WO2017090661A1 - Élément inhibant la propagation dans le moule - Google Patents
Élément inhibant la propagation dans le moule Download PDFInfo
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- WO2017090661A1 WO2017090661A1 PCT/JP2016/084753 JP2016084753W WO2017090661A1 WO 2017090661 A1 WO2017090661 A1 WO 2017090661A1 JP 2016084753 W JP2016084753 W JP 2016084753W WO 2017090661 A1 WO2017090661 A1 WO 2017090661A1
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- protrusion
- present disclosure
- mold
- mold growth
- meth
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/10—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material
- B32B3/14—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a discontinuous layer, i.e. formed of separate pieces of material characterised by a face layer formed of separate pieces of material which are juxtaposed side-by-side
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
Definitions
- the embodiment of the present disclosure relates to a mold growth suppression member.
- Patent Literature 1 describes a method of suppressing the growth of mold at the applied portion by applying a fungicide.
- Patent Document 2 describes a laminate having an antibacterial / antifungal layer containing an antibacterial / antifungal agent in a synthetic resin as an outermost layer.
- Patent Document 3 as a material for achieving both high antifouling properties and high antibacterial and antiviral properties even under weak light such as indoor spaces, a water repellent resin binder, A water repellent photocatalyst composition containing a photocatalyst material and cuprous oxide, wherein the photocatalyst material and the cuprous oxide are combined, and a coating film thereof are disclosed.
- Patent Document 4 discloses an article having an antibacterial surface that has a specific raised structure on the surface of a substrate and the surface is superhydrophobic.
- Patent Documents 1 to 3 above antibacterial properties have been imparted to various articles by using antibacterial agents and the like. Further, as in Patent Document 4, it is necessary to use a special material in order to make the surface superhydrophobic. Under such circumstances, as a result of examining a means different from the method using an antibacterial agent as a means for imparting antibacterial properties, the present inventors have provided a specific group of protrusions on the surface of the article. It has been found that an excellent fungal growth inhibitory effect can be exhibited.
- the mold growth inhibiting member of the present disclosure has been completed based on such knowledge, and an object thereof is to provide a mold breeding inhibiting member having an excellent mold growth inhibiting effect.
- 1 embodiment of this indication is provided with the concavo-convex layer which has the projection structure provided with the projection group in which a plurality of projections are arranged on the surface,
- a mold growth suppressing member in which a width W of the protrusion is 1 ⁇ m or more and 20 ⁇ m or less, a height H of the protrusion is 1 ⁇ m or more and 20 ⁇ m or less, and a distance D between adjacent protrusions is 1 ⁇ m or more and 30 ⁇ m or less.
- a mold growth suppressing member in which a contact angle of water on the surface having the protrusion group is more than 10 degrees and less than 120 degrees by the ⁇ / 2 method.
- a mold growth suppressing member in which the protrusion rising angle ⁇ is not less than 30 degrees and not more than 120 degrees.
- the embodiment of the present disclosure can provide a mold growth suppression member having an excellent mold growth suppression effect.
- FIG. 1 is a schematic plan view schematically illustrating an example of a mold growth suppressing member according to the present disclosure.
- FIG. 2 is a schematic sectional view schematically showing an example of the A-A ′ sectional view of FIG. 1.
- FIG. 3 is a schematic cross-sectional view schematically illustrating another example of the mold growth suppressing member according to the present disclosure.
- FIG. 4 is a schematic cross-sectional view schematically illustrating another example of the mold growth suppressing member according to the present disclosure.
- FIG. 5 is a schematic plan view schematically illustrating another example of the mold growth suppressing member according to the present disclosure.
- FIG. 6 is a schematic plan view schematically illustrating another example of the mold growth suppressing member according to the present disclosure.
- FIG. 1 is a schematic plan view schematically illustrating an example of a mold growth suppressing member according to the present disclosure.
- FIG. 2 is a schematic sectional view schematically showing an example of the A-A ′ sectional view of FIG. 1.
- FIG. 3 is
- FIG. 7 is a diagram for describing a measurement region when measuring a surface having a protrusion group in the present disclosure.
- FIG. 8 is a diagram for explaining a method of measuring the rising angle ⁇ of the protrusion in the present disclosure.
- FIG. 9 is a diagram schematically illustrating an example of a usage mode of the mold growth suppressing member according to the present disclosure.
- FIG. 10 is a schematic cross-sectional view schematically showing an example of the B-B ′ cross-sectional view of FIG. 9.
- FIG. 11 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure.
- FIG. 12 is a schematic cross-sectional view schematically showing an example of a cross-sectional view taken along the line D-D ′ of FIG. 11.
- FIG. 13 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure.
- FIG. 14 is a schematic cross-sectional view schematically showing an example in which a part of the F-F ′ cross section of FIG. 13 is enlarged.
- FIG. 15 is a diagram schematically illustrating an example of a usage mode of an agricultural mold growth suppressing member according to the present disclosure.
- FIG. 16 is a diagram schematically illustrating another example of the usage mode of the agricultural mold growth suppressing member according to the present disclosure.
- FIG. 17 is a photomicrograph of an example of the surface of the mold growth inhibiting member according to the present disclosure after the mold resistance test.
- FIG. 18 is a photomicrograph at a different magnification of an example of the surface of the mold growth inhibiting member according to the present disclosure after the mold resistance test.
- FIG. 19 is a photomicrograph of the member surface after the mold resistance test in Comparative Example 1.
- the mold growth suppression member according to the present disclosure will be described in detail.
- the shape and geometric conditions and the degree thereof are specified.
- terms such as “orthogonal” and “identical”, length and angle values, and the like are bound to a strict meaning. Therefore, it should be interpreted including the extent to which similar functions can be expected.
