JP6918295B2 - Anti-slip sheet - Google Patents

Description

The present invention relates to a non-slip sheet. Specifically, the unevenness of the soft resin itself not derived from the micropores (A) in which the outer shell of the microhollow sphere (s) is destroyed and the micropores (A) in which the outer shell of the microhollow sphere (s) is destroyed. The present invention relates to a non-slip sheet having (B).

Conventionally, there are many harmful effects due to slipping, such as the problem of slipping on stairs, the problem of cutting boards slipping on a wet stainless steel countertop, and the problem of slipperiness due to the presence of water in the bathtub. On the other hand, generally, adhesive rubber, cork plate, etc. are used, and in addition, a non-slip sheet formed of a rubber-like elastic material and having an uneven pattern, a suction cup, etc. on the surface (for example, patent documents). 1) A non-slip sheet (for example, patented) in which a thin foam rubber layer having fine irregularities on the surface of open cells is formed on the surface of the sheet, and the contact resistance between the foam rubber layer and the object is increased by the foam rubber layer. Document 2) and the like have been developed.

Japanese Unexamined Patent Publication No. 2006-501017 Japanese Unexamined Patent Publication No. 62-178337

However, with sticky rubber, the resin sticks to the object and causes stickiness, and cork has low durability because the material itself is brittle, and rubber-like elastic material is used to prevent slipping, such as a suction cup. However, although it has excellent suction force in the vertical direction, it is still slippery in the horizontal direction in a wet environment, and the anti-slip effect is not sufficient. Further, even a thin foam rubber layer having fine irregularities on the surface of open cells could not be said to have a sufficient anti-slip effect in a water-wet environment.

An object of the present invention is to have a sufficient anti-slip function not only in a dry environment but also in a wet environment, to have a good contact feeling with limbs and the body, and to stabilize the laying state in a bathtub, a floor surface, or an inclined surface. It is to provide a non-slip sheet that can be made to.

In view of the above problems, as a result of diligent research, the present inventors have destroyed the micropores (a) and the outer shell of the microhollow sphere (s) on the surface due to the destruction of the outer shell of the microhollow sphere (s). It has been found that if a sheet having minute irregularities of a soft resin not derived from the fine pores (a) is used, the contact feeling of the body is good and the anti-slip property is improved, and the present invention has been completed.

That is, the present invention is a method for producing a non-slip sheet formed of a soft resin in which micro hollow spheres (s) are dispersed.
A non-slip sheet comprising slicing a soft resin in which the micro hollow spheres (s) are dispersed to cut the micro hollow spheres (s) and then polishing the sliced surface of the soft resin. It is a manufacturing method .
Further, the present invention is a non-slip sheet manufactured by the method for manufacturing a non-slip sheet according to claim 1.
The surface of the anti-slip sheet has micropores (A) in which the outer shell of the microhollow sphere (s) is cut, and irregularities (B) of the soft resin itself not derived from the microhollow sphere (s). It is a non-slip sheet characterized by .

Further, the present invention is characterized in that the micropores (A) are present at both locations of the concave and convex portions of the unevenness (B) of the soft resin itself.
Further, the present invention is characterized in that the soft resin is a thermosetting urethane resin.

Further, in the present invention, the diameter of the micropores (A) in which the outer shell of the microhollow sphere (s) is cut is 5 μm or more and 200 μm or less, and the surface of the soft resin not derived from the microhollow sphere (s). The width of the concave and convex recesses in the above is 10 μm or more and 500 μm or less.

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According to the present invention, in the non-slip sheet, the surface of the sheet has micropores (A) due to cutting of the outer shell of the microhollow sphere and minute irregularities (B) of the soft resin itself not derived from the microhollow sphere (s). ), And the surface has micro-concavities and convexities, so a good feel to the body can be obtained, and the suction cups of the micropores (A) have a non-slip effect, not only in a dry environment but also in a wet environment. Has good anti-slip performance.

