JP2023033243A - Laminate for drawing, secondary molding and antiviral member - Google Patents

Abstract

To provide a laminate for drawing that can be drawn and can also keep excellent antiviral properties even after the drawing.SOLUTION: A laminate for drawing has a substrate, and an anti-virus layer disposed on a first surface side of the substrate. The anti-virus layer includes an antiviral agent, and a resin part.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a stretchable laminate comprising a substrate and an antiviral layer containing an antiviral agent. The present invention also relates to a secondary molded product using the above stretchable laminate. Furthermore, the present invention relates to an antiviral member comprising the secondary molded product.

In recent years, infectious diseases caused by viruses such as severe respiratory infection (SARS) virus, avian influenza virus, foot-and-mouth disease virus, novel influenza virus, and novel coronavirus have become a social problem.

For this reason, the development of techniques for applying antiviral processing to members that are touched by an unspecified number of people or that may be touched is underway.

As an example of a member having antiviral properties, Patent Document 1 below discloses a polyvinyl chloride-based resin interior sheet including a base material layer and an antiviral polyvinyl chloride-based resin layer. In this interior sheet, the material of the antiviral polyvinyl chloride resin layer is 100 parts by weight of polyvinyl chloride resin, 0.1 to 7.5 parts by weight of sulfonic acid surfactant, and 10 parts by weight of plasticizer. parts by weight to 100 parts by weight. Further, Patent Document 1 describes that the interior sheet is produced by coating the surface of the base material layer with the material for the antiviral polyvinyl chloride resin layer.

JP 2015-077752 A

As described in Patent Document 1, conventional antiviral members are manufactured by coating a member body or the like with an antiviral material. In addition, conventionally, it has not been assumed to further process and use a member having antiviral properties.

An object of the present invention is to provide a laminate for stretching which can be used after being stretched and which has excellent antiviral properties even after stretching. Another object of the present invention is to provide a secondary molded article and an antiviral member using the above-described stretchable laminate.

In this specification, the following stretchable laminates, secondary molded articles and antiviral members are disclosed.

Section 1. A laminate for stretching (hereinafter referred to as laminate (Sometimes abbreviated as body).

Section 2. Item 2. The laminate according to item 1, wherein the antiviral agent has a heat resistant temperature of 200°C or higher.

Item 3. Item 3. The laminate according to Item 1 or 2, wherein the base material contains a thermoplastic resin, and the resin contained in the resin portion is a thermoplastic resin.

Section 4. 4. The laminate according to any one of Items 1 to 3, wherein the resin contained in the resin portion is an olefin resin, a vinyl resin, an ester resin, an ABS resin, or a copolymer resin of these resins. .

Item 5. Item 5. The laminate according to any one of Items 1 to 4, wherein the ratio of the average thickness of the antiviral layer to the average particle size of the antiviral agent is 1.0 or more.

Item 6. Item 6. The laminate according to Item 5, wherein the ratio of the average thickness of the antiviral layer to the average particle size of the antiviral agent is 1.69 or more.

Item 7. A secondary molded product obtained by stretching the laminate according to any one of Items 1 to 6.

Item 8. Item 8. The secondary molded product according to Item 7, wherein the ratio of the average thickness of the layer derived from the antiviral layer to the average particle size of the antiviral agent is 0.5 or more.

Item 9. Item 9. An antiviral member comprising an antiviral member main body and the secondary molded article according to item 7 or 8.

The stretchable laminate according to the present invention includes a base material and an antiviral layer disposed on the first surface side of the base material, and the antiviral layer includes an antiviral agent and a resin portion. include. Since the laminate for stretching according to the present invention has the above structure, it can be used after being stretched, and has excellent antiviral properties even after stretching.

FIG. 1 is a cross-sectional view schematically showing a stretchable laminate according to one embodiment of the present invention. FIG. 2 is a diagram for explaining the height of the exposed portion of the antiviral agent A. FIG. FIG. 3 is a diagram for explaining the method of manufacturing the stretchable laminate in the example.

The present invention will be described in detail below.

[Laminate for stretching]
The laminate for stretching (hereinafter sometimes abbreviated as "laminate") according to the present invention is a laminate that is used after being stretched. The laminate according to the present invention is an antiviral laminate. The stretchable laminate according to the present invention includes a base material and an antiviral layer disposed on the first surface side of the base material, and the antiviral layer includes an antiviral agent and a resin portion. include.

Since the laminate according to the present invention has the above structure, it can be used after being stretched, and has excellent antiviral properties even after being stretched. If the laminate can be stretched, the laminate can be used after being stretched, or the laminate can be used without being stretched, thereby considerably increasing the versatility of the laminate.

For example, the laminate is stretched by vacuum forming, pressure forming, blow molding, etc., and the stretched laminate is placed on the surface of the target member from the layer derived from the base material. Used. Since the laminate can be stretched into various shapes according to the shape of the target member, antiviral performance can be easily imparted to the target member.

The laminate can exhibit good antiviral properties even after being stretched. In the present invention, even a laminate (secondary molded product) after stretching can exhibit the same antiviral performance as the laminate before stretching.

Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing a stretchable laminate according to one embodiment of the present invention.

The stretchable laminate 10 shown in FIG. 1 is used after being stretched. The laminate 10 has antiviral performance. A laminate 10 includes a base material 1 and an antiviral layer 2 . The antiviral layer 2 is arranged on the first surface 1a side of the substrate 1 . The antiviral layer 2 is arranged and laminated on the first surface 1a of the substrate 1 .