- the “plan view” in this specification means visual recognition from the vertical direction (FIG. 1) with respect to the upper surface of the mold growth suppressing member. Usually, this corresponds to visual recognition from the direction perpendicular to the surface having the projection group of the mold growth suppressing member.
- (meth) acryl represents each of acryl and methacryl
- (meth) acrylate represents each of acrylate and methacrylate
- (meth) acryloyl represents each of acryloyl and methacryloyl.
- cured material of a resin composition means what solidified through or without undergoing a chemical reaction.
- the mold growth inhibiting member of the present disclosure includes a concavo-convex layer having a protrusion structure including a protrusion group in which a plurality of protrusions are arranged on the surface,
- the width W of the protrusion is 1 ⁇ m or more and 20 ⁇ m or less
- the height H of the protrusion is 1 ⁇ m or more and 20 ⁇ m or less
- the distance D between adjacent protrusions is 1 ⁇ m or more and 30 ⁇ m or less.
- the action of the mold growth inhibiting member according to the present disclosure has not yet been clarified as to the action of inhibiting mold growth, but is estimated as follows.
- mold spores adhere to a substrate or the like, they germinate and generate hyphae.
- the mycelium usually has a thread-like structure with a diameter of about 1 to 10 ⁇ m, and extends by tip growth while branching the substrate surface.
- some tips form a structure related to reproduction, that is, a spore sac or conidia. And a spore is formed from the structure, and mold grows.
- FIG. 17 is a photomicrograph of an example of the mold growth inhibiting member surface according to the present disclosure after the mold resistance test
- FIG. 18 is a different example of the mold propagation inhibiting member surface according to the present disclosure after the mold resistance test. It is a microscope picture of a magnification.
- the distance D between adjacent protrusions in the protrusion group is 1 ⁇ m or more and 30 ⁇ m or less, and the height H of the protrusion is 1 ⁇ m or more and 20 ⁇ m or less.
- the mold propagation suppressing member of the present disclosure has a protrusion width W of 1 ⁇ m or more and 20 ⁇ m or less, there is not enough space on the protrusion to grow a mycelium.
- the mold growth suppression member of the present disclosure it is estimated that the growth of hyphae, in particular, the branching of the hyphae is suppressed. Accordingly, the number of hyphae tips does not increase, and the formation of the structure related to reproduction at the tip of the hypha is suppressed. From such a thing, it is estimated that the mold propagation suppression member of this indication is suppressed mold growth.
- the mold growth suppression member of the present disclosure exhibits an effect of suppressing mold growth even under conditions (for example, a temperature of 20 ° C. or higher and 30 ° C. or lower and a humidity of 80% or higher) that are generally suitable for mold growth.
- the mold growth suppressing member of the present disclosure exhibits the effect of suppressing mold growth regardless of the contact angle of water due to the above-described action.
- FIG. 1 is a schematic plan view schematically illustrating an example of a mold growth suppressing member according to the present disclosure.
- FIG. 2 is a schematic cross-sectional view schematically showing an example of the AA ′ cross-sectional view of FIG.
- the mold growth suppressing member 10 according to the present disclosure is a protrusion structure including a protrusion group 2 in which a plurality of protrusions 3 are arranged on the surface of a base material 1.
- each protrusion constituting the protrusion group is formed so as to be planted with respect to the surface on the side having the protrusion group.
- the mold growth inhibiting member of the present disclosure may have any shape, but typically, the mold propagation suppressing member may have a protrusion group on one entire surface of the sheet-like base material.
- the mold growth suppressing member according to the present disclosure is a molded body molded into a predetermined shape, it may have a protrusion group on the entire surface or a protrusion group on a part of the surface. It may be.
- the sheet-like shape may be any one that bends so that it can be wound, one that does not bend enough to be wound, but that is bent by applying a load, or one that does not bend completely.
- FIG.3 and FIG.4 is a schematic cross section which shows the example different from FIG. 2 of the mold growth suppression member of this indication.
- the cross-sectional shape in the height direction of each protrusion is not particularly limited, and may be a rectangle as shown in the example of FIG. 2 or a tapered shape as shown in the example of FIG.
- the base of the substrate as shown in FIG. 4 may have a narrower shape (so-called reverse taper shape).
- 5 and 6 are schematic plan views illustrating another example of the mold growth suppressing member of the present disclosure that is different from FIG. When each projection in the present disclosure is viewed in plan, the planar view shape of the projection is not particularly limited, and may be a polygonal shape as illustrated in FIG. 1 or FIG.
- each protrusion is not particularly limited as long as the distance D between adjacent protrusions is 1 ⁇ m or more and 30 ⁇ m or less. It may be a regular arrangement as shown in FIGS. 1, 5 and 6, or may be a random arrangement in which the distance between the protrusions is in the range of 1 ⁇ m to 30 ⁇ m (not shown). ).
- the shape of the protrusion include a columnar shape such as a columnar shape, an elliptical columnar shape, a semicylindrical shape, a triangular columnar shape, a quadrangular columnar shape, and a hexagonal column; a conical shape, an elliptical cone shape, a triangular pyramid shape, a quadrangular pyramid shape, a hemispherical shape, Examples include tapered parabolic shapes, bell shapes, tapered shapes such as pencil shapes, and shapes similar to these.
- the plurality of protrusions may have the same shape or different shapes.
- the width W of the protrusion is 1 ⁇ m or more and 20 ⁇ m or less.
- the width W of the protrusion is 1 ⁇ m or more, the height H of the protrusion and the distance D between adjacent protrusions can be appropriately adjusted and combined to inhibit mycelial development, and the mechanical strength of the protrusion Also excellent.