FIG. 5 is an enlarged cross-sectional view of an intermediate sheet according to an embodiment measured using a digital ink oscilloscope VHX-500 manufactured by Keyence Corporation. It is an enlarged plan view which measured the intermediate sheet which is one Embodiment using the digital ink oscilloscope VHX-500 of Keyence. FIG. 5 is a schematic view showing the surface of a cross section measured by enlarging an intermediate sheet before polishing, which is one embodiment, with a digital ink oscilloscope VHX-500 manufactured by Keyence Corporation as a line. FIG. 5 is a schematic view showing the surface of a cross section measured by enlarging the intermediate sheet after polishing, which is one embodiment, with a digital ink oscilloscope VHX-500 manufactured by Keyence Corporation as a line.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments. Within the same and equal scope as the present invention, various modifications can be made to the following embodiments.

In the anti-slip sheet of the present invention, the surface of the anti-slip sheet formed of a soft resin in which the micro hollow spheres (s) are dispersed has micropores (A) in which the outer shell of the micro hollow spheres (s) is destroyed. ) (Hereinafter, it may be simply referred to as a micropore (A)) and an unevenness (B) of the soft resin itself not derived from the microhollow sphere (s).
This anti-slip sheet has a suction cup effect of the micropores (A) alone due to a synergistic effect of the suction cup effect of the micropores (A) and the antislip effect due to the unevenness (B) of the soft resin itself not derived from the microhollow spheres (s). It has a better anti-slip effect than the anti-slip effect of.

Further, it is preferable that the surface of the concave portion of the unevenness (B) of the soft resin itself includes the micropores (A) in which the outer shell of the microhollow sphere (s) is broken.
When the micropores (A) are the surface of the concave portion (B) of the soft resin itself and are inside the concave portion, a double suction cup effect of large and small is exerted, the synergistic effect becomes more remarkable, and even better anti-slip. It works.

[Manufacturing method of soft resin containing micropores (A)]
The soft resin containing the micropores (A) in the present invention is produced as follows.
The micro hollow sphere (s) used in the present invention is not limited as long as it has a cavity inside and is a micro sphere. For example, a phenol resin, a vinylidene chloride-acrylonitrile copolymer, an epoxy resin, a urea resin, etc. Examples include organic materials such as melamine resin and inorganic materials such as glass, alumina silicate, ceramics, and carbon. A composite type in which an inorganic substance is mixed with an organic type can also be used. Thermally expanding hollow particles in which a leavening agent is added to the cavities of the hollow particles can also be preferably used.
Among these, in particular, from the viewpoint of flexibility and weight reduction, organic-based microhollow spheres and composite-based ones in which an inorganic substance such as calcium carbonate is mixed with an organic-based one having increased strength can be preferably used.

The size of the micro hollow sphere is not limited, but the average particle size is preferably 5 to 200 μm, more preferably 10 to 150 μm. Those having various particle sizes may be mixed and used.

The soft resin is not limited to its molecular structure, the type of functional group contained therein, and its production method, and may be any soft resin, and may be either a thermoplastic resin or a thermosetting resin.

Specifically, as soft thermoplastic resins, soft vinyl chloride resin, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and styrene- (ethylene). A styrene-based elastomer such as a-butylene) -styrene block copolymer, a styrene-alkyl (meth) acrylate-acrylonitrile copolymer containing an alkyl (meth) acrylate as a main component, and a composite consisting of polyorganosiloxane and alkyl (meth) acrylate. Graft copolymer with vinyl monomer graft-polymerized on rubber, high rubber content acrylonitrile-butadiene-styrene copolymer, high rubber content acrylonitrile-acrylate-styrene copolymer, high rubber content acrylonitrile-ethylene-butene- Styrene copolymer, silicone resin, acrylic-modified silicone resin, low-density polyethylene-methylmethacrylate graft copolymer, (ethylene-ethylacrylate) -methylmethacrylate graft copolymer, low-density polyethylene-glycidyl methacrylate-graft copolymer, polyester -Polyester block copolymer, polyester-polyether block copolymer, urethane resin-based elastomer, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, acid group-containing ethylene Examples thereof include a-propylene copolymer, an epoxy group-containing ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer, an ethylene-methyl methacrylate copolymer, and an amide resin-based elastomer.

As the soft thermosetting resin, a softened curable resin can be used. For example, urethane resin, unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, urea resin, melamine resin, alkyd resin, silicone resin and the like can be mentioned.
The above-mentioned resins can be used alone or in combination of two or more.

