts of silver and zinc supported on the surface were measured using an inductively coupled plasma atomic emission spectrometer (ICP-AES). Specifically, the surface of each sample was washed with 70% nitric acid, and the resulting washings were measured by ICP-AES. The ICP-AES measurement was performed using the calibration curve method. The instrument used was a Hitachi High-Tech Science PS-7800.

[0178] The measured samples and the amounts of silver and zinc supported by each sample measured by ICP-AES are shown in Figures 16 and 17. Figure 16 shows the results when the concentration of the zinc nitrate aqueous solution used was fixed at 100 mM and the concentration of the silver nitrate aqueous solution was changed. Figure 17 shows the results when the concentration of the silver nitrate aqueous solution used was fixed at 5 mM and the concentration of the zinc nitrate aqueous solution was changed. [Industrial Applicability]

[0179] INDUSTRIAL APPLICABILITY The present invention can provide members and products having excellent antibacterial or antiviral properties and mechanical properties, and has industrial applicability, for example, in the field of improving public health. [Explanation of symbols]

[0180] 100, 110... Molded body, 101, 111, 221... Surface, 102... Inositol phosphate, 103... Metal element, 104... Calcium compound, 200... Fiber reinforced plastic product, 210... Fiber reinforced plastic layer, 220... Outer layer, 300... Fiber reinforced plastic, 310... Mold

Claims

1. Contains a calcium compound and a resin, having a salt of inositol phosphate with silver and zinc on its surface; The amount of silver carried on the surface is 10.0 μg / cm 2 is as follows: The amount of zinc carried on the surface is 1.0 μg / cm 2 That's all. Molded body.

2. A reference molded body having the same structure as the molded body except that it does not have a salt of inositol phosphate with silver and zinc on its surface was used as a standard. The color difference between the surface of the molded body and the surface of the reference molded body is 3.2 or less. The molded article according to claim 1.

3. A reference molded body having the same structure as the molded body except that it does not have a salt of inositol phosphate with silver and zinc on its surface was used as a standard. At least one of an antibacterial activity value against gram-negative bacteria, an antibacterial activity value against gram-positive bacteria, an antiviral activity value against enveloped viruses, and an antiviral activity value against non-enveloped viruses of the surface of the molded body is 2.0 or more. The molded article according to claim 1.

4. The resin includes any one of an unsaturated polyester resin, a vinyl ester resin, and a mixed resin of an unsaturated polyester resin and a vinyl ester resin. The molded article according to claim 1.

5. The calcium compound includes calcium carbonate. The molded article according to claim 1.

6. the number of phosphate groups contained in the inositol phosphate is 3 or more and 6 or less; The molded article according to claim 1.

7. The inositol phosphate is phytic acid. The molded article according to claim 6.

8. The molded body includes a fiber-reinforced plastic layer and an outer layer provided on the fiber-reinforced plastic layer, the outer layer contains the calcium compound and the resin, and has on its surface salts of inositol phosphate with silver and zinc; The molded article according to any one of claims 1 to 7.

9. The average thickness of the outer layer is 0.1 mm or more and 5.0 mm or less. The molded article according to claim 8.

10. Bathtubs, sanitary products, play equipment, flower vases, champagne coolers, portable toilet boxes, washing machine tubs, stationery, car steering wheels, door handles, food court trays or tables, station or park benches, or interior components of vehicles, aircraft or buildings. The molded article according to any one of claims 1 to 7.

11. A step A1 of providing inositol phosphate to at least a part of the surface of a molded article of a resin composition containing a calcium compound and a resin; A step A2 of applying silver ions and zinc ions to the surface to which the inositol phosphate has been applied; Including, a color difference between the surface of the molded body after the step A2 and the surface of the molded body before the step A1 is 3.2 or less; With respect to the surface of the molded body before the step A1 as a reference, at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the molded body after the step A2 is 2.0 or more. A method for manufacturing a molded body.

12. The amount of silver supported on the surface of the molded body after step A2 is 10.0 μg / cm 2 is as follows: The amount of zinc supported on the surface of the molded body after step A2 is 1.0 μg / cm 2 That's all. The method of claim 11.

13. The step A2 is a step of contacting the surface of the molded body obtained in the step A1 with a solution containing silver ions and zinc ions, The silver ion concentration of the solution is 0.8 to 30 mM; The zinc ion concentration of the solution is 50 mM or more. The method according to claim 11 or 12.

14. When the concentration of zinc ions in the solution is x (mM) and the concentration of silver ions in the solution is y (mM), the following formulas (A) and (B) are satisfied: (A)y≧0.042x+0.2 (B)y≦0.080x+0.4 The method of claim 13.

15. A step B1 of applying inositol phosphate to a surface of an outer layer of a fiber-reinforced plastic having an outer layer containing a calcium compound and a resin on at least a part of the surface of the outer layer; Step B2 of applying silver ions and zinc ions to the surface to which the inositol phosphate has been applied; Including, a color difference between the surface of the outer layer after step B2 and the surface of the outer layer before step B1 is 3.2 or less; With respect to the surface of the outer layer before step B1 as a reference, at least one of the antibacterial activity value against gram-negative bacteria, the antibacterial activity value against gram-positive bacteria, the antiviral activity value against enveloped viruses, and the antiviral activity value against non-enveloped viruses of the surface of the outer layer after step B2 is 2.0 or more. A method for manufacturing fiber-reinforced plastic products.

16. A method for improving antibacterial or antiviral properties of a molded article containing a calcium compound and a resin and having inositol phosphate on its surface, or imparting antibacterial or antiviral properties to the molded article, comprising: a step C1 of providing silver ions and zinc ions to the surface having inositol phosphate; The amount of silver supported on the surface of the molded body after the step C1 is 10.0 μg / cm 2 is as follows: The amount of zinc supported on the surface of the molded body after the step C1 is 1.0 μg / cm 2 That's all. method.

17. the molded article has lost its antibacterial or antiviral properties, Restoring the antibacterial or antiviral properties of the molded body, 17. The method of claim 16.

18. The molded body includes a fiber-reinforced plastic layer and an outer layer provided on the fiber-reinforced plastic layer, The outer layer contains a calcium compound and a resin and has inositol phosphate on its surface.

18. The method of claim 16 or 17.

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