The antiviral layer 2 includes a resin portion 21 (layer body) and an antiviral agent 22 . The antiviral layer 2 contains resin and a plurality of antiviral agents 22 . The antiviral layer 2 is the surface layer of the laminate 10 . The antiviral layer 2 is one surface layer of the laminate 10 .

In the laminate 10 , the antiviral agent 22 has a portion exposed from the surface 21 a of the resin portion 21 opposite to the substrate 1 side. The antiviral agent 22 includes an antiviral agent 22A having a portion exposed from the surface 21a of the resin portion 21 and an antiviral agent 22B having no portion exposed from the surface 21a of the resin portion 21.

In the laminate, the antiviral layer is preferably the surface layer of the laminate, from the viewpoint of further enhancing the immediate antiviral action.

In the laminate, the antiviral agent may include an antiviral agent having a portion exposed from the surface of the resin portion and an antiviral agent having no portion exposed from the surface of the resin portion. preferable.

In this specification, an antiviral agent having a portion exposed from the surface of the resin portion is referred to as "antiviral agent A", and an antiviral agent having no portion exposed from the surface of the resin portion is referred to as "antiviral agent A". It is sometimes called "antiviral agent B".

The antiviral agent preferably has a portion exposed from the surface of the resin portion opposite to the substrate side. The antiviral agent preferably contains an antiviral agent A having a portion exposed from the surface of the resin portion opposite to the substrate side. In this case, the immediate effect of the antiviral action can be further enhanced.

The average particle size of the antiviral agent is preferably 0.1 µm or more, more preferably 1 µm or more, preferably 10 µm or less, and more preferably 5 µm or less. When the average particle size of the antiviral agent is equal to or more than the lower limit and equal to or less than the upper limit, an antiviral layer having excellent dispersibility of the antiviral agent can be obtained satisfactorily. can be further enhanced.

The average particle size of the antiviral agent is the average particle size of the entire antiviral agent. Therefore, for example, when the laminate contains the antiviral agent A and the antiviral agent B, the average particle size of the antiviral agent contains the antiviral agent A and the antiviral agent B. It is the average particle size of the entire antiviral agent. The average particle size of the antiviral agent is preferably the number average particle size. The average particle size of the antiviral agent can be obtained, for example, by dispersing the antiviral agent in a solvent such as squalane and performing laser diffraction particle size distribution measurement.

In the laminate, the average height of the portion where the antiviral agent A is exposed is the average height of the portion where the antiviral agent A is exposed from the surface of the resin portion opposite to the base material side. It is. The height of the exposed portion of the antiviral agent A is, as shown in FIG. . The average height of the exposed portion of the antiviral agent A is the average height of the exposed portion of the antiviral agent A (distance h). When calculating the average height of the exposed portion of the antiviral agent A, the antiviral agent B, which does not have a portion exposed from the surface of the resin portion, is not included in the measurement target.

Using a laser microscope, the average height of the exposed portion of the antiviral agent A was determined for 20 arbitrary antiviral agents A having exposed portions in the laminate. It can be obtained by obtaining the height of the exposed portion and averaging them.

In the laminate, the ratio of the average height of the exposed portion of the antiviral agent A to the average particle size of the antiviral agent (average height of the exposed portion of antiviral agent A/antiviral The average particle diameter of the agent) is preferably 0.1 or more, more preferably 0.3 or more, and preferably 0.6 or less, more preferably 0.4 or less. When the above ratio (average height of exposed portion of antiviral agent A/average particle size of antiviral agent) is at least the above lower limit, the immediate antiviral action can be further enhanced even after stretching. can. When the above ratio (average height of exposed portion of antiviral agent A/average particle size of antiviral agent) is equal to or less than the above upper limit, the antiviral agent is removed from the surface of the laminate and the surface of the secondary molded product. It can be made more difficult to peel off.

Details of the base material and the antiviral layer are further described below.

(Base material)
The laminate comprises a stretchable substrate. The base material can be stretched. The material of the base material is not particularly limited as long as it can be stretched.

From the viewpoint of stretching, the substrate preferably contains a resin. The substrate is preferably a resin substrate.

The resin contained in the base material is not particularly limited. The resin contained in the base material may be a thermoplastic resin or a cured product of a thermosetting resin. Only one kind of the resin contained in the base material may be used, or two or more kinds thereof may be used in combination.

Examples of the resin contained in the base material include polypropylene (PP) resin, polyvinyl chloride (PVC) resin, polymethyl methacrylate (PMMA) resin, polystyrene (PS) resin, polycarbonate resin, polyethylene terephthalate (PET) resin, aromatic group polyester resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, methyl methacrylate-styrene (MS) resin, methyl methacrylate-butadiene-styrene (MBS) resin, epoxy resin, polyurethane resin, polyethylene ( PE) resin, polyetheretherketone (PEEK) resin, polyetherketoneketone (PEKK) resin, thermoplastic olefin (TPO) resin, polytetrafluoroethylene resin, polyvinyl fluoride (PVF) resin, and silicone resin. be done.

From the viewpoint of obtaining a good secondary molded product by stretching the laminate, the substrate preferably contains a thermoplastic resin, and the resin contained in the substrate is preferably a thermoplastic resin. preferable. However, even when the laminate is stretched and used, a cured product of a thermosetting resin or a cured product of a photocurable resin can be used as the resin contained in the base material.