- the width W of the protrusion is sufficient to be 20 ⁇ m or less, and if the width W is too large, the hypha may grow on the protrusion.
- the width W of the protrusion is preferably 10 ⁇ m or less from the viewpoint of improving the fungus growth inhibition effect.
- the plurality of protrusions may have the same width or different widths.
- the width W of the protrusion is the maximum value between two points on the outline of the protrusion when the protrusion is viewed in plan.
- the cross-sectional profile analysis is used to measure the distance between two points at each height in the cross section of the protrusion cut in the height direction, and the distance between the two largest points is defined as the width W of the protrusion.
- the width of the protrusion is the length of the diagonal line.
- the width of the protrusion is a diameter.
- the width of the protrusion is the maximum diameter of the bottom surface at the base position of the protrusion
- the width of the protrusion is It is the maximum diameter of the upper end surface or a surface in the vicinity thereof.
- the width of the protrusion when the planar view of the protrusion is a polygon other than a quadrangle is the maximum diagonal length.
- the width of the protrusion is the major axis of the ellipse.
- the base position of the protrusion refers to a position where the bottom surface of the protrusion, which is a surface connecting the minimum points of the protrusion base, intersects the protrusion side surface.
- the minimum point of the base of the protrusion can be measured using a cross section of the protrusion cut in the height direction.
- the cross-sectional profile analysis can be performed using, for example, a laser microscope or a three-dimensional optical profiler, and more specifically, can be performed using, for example, Olympus LEXT OLS4100 or Zygo ZeGage. .
- when measuring a surface having a projection group as shown in FIG.
- the height H of the protrusion is 1 ⁇ m or more and 20 ⁇ m or less.
- the height H of the protrusion is 1 ⁇ m or more, the mycelium is inhibited from growing on the protrusion, and the growth of mold can be suppressed.
- the protrusion height H is 20 ⁇ m or less, the mechanical strength is also excellent.
- the height H of the protrusion is preferably 2 ⁇ m or more, more preferably 4 ⁇ m or more from the viewpoint of improving the effect of inhibiting mold growth, and is preferably 10 ⁇ m or less from the viewpoint of mechanical strength. Is preferred.
- the plurality of protrusions may have the same height or different heights.
- the ratio (W / H) of the width W of the protrusion to the height H of the protrusion is not particularly limited, but is preferably 0.3 or more from the viewpoint of further suppressing the growth of mold. , 0.5 or more, more preferably 8 or less, and even more preferably 5 or less.
- the height H of the protrusion is a vertical distance from the base position of the protrusion to the apex of the protrusion, that is, the highest point. Specifically, the height of the protrusion can be measured using the cross-sectional profile analysis.
- the distance D between adjacent protrusions is 1 ⁇ m or more and 30 ⁇ m or less.
- the distance D between adjacent projections is within the range, the spores or mycelium attached to the mold growth-inhibiting member are likely to adhere between the projections, not the tip of the projection, and the mycelium that grows between the projections is branched. Inhibits mold growth.
- the distance D between adjacent protrusions is preferably 4 ⁇ m or more, more preferably 5 ⁇ m or more, from the viewpoint that spores or mycelium are likely to adhere between the protrusions and the effect of inhibiting mold growth is improved.
- the ratio (W / D) of the width W of the protrusion to the distance D between adjacent protrusions is not particularly limited, but may be 0.05 or more from the viewpoint of further suppressing the growth of mold. Preferably, it is preferably 0.1 or more, more preferably 5 or less, and even more preferably 3 or less.
- the distance D between adjacent protrusions is defined as follows.
- a projection belonging to a Voronoi region adjacent to the Voronoi region of one projection is adjacent to the projection It is defined as And about the protrusions contained in this adjacent Voronoi area
- the distance D between the protrusions can be defined by the repetition period of the protrusions.
- the distance D between adjacent protrusions can be measured from a plan view micrograph of the mold growth inhibitory member as appropriate in combination with the cross-sectional profile analysis.
- the rising angle ⁇ of the protrusion is preferably 30 degrees or more and 120 degrees or less.
- the rising angle ⁇ of the protrusion is 30 degrees or more, the mechanical strength of the protrusion is excellent.
- the rising angle ⁇ is 120 degrees or less, it is possible to suppress the development of the hyphae that run on the protrusions.
- the rising angle of the protrusion is preferably 40 degrees or more, more preferably 45 degrees or more, still more preferably 60 degrees or more, from the viewpoint of mechanical strength of the protrusion, Is preferably 110 degrees or less, and more preferably 100 degrees or less from the viewpoint of suppressing the development on the protrusions.
- the plurality of protrusions may have the same rising angle or may have different angles.
- the rising angle ⁇ of the protrusions is the base position b1 of the protrusion and the protrusion adjacent to the protrusion in the cross section used for the measurement of the width W of the protrusion, as shown in FIG.
- the point H 30 is 30% higher than the height H of the protrusion on the side surface of the protrusion.
- % a straight line L4 ′ passing through a 70% high point H 70% .
- the number of the protrusions per unit area in a plan view of the surface having the protrusion group is appropriately determined by a combination of the height H of the protrusion and the distance D between adjacent protrusions.
- it is preferably 40,000 pieces / cm 2 or more, more preferably 100,000 pieces / cm 2 or more, more preferably 600,000 pieces / cm 2 from the viewpoint of improving the effect of inhibiting mold growth. More preferably, it is more than cm 2, more preferably less than 5 million pieces / cm 2 , more preferably less than 4 million pieces / cm 2, and less than 3 million pieces / cm 2. Is even more preferable.