When the substrate contains the resin or is the resin substrate, the content of the resin in 100% by weight of the substrate is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably is at least 95% by weight, particularly preferably at least 98% by weight. In 100% by weight of the base material, the content of the resin may be 100% by weight, may be 100% by weight or less, may be less than 100% by weight, or may be less than 99% by weight. good too.

When the resin contained in the substrate is the thermoplastic resin, the content of the thermoplastic resin in 100% by weight of the substrate is preferably 80% by weight or more, more preferably 90% by weight or more, More preferably 95% by weight or more, particularly preferably 98% by weight or more. In 100% by weight of the base material, the content of the thermoplastic resin may be 100% by weight, may be 100% by weight or less, may be less than 100% by weight, or may be less than 99% by weight. There may be.

The base material may be sheet-like, or may be in a shape other than a sheet-like shape.

The thickness of the sheet-like substrate (thickness of the substrate sheet) may be 1 mm or more, 3 mm or more, 15 mm or less, or 10 mm or less.

The substrate may contain other ingredients such as, for example, colorants, thickeners, fillers, antimicrobial agents, flame retardants, antifungal agents, UV absorbers, and tackifiers. Only one of the other components may be used, or two or more thereof may be used in combination.

(antiviral layer)
The antiviral layer includes an antiviral agent and a resin portion.

The visible light transmittance of the antiviral layer is preferably 70% or more, more preferably 75% or more, even more preferably 80% or more, still more preferably 85% or more, even more preferably 90% or more, and particularly preferably is 95% or more, most preferably 99% or more. When the visible light transmittance of the antiviral layer is equal to or higher than the lower limit, the transparency of the antiviral layer can be further enhanced. The visible light transmittance of the antiviral layer may be 100% or less, may be less than 100%, may be 90% or less, may be 80% or less, or may be 75% or less. may be

The visible light transmittance of the antiviral layer is the average value of the measured values obtained when the transmittance in the wavelength range of 380 nm to 780 nm is measured at wavelength intervals of 5 nm. The visible light transmittance of the antiviral layer can be measured, for example, using a spectrophotometer (for example, "Spectroscopic Haze Meter SH7000" manufactured by Nippon Denshoku Kogyo Co., Ltd.).

The average thickness of the antiviral layer is preferably 2 μm or more, more preferably 5 μm or more, still more preferably 6 μm or more, particularly preferably 10 μm or more, and preferably 30 μm or less, more preferably 20 μm or less. When the average thickness of the antiviral layer is at least the lower limit, the antiviral agent can be made more difficult to peel off from the surface of the laminate and the surface of the secondary molded product. When the average thickness of the antiviral layer is equal to or less than the upper limit, the transparency of the antiviral layer can be enhanced. Moreover, when the average thickness of the antiviral layer is equal to or more than the lower limit and equal to or less than the upper limit, it is possible to effectively suppress breakage of the antiviral layer during stretching.

The average thickness of the antiviral layer can be measured with a spectroscopic interference film thickness meter or by observing a cross section of the antiviral layer with a scanning electron microscope (SEM).

The ratio of the average thickness of the antiviral layer to the average particle size of the antiviral agent is described as a ratio (average thickness of antiviral layer/average particle size of antiviral agent). The above ratio (average thickness of antiviral layer/average particle size of antiviral agent) is preferably 1.0 or more, more preferably 1.50 or more, still more preferably 1.69 or more, and particularly preferably 2.0 or more. , most preferably 2.2 or more, preferably 5.0 or less, more preferably 3.5 or less, still more preferably 2.5 or less. When the above ratio (average thickness of antiviral layer/average particle size of antiviral agent) is at least the above lower limit, the antiviral agent can be made more difficult to peel off from the surface of the secondary molded product even after stretching. . In particular, when the ratio (average thickness of the antiviral layer/average particle size of the antiviral agent) is 1.0 or more, the antiviral agent is released from the surface of the laminate more than when it is less than 1.0. It becomes considerably difficult to peel off, and the antiviral agent becomes considerably difficult to peel off from the surface of the secondary molded product even after stretching. In particular, when the ratio (average thickness of the antiviral layer/average particle size of the antiviral agent) is 1.69 or more, the antiviral agent is released from the surface of the laminate more than when it is less than 1.69. It becomes remarkably difficult to peel off, and furthermore, it becomes remarkably difficult to peel off the antiviral agent from the surface of the secondary molded product even after stretching. When the ratio (average thickness of the antiviral layer/average particle size of the antiviral agent) is equal to or less than the upper limit, the antiviral layer can maintain good transparency.

<Antiviral agent>
The antiviral layer contains the antiviral agent. Conventionally known antiviral agents can be used as the antiviral agent. Only one type of the antiviral agent may be used, or two or more types may be used in combination.

Examples of the antiviral agent include an inorganic antiviral agent, an organic antiviral agent, and an antiviral agent in which a surfactant is supported on inorganic particles.

Inorganic antiviral agents:
Examples of the inorganic antiviral agents include antiviral agents containing metals, metal ions, or metal compounds. Examples of the inorganic antiviral agents include silver-based antiviral agents such as silver-containing particles and copper-based antiviral agents such as copper-containing particles.

Examples of the silver-based antiviral agent (silver-containing particles) include silver particles, silver salt particles, silver complex particles, and the like. Examples of the silver salt include silver nitrate, silver sulfate, and silver chloride. Examples of the silver complex include a thiosulfite silver complex and a silver sodium chloride complex.