- the portion without the specific protrusion is typically a substantially flat surface, but the surface of the mold growth suppression member itself is curved. Or may have resentment.
- a substantially flat surface means that it may have, for example, scratches or fine irregularities derived from a material, such as 1/100 or less than the lower limit of the height of the specific protrusion.
- a convex portion different from the specific projection may be included in a part of the surface unless the effect of the present disclosure can be obtained.
- the area where a plurality of the specific protrusions are arranged at the specific distance D between adjacent protrusions is 70% or more with respect to the total area where the protrusions are arranged. Is more preferable, 80% or more is preferable, and 90% or more is more preferable.
- the protrusion group is formed on the surface of a concavo-convex layer made of a material different from the substrate described later, and the protrusion group is the same as the substrate described later.
- examples thereof include those made of a material and formed on the surface of a concavo-convex layer integrated with the base material, and those having no base material and the projection group formed on the surface of a single concavo-convex layer.
- the uneven layer on which the projection group is formed may be a single layer or a multilayer.
- the material of the projection group described below is a material used for forming the uneven layer.
- the material of the concavo-convex layer is not particularly limited as long as it is a material that can form the protruding structure, and can be appropriately selected according to the application. Even if it is a transparent material, it is an opaque material. Also good.
- various resin compositions soda glass, potassium glass, alkali-free glass, glass such as lead glass, ceramics such as lead lanthanum zirconate titanate (PLZT), quartz, fluorite, various metal oxides Examples thereof include inorganic materials such as materials, metals such as silver, copper, and iron and alloys thereof, and combinations of these materials.
- the material of the uneven layer is preferably made of a cured product of the resin composition because the shape of the projection group can be maintained for a longer period.
- the resin composition contains at least a resin and optionally contains other components such as a polymerization initiator.
- by forming the projection group by molding by appropriately adjusting the composition of the resin composition by forming the projection group from a cured product of the resin composition it is possible to easily improve the fungal growth suppression effect by improving the properties and adding various additives. Furthermore, in the combination of various additives and the protruding structure, an effect of reducing the amount of additives for obtaining a sufficient antifungal effect can be expected.
- the temperature and time for curing the resin composition can be adjusted by adjusting the type and content of the resin and the polymerization initiator.
- the curing conditions can be adjusted so that the protrusion group does not change.
- the resin examples include, but are not limited to, ionizing radiation curable resins such as (meth) acrylate, epoxy, and polyester, melamine, phenol, polyester, (meth) acrylate, urethane, and urea. , Epoxy, polysiloxane, and other thermosetting resins, polyamide, polyolefin, polyvinyl chloride, (meth) acrylate, polyester, polycarbonate, polyethylene, polypropylene, polystyrene, etc. Examples thereof include resins.
- the ionizing radiation means electromagnetic waves or charged particles having energy that can be cured by polymerizing molecules.
- An ionizing radiation curable resin is a mixture of a monomer having a radical polymerizable and / or cationic polymerizable bond in the molecule, a polymer having a low polymerization degree, and a reactive polymer, and is cured by a polymerization initiator. It is what is done.
- an ionizing radiation curable resin composition including an ionizing radiation curable resin and a thermosetting resin composition including a thermosetting resin are particularly preferable from the viewpoint of excellent moldability and mechanical strength of the protruding structure. Things are preferred.
- the said resin composition contains (meth) acrylate type resin. Since the (meth) acrylate resin can generate a sterilization gas, antibacterial properties can be improved.
- the ionizing radiation curable resin composition containing (meth) acrylate that is particularly preferably used among the ionizing radiation curable resins that are preferably used from the viewpoint of excellent moldability and mechanical strength of the protrusions will be described below in detail. Explained.
- the (meth) acrylate is a polyfunctional acrylate having two or more (meth) acryloyl groups in one molecule, even if it is a monofunctional (meth) acrylate having one (meth) acryloyl group in one molecule.
- monofunctional (meth) acrylate and polyfunctional (meth) acrylate may be used in combination.
- polyfunctional acrylate examples include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene di (meth) acrylate, hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and bisphenol.
- content of the said polyfunctional (meth) acrylate is 40 mass% or more and 99.9 mass% or less with respect to the total solid of the said ionizing radiation-curable resin composition, and 50 mass% or more and 99.99 mass%. It is preferable that it is 5 mass% or less.
- content of the said polyfunctional (meth) acrylate is 40 mass% or more and 99.9 mass% or less with respect to the total solid of the said ionizing radiation-curable resin composition, and 50 mass% or more and 99.99 mass%. It is preferable that it is 5 mass% or less.
- the solid content represents all components excluding the solvent.
- monofunctional (meth) acrylates include, for example, methyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate , Butoxyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) Chroch
- the content of the monofunctional (meth) acrylate is preferably 1% by mass or more and 30% by mass or less with respect to the total solid content of the ionizing radiation curable resin composition. More preferably, the content is 3% by mass or more and 15% by mass or less.
- a photopolymerization initiator may be appropriately selected and used as necessary.
- the photopolymerization initiator include, for example, in the case of a radical polymerization type ionizing radiation curable resin such as (meth) acrylate, bisacylphosphinoxide, 1-hydroxycyclohexyl phenyl ketone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy -2-Methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenyl-propane-1-
- the content of the photopolymerization initiator is usually preferably 0.1% by mass or more and 10% by mass or less based on the total solid content of the ionizing radiation curable resin composition. More preferably, the content is 0.5% by mass or more and 5% by mass or less.
- the ionizing radiation curable resin composition may further contain other components as long as the effects of the present disclosure are not impaired.
- Other components include, for example, surfactants for adjusting wettability, fluorine compounds, silicone compounds, stabilizers, antifoaming agents, anti-repellent agents, antioxidants, and aggregation prevention. Agents, viscosity modifiers, release agents and the like.
- the surface of the member having the projection group on the surface may be further subjected to surface treatment.
- a vapor deposition film such as a fluorine-based compound or a silicone-based compound may be provided on the surface including the protrusion group.
- the mold growth inhibiting member according to the present disclosure may include a base material as a support.
- the base material used for the mold growth inhibiting member of the present disclosure can be appropriately selected depending on the application, and may be a transparent base material or an opaque base material, and is not particularly limited.
- the material for the transparent substrate include acetyl cellulose resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, olefin resins such as polyethylene and polymethylpentene, and (meth) acrylic resins.
- Polyurethane resin Polyethersulfone, polycarbonate, polysulfone, polyether, polyetherketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer resin, soda glass, potassium glass, alkali-free glass, lead glass Glass, ceramics such as lead lanthanum zirconate titanate (PLZT), and transparent inorganic materials such as quartz and fluorite.
- PZT lead lanthanum zirconate titanate
- transparent inorganic materials such as quartz and fluorite.
- the material for the opaque base material include metal, paper, fabric, wood, stone, and composite materials thereof, and composite materials of these materials with the transparent base material.
- the base material and the projection group are integrally formed, as the material of the base material, for example, a thermoplastic resin or the above-described resin composition for forming a projection can be used.
- the substrate may be a sheet or a film, and may be any of those that can be wound, those that do not bend enough to be wound, but that can be bent by applying a load, and those that do not bend completely. May be.
- the thickness of a base material can be suitably selected according to a use and is not specifically limited, Usually, they are 10 micrometers or more and 5000 micrometers or less.
- the configuration of the base material used for the mold growth inhibiting member of the present disclosure is not limited to a configuration composed of a single layer, and may have a configuration in which a plurality of layers are stacked.
- the layer of the same composition may be laminated
- the projection group is formed on a concavo-convex layer made of a material different from the base material, the adhesion between the base material and the concavo-convex layer is improved, and as a result, the wear resistance (scratch resistance) is improved.
- the primer layer may be formed on the substrate.
- a transparent substrate is preferably used as the substrate.
- a transparent substrate is preferably used as the substrate.
- a transparent substrate is preferably used as the substrate.
- a polyester-based resin base material such as polyethylene terephthalate (PET) from the viewpoint of imparting scattering resistance when the glass is broken.
- the mold growth suppressing member according to the present disclosure may be a laminate with an adhesive layer.
- the adhesive layer is typically located on the surface side that does not have the protruding structure.
- the adhesive layer is provided on the outermost surface or under a peelable protective film, which will be described later, in order to attach the mold propagation inhibiting member according to the present disclosure to another article or the like.
- the mold propagation suppressing member according to the present disclosure has two or more layers, it may be located between the layers in order to bond the layers.
- a well-known adhesive agent can be used as a material of the said contact bonding layer and it does not specifically limit.
- the mold growth inhibiting member according to the present disclosure may have a peelable protective film on at least a part of its surface.
- the mold growth inhibiting member according to the present disclosure is a form in which a protective film that can be peeled at least partially is temporarily attached, stored, transported, traded, post-processed or constructed, and the protective film is peeled and removed in a timely manner. It can also be.
- the mold growth suppressing member according to the present disclosure is not particularly limited, but the total light transmittance in the visible region can be 80% or more depending on the application.
- the transmittance is equal to or higher than the lower limit value, in the aspect of using the mold growth suppressing member according to the present disclosure attached to another article, it is possible to suppress damage to the design property of the base, and visibility Can be excellent.
- the transmittance can be measured by JIS K7361-1 (Plastic—Testing method for total light transmittance of transparent material).
- the static contact angle of water on the surface of the mold growth inhibiting member according to the present disclosure is not particularly limited, but the contact angle of water on the surface having the protrusion group is more than 10 degrees and less than 120 degrees by the ⁇ / 2 method. Even so, it is possible to suitably suppress the growth of mold. In general, when the contact angle of water is more than 10 degrees and less than 120 degrees by the ⁇ / 2 method, there is a problem that water tends to remain on the surface and mold tends to propagate. In addition, in the mold growth suppressing member according to the present disclosure, the contact angle of water on the surface having the protrusion group is preferably 40 degrees or more and 100 degrees or less, more preferably 45 degrees or more and 85 degrees, by the ⁇ / 2 method.
- the angle is 60 degrees or more and 80 degrees or less from the viewpoint that both the effect of inhibiting mold growth and the strength of the protrusions can be easily achieved.
- the static contact angle of water is defined as a straight solid that connects 1.0 ⁇ L of pure water to the surface of the object to be measured, and one second after the landing, connecting the left and right end points and the vertex of the dropped liquid.
- the contact angle measured according to the ⁇ / 2 method for calculating the contact angle from the angle to the surface is used.
- a contact angle meter DM 500 manufactured by Kyowa Interface Science Co., Ltd. can be used as the measuring device.
- the pencil hardness on the surface having the protrusion group of the mold growth suppressing member according to the present disclosure is not particularly limited, but is preferably H or more from the viewpoint of excellent mechanical strength of the mold growth suppressing member. More preferably.
- the pencil hardness is measured according to JIS K5600-5-4 (Test pencil specified in JIS-S-6006) after the measurement sample is conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60%. 1999) can be performed by performing a pencil hardness test (0.98N load) as defined in 1999) on the surface of the measurement sample having the projection group and evaluating the highest pencil hardness without scratches.
- a pencil scratch coating film hardness tester manufactured by Toyo Seiki Co., Ltd. can be used.