Further, examples of the silver-based antiviral agent (silver-containing particles) include particles in which a silver-containing compound is supported on a carrier. Examples of the silver-containing compound include silver, silver salts and silver complex particles. Examples of the carrier include zeolite, silica gel, silicate, phosphate, soluble glass, activated carbon and metal carrier.

Furthermore, colloidal silver is also exemplified as the silver-based antiviral agent (silver-containing particles). The average particle size of the colloidal silver is, for example, 1 nm or more and 1 μm or less. The average particle size of the colloidal silver is preferably a number average particle size.

Organic antiviral agents:
Examples of the organic antiviral agent include an antiviral agent containing a surfactant, and examples thereof include an antiviral agent in which a surfactant is supported on organic particles.

Examples of the material of the organic particles include resins. The organic particles are preferably resin particles.

The resin contained in the organic particles (resin particles) may be a thermoplastic resin or a cured product of a thermosetting resin.

Examples of the resin contained in the organic particles include polypropylene (PP) resin, polyvinyl chloride (PVC) resin, polymethyl methacrylate (PMMA) resin, polystyrene (PS) resin, polycarbonate resin, polyethylene terephthalate (PET) resin, aromatic group polyester resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, methyl methacrylate-styrene (MS) resin, methyl methacrylate-butadiene-styrene (MBS) resin, epoxy resin, polyurethane resin, polyethylene ( PE) resin, polyetheretherketone (PEEK) resin, polyetherketoneketone (PEKK) resin, thermoplastic olefin (TPO) resin, polytetrafluoroethylene resin, polyvinyl fluoride (PVF) resin, and silicone resin. be done.

Examples of the surfactant include anionic surfactants and cationic surfactants. Only one type of the surfactant may be used, or two or more types may be used in combination.

From the viewpoint of enhancing the immediate antiviral action, the surfactant is preferably a sulfonic acid-based surfactant.

Examples of the sulfonic acid-based surfactants include alkylbenzenesulfonic acid compounds, alkyldiphenyletherdisulfonic acid compounds, alkylnaphthalenesulfonic acid compounds, alkylsulfuric acid ester compounds, polyoxyethylene alkylsulfuric acid ester compounds, and formalin naphthalenesulfonic acid. A condensate type compound etc. are mentioned. The above sulfonic acid-based surfactants may be used alone or in combination of two or more.

From the viewpoint of further enhancing the immediate antiviral action, the sulfonic acid-based surfactant is preferably an alkylbenzenesulfonic acid-based compound, an alkyldiphenyletherdisulfonic acid-based compound, or an alkylnaphthalenesulfonic acid-based compound.

In the antiviral agent in which a surfactant is supported on the organic particles, the content of the surfactant with respect to 100 parts by weight of the organic particles (the amount of the surfactant supported with respect to 100 parts by weight of the organic particles) is It is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, preferably 50 parts by weight or less, and more preferably 40 parts by weight or less. When the content of the surfactant is equal to or more than the lower limit and equal to or less than the upper limit, the immediate effect of the antiviral action can be further enhanced.

Antiviral agent in which a surfactant is supported on inorganic particles:
Examples of the inorganic particles include calcium carbonate particles, talc particles, silica particles, aluminum hydroxide particles, magnesium hydroxide particles, titanium oxide particles, clay particles, mica particles, wollastonite particles, zeolite particles, zinc oxide particles, and magnesium oxide. particles, carbon black particles, graphite particles, glass bead particles, and the like.

Examples of the surfactant include the surfactants described in the organic antiviral agent section above.

In the antiviral agent in which a surfactant is supported on the inorganic particles, the content of the surfactant with respect to 100 parts by weight of the inorganic particles (the amount of the surfactant supported with respect to 100 parts by weight of the inorganic particles) is It is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, preferably 50 parts by weight or less, and more preferably 40 parts by weight or less. When the content of the surfactant is equal to or more than the lower limit and equal to or less than the upper limit, the immediate effect of the antiviral action can be further enhanced.

The heat resistant temperature of the antiviral agent is preferably 160° C. or higher, more preferably 200° C. or higher, still more preferably 215° C. or higher, and particularly preferably 230° C. or higher. When the heat resistant temperature of the antiviral agent is equal to or higher than the above lower limit, stretching can be easily performed. In particular, when the heat resistant temperature of the antiviral agent is 200° C. or higher, the drawing process can be performed more easily than when the heat resistance temperature is lower than 200° C., and the antiviral effect after the drawing process can be significantly enhanced. can. The heat resistant temperature of the antiviral agent may be 400° C. or lower, or 300° C. or lower.

The heat resistant temperature of the antiviral agent can be measured by an antiviral test. The temperature at which the antiviral agent maintains its antiviral properties even after being heated with a heater is defined as the heat resistant temperature of the antiviral agent. The above-mentioned "maintaining antiviral properties" means that the antiviral activity value determined in accordance with ISO21702, which will be described later, is 2.0 or more.

The content of the antiviral agent in 100% by weight of the antiviral layer is preferably 2% by weight or more, more preferably 5% by weight or more, still more preferably 10% by weight or more, and preferably 50% by weight or less, More preferably, it is 40% by weight or less. When the content of the antiviral agent is equal to or higher than the lower limit, the immediate effect and durability of the antiviral action can be further enhanced even after stretching. When the content of the antiviral agent is equal to or less than the above upper limit, an antiviral layer having excellent dispersibility of the antiviral agent can be obtained satisfactorily, and as a result, the antiviral properties can be further enhanced even after stretching. can be done.

The content of the antiviral agent in the antiviral layer is preferably 2 parts by weight or more, more preferably 10 parts by weight or more, relative to 100 parts by weight of the resin part in the antiviral layer. It is 100 parts by weight or less, more preferably 70 parts by weight or less. When the content of the antiviral agent is equal to or higher than the lower limit, the immediate effect and durability of the antiviral action can be further enhanced even after stretching. When the content of the antiviral agent is equal to or less than the above upper limit, an antiviral layer having excellent dispersibility of the antiviral agent can be obtained satisfactorily, and as a result, the antiviral properties can be further enhanced even after stretching. can be done.

<Resin part>
The resin portion contains a resin. From the viewpoint of improving designability, the resin portion is preferably a transparent resin portion.

The resin contained in the resin portion may be a thermoplastic resin, a cured thermosetting resin, or a cured photocurable resin.

Examples of the resin contained in the resin portion include olefin resins, vinyl resins, ester resins, and the like. More specifically, the resin contained in the resin portion includes polypropylene (PP) resin, polyvinyl chloride (PVC) resin, polymethyl methacrylate (PMMA) resin, polystyrene (PS) resin, polycarbonate resin, and polyethylene terephthalate. (PET) resin, aromatic polyester resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, methyl methacrylate-styrene (MS) resin, methyl methacrylate-butadiene-styrene (MBS) resin, epoxy resin , polyurethane resin, polyethylene (PE) resin, polyetheretherketone (PEEK) resin, polyetherketoneketone (PEKK) resin, thermoplastic olefin (TPO) resin, polytetrafluoroethylene resin, polyvinyl fluoride (PVF) resin, and silicone resins. The resin contained in the resin portion may be a copolymer resin of each of the resins described above.

The resin contained in the base material and the resin contained in the resin portion may be the same or different.

From the viewpoint of obtaining a good secondary molded product by stretching the laminate, the resin portion preferably contains a thermoplastic resin, and the resin contained in the resin portion is preferably a thermoplastic resin. preferable. However, even when the laminate is stretched and used, a cured product of a thermosetting resin or a cured product of a photocurable resin can be used as the resin contained in the resin portion.

The resin contained in the resin portion is preferably an olefin resin, a vinyl resin, an ester resin, an ABS resin, or a copolymer resin of these resins, and more preferably an MS resin. In this case, the transparency of the antiviral layer can be further enhanced, and the laminate can be stretched to obtain a good secondary molded product.

The total content of the antiviral agent and the resin part in 100% by weight of the antiviral layer is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 98% by weight or more, and particularly preferably 99% by weight or more, most preferably 100% by weight. However, the above total content may be 100% by weight or less, or may be less than 100% by weight.

<Other ingredients>
The antiviral layer may contain other ingredients different from both the resin and the antiviral agent. The antiviral layer may contain other ingredients such as, for example, thickeners, fillers, antimicrobial agents, flame retardants, antifungal agents, UV absorbers, and tackifiers. Only one of the other components may be used, or two or more thereof may be used in combination.

(Other Details of Stretching Laminate)
In the laminate, the antiviral activity value determined according to ISO21702 is preferably 2.0 or more when the antiviral layer and the virus solution are brought into contact for 10 minutes. In this case, the immediate effect of the antiviral action can be further enhanced.

In the laminate, when the antiviral layer and the virus solution are brought into contact for 24 hours, the antiviral activity value determined in accordance with ISO21702 is preferably 2.0 or more, more preferably 2.5 or more, More preferably, it is 3.0 or more. In this case, the antiviral action can be further enhanced.

As the virus liquid for measuring the antiviral activity value, for example, an influenza virus liquid can be used. The antiviral activity value can be obtained as follows.

A sample for evaluation is obtained by cutting the laminate so that the size of the antiviral layer is 50 mm long and 50 mm wide. The obtained antiviral layer of the evaluation sample is brought into contact with a virus solution (eg, influenza virus solution) at 25° C. for 10 minutes or 24 hours. Next, the virus fluid is collected, and the antiviral activity value is determined by the plaque method according to ISO21702. The antiviral activity value is preferably an average value of antiviral activity values calculated using two or more samples for evaluation.

In the laminate, the substrate and the antiviral layer may or may not be directly laminated. The laminate may have another layer between the substrate and the antiviral layer.

An adhesion layer etc. are mentioned as said another layer. Examples of materials for the adhesive layer include adhesives and the like.

The thickness of the adhesive layer is preferably 1 nm or more, preferably 100 nm or less, and more preferably 10 nm or less.

A method for forming the adhesive layer is not particularly limited. Examples of the method of forming the adhesive layer include a method of forming by sputtering. When the adhesive layer is formed by sputtering, the thickness of the adhesive layer is preferably 10 nm or less.

The shape of the laminate is not particularly limited. The laminate may be sheet-like, rod-like, or tubular. From the viewpoint of facilitating stretching, the laminate is preferably in the form of a sheet, and is preferably a laminated sheet for stretching.

The sheet-like laminate preferably has an average thickness of 1 mm or more, more preferably 3 mm or more, preferably 15 mm or less, and more preferably 10 mm or less.

The average thickness of the sheet-like laminate can be measured using a micrometer.