- the method for producing a mold growth inhibiting member is not particularly limited as long as it is a method capable of producing the mold propagation inhibiting member according to the present disclosure as described above.
- the uneven shape of the projection group forming original plate is shaped.
- a coating film of the resin composition for forming an uneven layer is subjected to pattern exposure and development to form a desired pattern. And a method of performing etching.
- the pattern exposure may be performed so as to be a pattern corresponding to the planar shape of the projection group structure.
- a general method such as a method of exposing through a photomask or a laser drawing method may be used. it can.
- a projection group forming original plate having a surface having a concavo-convex shape in which a large number of holes are formed is prepared, and the surface having the concavo-convex shape of the projection group forming original plate is applied to the coating film surface of the resin composition for forming the concavo-convex layer.
- the method for curing or solidifying the resin composition for forming an uneven layer can be appropriately selected according to the type of the resin composition for forming an uneven layer.
- a thermoplastic resin composition containing a thermoplastic resin is used as the resin composition for forming an uneven layer, it is heated at a temperature appropriately selected in accordance with the softening temperature of the thermoplastic resin, and the projection group forming original plate
- the surface having the concavo-convex shape is pressed against the surface of the thermoplastic resin composition to mold the projection group, and after cooling and solidifying, the surface of the thermoplastic resin composition is peeled off from the projection group forming original plate.
- a desired projection group can be formed by molding.
- the projection group forming original plate is not particularly limited as long as it is not deformed and worn when repeatedly used, and may be made of metal or resin, A metal is preferably used. This is because it is excellent in deformation resistance and wear resistance.
- the projection group forming original plate is formed by first spin-coating an appropriately selected resin resist on the surface of a steel or aluminum base material subjected to uniform chrome plating or copper plating to form a resist layer. . Next, laser drawing is performed using a laser drawing apparatus, and development processing is performed using a predetermined developer to form a resist pattern layer. Next, the metal pattern layer is formed by dry etching the chromium or copper metal film exposed from the opening of the resist pattern layer.
- etching of the base material is performed using the resist pattern layer and the metal pattern layer as an etching resistant layer.
- an electron beam drawing method can be used in addition to the laser drawing method.
- a thin film such as a DLC (diamond-like carbon) thin film may be further uniformly coated on the plate.
- a high-purity aluminum layer is provided by sputtering or the like on the surface of a metal base material such as stainless steel, copper, or aluminum, directly or via various intermediate layers. It is also possible to mention a layer in which the uneven shape is formed by an anodic oxidation method.
- the surface of the base material may be made into a super-mirror surface by an electrolytic composite polishing method that combines electrolytic elution action and abrasion action by abrasive grains before providing the aluminum layer.
- the purity (impurity amount), crystal grain size, anodizing treatment and / or etching treatment conditions of the aluminum layer are appropriately adjusted.
- a desired shape can be obtained.
- the shape of the projection group forming original plate is not particularly limited as long as a desired shape can be formed.
- the shape may be a flat plate shape or a roll shape.
- a roll shape is preferable from the viewpoint of easy mass production.
- a plate-shaped mold can also be suitably used as the projection group forming original plate because the projection group can be easily formed.
- a flat metal mold it is possible to easily suppress deformation of the protrusions and deformation of the protrusion group due to adhesion between the protrusions when the mold is peeled from the cured product of the resin composition.
- the roll-shaped mold used in the present disclosure include those in which a concavo-convex shape corresponding to the shape of the protrusion group is formed on the peripheral side surface of the base material as described above.
- the mold growth suppression member according to the present disclosure can be used for any application that requires suppression of mold growth, and is not particularly limited.
- Examples of applications in which the mold growth suppressing member according to the present disclosure can exert an effect include, for example, a room provided with water facilities such as a bathroom, a washroom, a washing machine storage place, a kitchen, and a toilet (including unit bath equipment)
- Interior materials such as interior walls, ceilings, and interior decorations used in spaces or rooms or spaces adjacent to watering facilities such as dressing rooms, clothes drying places, canteens; exterior members such as gates, fences, exterior walls, and carports ;
- Plant cultivation facilities such as greenhouses and plant cultivation tanks; Air conditioning equipment such as air conditioners and air purifiers; Household appliances such as refrigerators, washing machines, telephones, and vacuum cleaners; Cooking equipment such as microwave ovens and rice cookers; Medical Medical equipment such as equipment; office equipment for school equipment and other electronic equipment.
- these various devices include filters incorporated in these various devices, protective films such as electronic display units and touch panels provided in these various articles, casings, and films for window glass. it can.
- the mold growth inhibiting member according to the present disclosure can be suitably used for, among other things, parts that are difficult for humans to reach, for example, carport roofing materials, and preferably used as filters incorporated in the various devices. It is done.
- the container or packaging material such as a foodstuff and a pharmaceutical, it can also be set as the form which comprised this protrusion group on the surface of the inner side, the outer side, or the inner and outer sides.
- FIG. 9 is a diagram schematically illustrating an example of a usage mode of the mold growth suppressing member according to the present disclosure.
- FIG. 10 is a schematic cross-sectional view schematically showing an example of the B-B ′ cross-sectional view of FIG. 9, and FIG. 10 also shows an enlarged view of a C portion.
- 9 and 10 are examples of a container for storing a liquid material, which is an example of a so-called pouch container.
- the container 40 shown in the example of FIG. 9 and FIG. 10 has a shape in which two packaging materials 31 are overlapped and the peripheral part is bonded together, and the bottom part is three pieces to secure the volume of the container.
- the packaging material 31 is bonded together.
- an extraction port 32 that can be sealed is provided at the top.
- a space for accommodating the liquid material is formed between the two packaging materials 31.