The substrate is stretchable and stretchable. The substrate may be stretchable 1.5 times or more, or may be stretchable 2 times or more. The substrate is preferably stretchable 3 times or more, more preferably 5 times or more. It is preferable that the base material does not break even when stretched to the above magnification. When the drawable ratio (molding ratio) is at least the above lower limit, breakage of the base material during drawing can be effectively suppressed, and versatility of the secondary molded product can be enhanced. The substrate may be stretchable up to 8 times. The antiviral layer is stretchable. It is preferable that the antiviral layer can be stretched as the base material is stretched.

The laminate is stretchable and stretchable. The laminate may be stretchable by a factor of 1.5 or more, or may be stretchable by a factor of 2 or more. The laminate is preferably stretchable by a factor of 3 or more, more preferably by a factor of 5 or more. It is preferable that the laminate does not break even when stretched to the above magnification. When the drawable ratio (molding ratio) is equal to or higher than the lower limit, breakage of the laminate during drawing can be effectively suppressed, and versatility of the secondary molded product can be enhanced. The laminate may be stretchable up to 8 times.

The method for manufacturing the laminate is not particularly limited.

The laminate can be produced, for example, by disposing a material for the antiviral layer on the first surface of the base material and then drying the material for the antiviral layer to form an antiviral layer. .

Further, in the laminate, for example, after disposing the material of the resin portion that does not contain the antiviral agent on the first surface of the base material, a liquid containing the antiviral agent is applied to the surface of the material of the resin portion. It can be produced by spraying.

Methods of disposing the material on the first surface of the substrate include coating, physical vapor deposition, chemical vapor deposition, sputtering, spraying, coating, plasma coating, dip coating, laminating, and the like.

The laminate can also be produced, for example, by forming an antiviral layer and then arranging the formed antiviral layer on the first surface of the base material.

Moreover, in the laminate, the antiviral layer may be arranged on the second surface side opposite to the first surface side of the base material. In this case, antiviral properties can be exhibited on both sides of the laminate.

[Secondary molded product]
A secondary molded product according to the present invention is a secondary molded product obtained by stretching the laminate described above. A secondary molded product can be produced by subjecting the laminate to vacuum forming, pressure forming, blow molding, embossing, and the like, and stretching the laminate.

The secondary molded product may be a vacuum molded product, a pressure molded product, a blow molded product, or an embossed molded product of the laminate.

The secondary molded product may be a secondary molded product obtained by stretching the laminate at a molding ratio of 1.5 times or more, or a secondary molded product obtained by stretching at a molding ratio of 8 times or less. may be The secondary molded product is preferably a secondary molded product obtained by stretching the laminate at a molding ratio of 2 times or more, and is a secondary molded product obtained by stretching at a molding ratio of 2 times or more. It is preferably a secondary molded product stretched at a molding ratio of 3 times or more, more preferably a secondary molded product stretched at a molding ratio of 6 times or less, and 5 times or less. It is more preferable that the secondary molded product is stretched at a molding ratio of . Therefore, the laminate is preferably stretched at a molding ratio of 2 times or more, more preferably stretched at a molding ratio of 3 times or more, and stretched at a molding ratio of 6 times or less. It is preferably used after being processed, and more preferably used after being stretched at a molding ratio of 5 times or less. When the molding ratio is equal to or higher than the lower limit and equal to or lower than the upper limit, damage to the antiviral layer during stretching can be effectively suppressed, and versatility of the secondary molded product can be enhanced.

The molding ratio of the laminate is the ratio of the area of the surface of the laminate after stretching to the area of the surface of the laminate before stretching (area of the surface of the laminate after stretching / laminate before stretching surface area). For example, a molding ratio of 5 times means that a square region having an area of 1 cm ² on the surface of the laminate before stretching changes into a region having an area of 5 cm ² after stretching. In addition, the molding ratio of the base material means that the "laminate" in the description of the molding ratio of the laminate is read as "base material".

In the secondary molded product, the ratio of the average thickness of the layer derived from the antiviral layer to the average particle size of the antiviral agent (average thickness of the layer derived from the antiviral layer/average particle size of the antiviral agent) is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.5 or more, preferably 3.0 or less, and more preferably 2.0 or less. When the above ratio (average thickness of layer derived from antiviral layer/average particle size of antiviral agent) is at least the above lower limit, the antiviral agent can be made more difficult to peel off from the surface of the secondary molded product. . When the above ratio (average thickness of the layer derived from the antiviral layer/average particle size of the antiviral agent) is equal to or less than the above upper limit, the transparency of the layer derived from the antiviral layer can be maintained satisfactorily.

In the secondary molded product, the antiviral activity value obtained in accordance with ISO21702 is preferably 2.0 or more when the layer derived from the antiviral layer is brought into contact with the virus solution for 10 minutes. In this case, the immediate effect of the antiviral action can be further enhanced. The antiviral activity value may be 2.0 or less.

In the secondary molded product, when the layer derived from the antiviral layer and the virus solution are brought into contact for 24 hours, the antiviral activity value determined in accordance with ISO 21702 is preferably 2.0 or more, particularly preferably 2.0 or more. is greater than or equal to 2.5, most preferably greater than or equal to 3.0. When the antiviral activity value is equal to or higher than the lower limit, the antiviral action can be further enhanced. The antiviral activity value may be 3.0 or less, or 2.5 or less.

In the laminate, the antiviral activity value determined according to ISO21702 when the antiviral layer and the virus solution are brought into contact for 24 hours is referred to as antiviral activity value A. In the secondary molded product, the antiviral activity value determined according to ISO21702 when the layer derived from the antiviral layer and the virus solution are brought into contact for 24 hours is referred to as antiviral activity value B. The ratio of the antiviral activity value B to the antiviral activity value A is described as a ratio (antiviral activity value B/antiviral activity value A).

When the laminate is stretched at a molding ratio of 3 times to obtain a secondary molded product, the ratio (antiviral activity value B/antiviral activity value A) is 0.50 or more ( preferably 0.67 or more). The laminate has a ratio (antiviral activity value B/antiviral activity value A) of 2.0 or less when a secondary molded product is obtained by stretching the laminate at a molding ratio of 3 times. It may be a laminate satisfying the ratio (antiviral activity value B/antiviral activity value A) of 1.5 or less. In addition, the laminate exhibiting such properties may be stretched at a molding ratio other than 3 times for use. When the laminate is stretched at a molding ratio of 5 times to obtain a secondary molded product, the ratio (antiviral activity value B/antiviral activity value A) is 0.50 or more ( preferably 0.67 or more). The laminate has a ratio (antiviral activity value B/antiviral activity value A) of 2.0 or less when a secondary molded product is obtained by stretching the laminate at a molding ratio of 5 times. It may be a laminate satisfying the ratio (antiviral activity value B/antiviral activity value A) of 1.5 or less. The laminate exhibiting such properties may be stretched at a molding ratio other than 5 times for use.

The secondary molded product is a secondary product obtained by stretching the laminate so that the ratio (antiviral activity value B/antiviral activity value A) is 0.50 or more (preferably 0.67 or more). Molded articles are preferred. The secondary molded product may be a secondary molded product obtained by stretching the laminate so that the ratio (antiviral activity value B/antiviral activity value A) satisfies 2.0 or less, It may be a secondary molded product that has been stretched so that the above ratio (antiviral activity value B/antiviral activity value A) is 1.5 or less. Therefore, the laminate is preferably stretched so that the ratio (antiviral activity value B/antiviral activity value A) satisfies 0.50 or more (preferably 0.67 or more). The laminate may be stretched and used so that the ratio (antiviral activity value B/antiviral activity value A) satisfies 2.0 or less, and the ratio (antiviral activity value B/antiviral activity value It may be stretched and used so that the activity value A) is 1.5 or less.

The antiviral activity value of the secondary molded product can be determined in the same manner as the method for measuring the antiviral activity value of the laminate described above.

[Antiviral member]
An antiviral member according to the present invention includes an antiviral member main body and the secondary molded article described above. The antiviral member main body may be a member having antiviral properties or may be a member having no antiviral properties. In the antiviral member, it is preferable that a layer derived from the base material of the secondary molded article is arranged on the main body side of the antiviral member. In the antiviral member, the surface layer of the antiviral member is preferably a layer derived from the antiviral layer.

The antiviral member can be produced, for example, as follows. First, the laminate is heated and softened. Next, the softened laminate is conformed to the mold of the antiviral member main body and deformed by vacuum suction to dispose the secondary molded product on the surface of the antiviral member main body.

The laminate and the secondary molded product are, for example, interior and exterior materials, toilets and food preparation areas of transportation equipment such as railway vehicles, aircraft, ships and automobiles; interior and exterior materials of buildings, toilets and food preparation areas; station premises ticket vending machines; information terminals in commercial facilities; and medical equipment in hospitals.

EXAMPLES The present invention will be specifically described below with reference to examples. The invention is not limited to the following examples.

The following materials were prepared.

(Base material)
Resin base material (PVC resin base material, "Takiflex EVC8600" manufactured by C.I. Takiron)

(Material for antiviral layer)
MS resin ("TX-100S" manufactured by Denka)
Antiviral agent 1 (antiviral agent in which a sulfonic acid-based surfactant is supported on polystyrene resin particles, average particle size 5 μm, heat resistance temperature 300° C.)
Antiviral agent 2 (silver-based antiviral agent, average particle size 8 μm, heat resistance temperature 350° C.)
Antiviral agent 3 (carboxylic acid antiviral agent, average particle size 3 μm, heat resistance temperature 180° C.) Ketone solvent (4-methyl-2-pentanone, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

(Example 1)
Preparation of antiviral layer material:
A resin-containing solution was obtained by dissolving the MS resin in a ketone solvent. Next, the antiviral agent 1 was added to the resulting resin-containing solution and stirred to obtain the material for the antiviral layer. The content of each component was set to the content shown in Table 1 in the antiviral layer to be obtained.

Preparation of laminate for stretch processing:
As shown in FIG. 3, the obtained antiviral layer material 2X was dropped on the first surface 1a of the substrate 1. As shown in FIG. While pressing both ends of the bar coater B strongly against the first surface 1a of the substrate 1, the bar coater B was moved (in the direction of the arrow in FIG. 3). In this way, the antiviral layer material 2X was applied onto the first surface 1a of the substrate 1 .

Next, the substrate coated with the antiviral layer material was heated in an oven at 40° C. for 5 minutes to dry the antiviral layer material. Thus, a laminate (laminated sheet) having an antiviral layer on the surface of the substrate was obtained.

Fabrication of the secondary molded product:
Using a vacuum forming machine, the obtained laminate was stretched at a molding ratio of 3 to prepare a secondary molded product. The molding ratio of 3 was confirmed by drawing grid-like lines with a width of 1 cm on the laminate before stretching, and confirming that a mass having an area of 1 ^cm2 had an area of 3 ^cm2 after stretching. .