- the mold growth suppressing member of the present disclosure can be provided, for example, inside a space that stores liquid, and can suppress mold growth in a liquid state (see C in FIG. 10).
- the mold growth suppressing member of the present disclosure may be disposed on the outer surface of the packaging material 31 (not shown).
- FIG. 11 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure.
- 12 is a schematic cross-sectional view schematically showing an example of a cross-sectional view taken along the line D-D ′ of FIG. 11, and FIG. 12 also shows an enlarged view of the E portion.
- FIG.11 and FIG.12 is an example of the packaging material 50 for preserving foodstuffs, such as bread and vegetables, and is an example of what is called a wrapping film.
- the inner surface of the space for storing food is a surface having a group of protrusions.
- Contained items such as foods contained in the packaging material start to propagate mold from the portion that comes into contact with the packaging material, and then spread to the entire stored item and mold tends to propagate.
- the mold growth suppression member according to the present disclosure as a packaging material, the growth of mold in a portion that comes into contact with the packaging material in food or other contained items is prevented. Can be suppressed. Therefore, mold growth can be suppressed even in the entire contents.
- the inner surface is a surface having the projection group in order to improve the mold growth suppressing effect, More preferably, the inner surface is a surface having the projection group.
- FIG. 13 is a diagram schematically illustrating another example of the usage mode of the mold growth suppressing member according to the present disclosure.
- FIG. 14 is a schematic cross-sectional view schematically showing an example in which a part of the F-F ′ cross section of FIG. 13 is enlarged.
- FIGS. 13 and 14 are examples in which the mold propagation suppressing member of the present disclosure is used as the roof material 61 of the carport 60. As shown in FIG. 14, both surfaces of the roof material 61 of the carport 60 have a group of protrusions. It is a surface.
- the mold growth inhibiting member of the present disclosure can be preferably used for agricultural applications.
- An agricultural mold growth inhibitory member having at least a part of the mold growth inhibitory member according to the present disclosure can suppress the growth of bacteria and molds, which are also called plant pathogenic bacteria, and enables stable growth of crops. It is also possible to increase the yield.
- plant pathogens include those described in All of Hydroponic Culture-Basic Technology Supporting Plant Factories Japan Facility Horticultural Association (edit), Japan Hydroponic Culture Research Association (edit).
- the mold growth inhibitory member has high antifungal properties against molds such as Pythium and Fusarium.
- FIG. 15 is a diagram schematically illustrating an example of a usage mode of the agricultural mold growth suppressing member according to the present disclosure, and specifically, a schematic cross-sectional view of the greenhouse 20.
- the agricultural mold growth suppression member for agriculture according to the present disclosure may be disposed on the inner surface side of the ceiling portion 11 or the wall surface portion 12, for example, and is disposed on the surface of the reflection sheet provided on the soil surface 13. It may be a thing.
- the mold growth suppressing member of the present disclosure may be a sheet or plate that itself forms the ceiling 11 or the wall surface 12, and is provided on the inner surface side of the ceiling 11 or the wall surface 12.
- the film-like thing used by bonding may be used.
- FIG. 16 is a figure which shows typically another example of the usage condition of the fungal growth suppression member for agriculture which concerns on this indication, and specifically, of the plant cultivation unit 30 (it is also called LED house) in factory cultivation. It is typical sectional drawing which shows an example.
- the light source 22 such as an LED light source is arranged on the top plate side of one or two or more shelves, the shelf efficiently uses light source light,
- a reflection sheet 21 for maintaining temperature and humidity conditions is disposed.
- the agricultural mold growth suppressing member of the present disclosure may be, for example, disposed on the inner surface side of the reflection sheet 21 or may be disposed on a shelf board or a top board constituting the shelf. . By using the mold growth inhibiting member of the present disclosure, it is possible to reduce the amount of agricultural chemicals used, improve the crop yield, and enable stable production.
- the width W of the protrusion, the height H of the protrusion, and the rising angle ⁇ were measured by cross-sectional profile analysis using a laser microscope (manufactured by Olympus, LEXTXOLS4100).
- Preparation Example 1 Preparation of resin composition for forming uneven layer
- the following components were dissolved in 200 parts by mass of ethyl acetate to prepare a resin composition for an uneven layer.
- DPHA dipentaerythritol hexaacrylate
- Aronix M-260 manufactured by Toa Gosei Co., Ltd., polyethylene glycol diacrylate
- hydroxyethyl acrylate-Photoinitiator (Lucirin TPO, manufactured by BASF) 3 parts by mass
- Example 1 Production of mold growth inhibiting member
- the concavo-convex layer forming resin composition is applied and filled so that the surface having the concavo-convex shape of the projection group forming original plate is covered, and the thickness of the concavo-convex layer on which the projection group is formed is 20 ⁇ m after curing,
- a base material material: PET, thickness: 100 ⁇ m, product name: Lumirror U34, manufactured by Toray Industries, Inc.
- the resin composition was cured by irradiating ultraviolet rays with energy of 2000 mJ / cm 2 from the substrate side. Then, it peeled from the original plate for protrusion group formation, and the mold growth inhibitory member of Example 1 was obtained.
- the cross section of the surface of the obtained mold growth inhibiting member was observed with an SEM and a laser microscope (manufactured by Olympus, LEXT OLS4100), a plurality of protrusions having a protrusion width W of 4 ⁇ m, a height H of 4 ⁇ m, and a distance between the protrusions of 8 ⁇ m were found.
- a group of protrusions formed was formed.
- the rising angle ⁇ was 80 degrees.
- the contact angle with respect to water was 70 degrees. Since the present technology does not depend on the contact angle, the antifungal function can be stably maintained.