(Examples 2 to 4 and Comparative Examples 1 and 2)
A laminate was obtained in the same manner as in Example 1, except that the composition and average thickness of the antiviral layer were changed as shown in Table 1 below. A secondary molded product was obtained in the same manner as in Example 1, except that the obtained laminate was stretched at the molding ratio shown in Table 1.

(evaluation)
(1) Average thickness of antiviral layer The average thickness of the antiviral layer was measured by cross-sectional observation with SEM.

(2) Antiviral activity value (2-1) Preparation of virus solution MDCK cells cultured in a 10 cm dish were inoculated with influenza virus and cultured at 37°C for 1 hour. After culturing, the culture supernatant containing unsensitized virus was removed. A new DMEM medium was added to the 10 cm dish from which the supernatant was removed, and cultured at 37° C. for 4 days. After culturing, the culture supernatant was collected and centrifuged at 800 rpm for 5 minutes. The supernatant after centrifugation was used as the virus solution.

(2-2) Measurement of Antiviral Activity Value of Laminate The obtained laminate was cut so that the size of the antiviral layer was 50 mm long and 50 mm wide to obtain a sample for evaluation. The obtained sample for evaluation is placed in a petri dish, 0.4 ml of a virus solution diluted 10-fold with sterile water is dropped on the surface of the antiviral layer side of the sample for evaluation, a cover film is placed on the petri dish, and the lid is placed on the petri dish. and allowed to stand at 25°C for 24 hours. Next, 10 ml of washing solution was added, and the virus fluid was collected from the sample for evaluation. The recovered virus solution was serially diluted 10-fold with cell maintenance medium. The diluted virus solution was inoculated into MDCK cells cultured in a 6-well plate, and the number of plaques was counted according to ISO21702 to determine the antiviral activity value. The test was performed on two samples for evaluation, and the average antiviral activity value was calculated.

(2-3) Measurement of antiviral activity value of secondary molded product Similarly, the antiviral activity value was measured. In addition, when the determination result of the antiviral activity value of the secondary molded product was "x", it was determined to be "unsuitable for stretching".

The antiviral activity value was determined according to the following criteria.

[Criteria for determination of antiviral activity value]
○: Antiviral activity value is 2.0 or more ×: Antiviral activity value is less than 2.0

(3) Peeling suppression property of antiviral agent Using a laser microscope ("OLS4000" manufactured by OLYMPUS), the surface of the layer derived from the antiviral layer in the secondary molded product was observed, and the surface of the resin part of the layer was observed. The number of exposed antiviral agents A (A) was counted. After that, using a microfiber cloth impregnated with tap water, the surface of the layer derived from the antiviral layer in the secondary molded product was wiped off at a pressure of 150 Pa 3650 times. Next, similarly, the surface of the layer derived from the antiviral layer was observed using a laser microscope, and the number (Aa) of antiviral agent A exposed from the surface of the resin portion of the layer was counted. The residual ratio of the antiviral agent was determined by the formula: number of antiviral agents A (Aa)/number of antiviral agents A (A), and the anti-stripping property of the antiviral agent was evaluated according to the following criteria. In addition, when the evaluation result of the spalling suppression property of the secondary molded product was "x", it was judged to be "unsuitable for stretching".

[Determination Criteria for Inhibition of Exfoliation of Antiviral Agent]
○: Residual ratio of antiviral agent is 0.9 or more ×: Residual ratio of antiviral agent is less than 0.9

The laminate structure and results are shown in Table 1 below.

As shown in Table 1, the laminates of Comparative Examples 1 and 2 had low antiviral activity values after stretching, and the laminate of Comparative Example 2 could not sufficiently suppress the peeling of the antiviral agent after stretching. Therefore, it became clear that it is not suitable for use after being stretched.

REFERENCE SIGNS LIST 1 Base material 1a First surface 2 Antiviral layer 10 Stretching laminate 21 Resin part 21a Surface 22 Antiviral agent 22A Antivirus having a portion exposed from the surface of the resin part Agent 22B ... Antiviral agent that does not have a portion exposed from the surface of the resin part

Claims (9)

A base material and an antiviral layer disposed on the first surface side of the base material,
A laminate for stretching, wherein the antiviral layer contains an antiviral agent and a resin portion. The laminate for stretching according to claim 1, wherein the antiviral agent has a heat resistant temperature of 200°C or higher. the substrate comprises a thermoplastic resin,
The laminate for stretching according to claim 1 or 2, wherein the resin contained in the resin portion is a thermoplastic resin. 3. The stretchable laminate according to claim 1, wherein the resin contained in the resin portion is an olefin resin, a vinyl resin, an ester resin, an ABS resin, or a copolymer resin of these resins. 3. The stretchable laminate according to claim 1, wherein the ratio of the average thickness of the antiviral layer to the average particle size of the antiviral agent is 1.0 or more. 6. The stretchable laminate according to claim 5, wherein the ratio of the average thickness of the antiviral layer to the average particle size of the antiviral agent is 1.69 or more. A secondary molded product obtained by stretching the laminate for stretching according to claim 1 or 2. 8. The secondary molded article according to claim 7, wherein the ratio of the average thickness of the layer derived from the antiviral layer to the average particle size of the antiviral agent is 0.5 or more. an antiviral member main body;
An antiviral member comprising the secondary molded product according to claim 7.

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