- Example 2 Production of mold growth inhibiting member
- the projection group forming original plate was changed to form a projection group in which a plurality of projections having a projection width W of 10 ⁇ m, a height H of 2 ⁇ m, and a distance between projections of 20 ⁇ m were arranged.
- the rising angle ⁇ was 60 degrees.
- the contact angle with respect to the water of the surface which has a protrusion group was 78 degrees.
- Example 3 Production of mold growth inhibiting member
- the projection group forming original plate was changed to form a projection group in which a plurality of projections having a projection width W of 20 ⁇ m, a height H of 10 ⁇ m, and a distance between projections of 10 ⁇ m were arranged.
- the rising angle ⁇ was 90 degrees.
- the contact angle with respect to the water of the surface which has a protrusion group was 84 degrees.
- Example 4 Production of mold growth inhibiting member
- the projection group forming original plate was changed to form a projection group in which a plurality of projections having a projection width W of 20 ⁇ m, a height H of 10 ⁇ m, and a distance between projections of 10 ⁇ m were arranged.
- the rising angle ⁇ was 108 degrees.
- protrusion group was 96 degrees.
- Comparative Example 1 On the base material (material: PET, thickness: 100 ⁇ m, trade name: Lumirror U34, manufactured by Toray Industries, Inc.), the uneven layer forming resin composition was applied so that the thickness after curing was 20 ⁇ m. By irradiating ultraviolet rays with energy of 2000 mJ / cm 2 from the material side to cure the resin composition, a member of Comparative Example 1 having a flat surface was obtained.
- the test sample was produced by disinfecting the surface of the cured product of the resin composition for forming an uneven layer of each member with ethanol, and cutting the surface into 50 mm squares. Spray the whole surface of the test sample by spray inoculation to the extent that water droplets are attached, suspend the test sample so that the surface is in the vertical direction, and culture for 4 weeks under conditions of temperature 24 ⁇ 1 ° C. and humidity 95% RH. did.
- the surface of the test sample after culturing was observed with the naked eye and a stereomicroscope, and judged according to the following criteria. The determination results are shown in Table 1.
- FIG. 19 shows a micrograph of the surface of the cultured test sample of Comparative Example 1 used in the mold resistance test.
- FIG. 19 is a photomicrograph of the surface of the Aspergillus test sample of Comparative Example 1.
- the member with a flat surface obtained in Comparative Example 1 was found to have 5 levels of mold growth in the mold resistance test 1 performed in a wet state at a temperature of 24 ⁇ 1 ° C. and a humidity of 95% RH. It was.
- the mold growth inhibiting member obtained in Examples 1 to 4 is mold growth only at 1 or 2 level based on the standard in the mold resistance test performed in the same wet state as in Comparative Example 1. Was not observed, and the growth of mold was able to be suppressed in all types of mold used in the test.
- Mold resistance test 2 The mold resistance test 2 was performed in the same manner as the mold resistance test 1 except that the mold was Pythium vanterpoolii, Fusarium solani, Fusarium oxysporum, and Fusarium moniliforme. The results are shown in Table 2.
- the member with a flat surface obtained in Comparative Example 1 was found to have 5 levels of mold growth in the mold resistance test 2 performed in a wet state at a temperature of 24 ⁇ 1 ° C. and a humidity of 95% RH. It was.
- the mold growth inhibiting member obtained in Examples 1 to 4 is mold growth only at 1 or 2 level based on the standard in the mold resistance test performed in the same wet state as in Comparative Example 1. Was not observed, and the growth of mold was able to be suppressed in all types of mold used in the test.
- Example 5 Production of mold growth inhibiting member
- the projection group forming original plate was changed so that the projection width W, the projection height H, and the interprotrusion distance D were the values shown in Table 3, respectively, and the thickness of the uneven layer after curing was 30 ⁇ m.
- the mold growth inhibiting member of Examples 5 to 21 was produced in the same manner as Example 1. With respect to the mold growth inhibitory members of Examples 5 to 21, the rising angle ⁇ and the contact angle of the surface having the protrusion group with water were measured, and the mold resistance test 1 was conducted. Table 3 shows the measurement results and test results.
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Abstract
L'invention concerne un élément d'inhibition de la propagation dans le moule qui comprend une couche irrégulière dont la surface présente des parties saillantes comprenant des groupes de parties saillantes formés par la disposition de plusieurs parties saillantes. La largeur L des parties saillantes est comprise entre 1 et 20 µm, la hauteur H des parties saillantes est comprise entre 1 et 20 µm, et la distance D entre des parties saillantes adjacentes est comprise entre 1-30 µm.
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WO2018128092A1 (fr) * | 2017-01-05 | 2018-07-12 | パナソニックIpマネジメント株式会社 | Corps moulé |
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US10968292B2 (en) | 2017-09-26 | 2021-04-06 | Sharp Kabushiki Kaisha | Synthetic polymer film whose surface has microbicidal activity, photocurable resin composition, manufacturing method of synthetic polymer film, and sterilization method with use of surface of synthetic polymer film |
US11364673B2 (en) | 2018-02-21 | 2022-06-21 | Sharp Kabushiki Kaisha | Synthetic polymer film and production method of synthetic polymer film |
WO2022162528A1 (fr) * | 2021-01-28 | 2022-08-04 | 3M Innovative Properties Company | Surface microstructurée à élimination accrue des micro-organismes après nettoyage, articles et procédés |
WO2022230533A1 (fr) * | 2021-04-30 | 2022-11-03 | 株式会社クレハ | Corps moulé antimicrobien, matériau d'emballage alimentaire, et dispositif à demeure in vivo |
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JPWO2017090661A1 (ja) | 2017-11-24 |
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