Among these, the lower the viscosity of the resin, the easier it is to disperse in terms of mixing the minute hollow spheres (s). In that respect, a thermosetting resin is preferable. That is, since the raw material before producing the thermosetting resin has a low viscosity, the micro hollow spheres (s) are mixed in a part thereof, and the resin raw material is blended before the curing to form the micro hollow spheres (s). ) Can be uniformly dispersed.
Further, among the thermosetting resins, urethane resin is particularly preferable. The thermosetting urethane resin makes the sheet flexible, and the hardness of the resin is easy to adjust, so that it can be easily processed into a sheet.

Hereinafter, urethane resin as a thermosetting resin will be described, but other soft resins can be similarly applied when manufacturing by a known manufacturing method. Further, if the thermoplastic resin is in a molten state and the micro hollow spheres (s) are dispersed and cooled, a thermoplastic resin in which the micro hollow spheres (s) are dispersed can be obtained.
The urethane resin is obtained by reacting the polyol (a) and / or the polyamine (b) with the isocyanate (c).

The polyol is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and those conventionally used in urethane resins can be used. Examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, polylactone polyols, polyolefin polyols, acrylic polyols, castor oil-based polyols, silicone-based polyols, and polymer polyols modified with ethylenically unsaturated monomers. , These can be used alone or in combination of two or more.

Among these polyols, a polyether polyol and a polycarbonate polyol are preferably used from the viewpoint of durability of the urethane resin, and further, a polyether polyol is particularly preferably used from the viewpoint of workability and economy during production.

The urethane resin has softness, and the softness is preferably determined from the viewpoint of strength. In order to adjust the softness, the type of polyol or isocyanate may be selected, or the average number of functional groups, hydroxyl value and terminal functional group of the polyol and the average number of functional groups of isocyanate described later may be adjusted. Polyols and isocyanates containing a long-chain skeleton in the molecule tend to impart softness.

The average number of functional groups of the polyol is preferably 1.5 to 3.0, more preferably 1.7 to 2.5, and the hydroxyl value of the polyol is preferably from the viewpoint of imparting softness to the urethane resin. Is 20 to 200 mgKOH / g, more preferably 28 to 160 mgKOH / g.

The primary OH ratio of the terminal hydroxyl group of the polyol (that is, the ratio of the primary hydroxyl group among the hydroxyl groups located at the terminal) is 40 to 100%, preferably 50 to 90% from the viewpoint of improving the tensile strength. Is. When the primary OH ratio of the terminal hydroxyl group is 40% or more, the mechanical properties of the urethane resin are good.

Examples of such a polyoxypropylene-based polyol in which ethylene oxide is ring-opened added to the terminal hydroxyl group of the polyoxypropylene polyol, and a polyoxyalkylene-based polyol in which the added molar distribution of the ethylene oxide is narrow can be mentioned. .. For these, the techniques disclosed in JP-A-2002-308811 and JP-A-2003-135951 can be adopted.

The isocyanate is not particularly limited as long as it has two or more isocyanate groups at the terminals, and is, for example, 2,4-toluenediisocyanate, 2,6-toluenediisocyanate, 4,4'-diphenylmethanediisocyanate, 2,2'. -Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, phenylenediisocyanate, 1,5-naphthalenediisocyanate, hydrogenated diphenylmethane diisocyanate, Aromatic polyisocyanates such as hydrogenated xylylene diisocyanate and hydrogenated products thereof; alicyclic polyisocyanates such as 1,4-cyclohexanediisocyanate, isophorone diisocyanate and norbornan diisocyanate; tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate and the like. Aliphatic polyisocyanates; said polyisocyanate modified products having one or more isocyanurate bonds, carbodiimide bonds, urethane bonds, urea bonds, burette bonds, allophanate bonds, etc., and these may be used alone or in admixture of two or more. Can be used.

The average number of functional groups of isocyanate is 1.8 to 4.5 from the viewpoint of crosslink density and softness.
In the reaction between the polyol and the isocyanate, from the viewpoint of the crosslink density and the softness, the blending ratio of both is preferably adjusted so that the isocyanate index is 70 to 120, and more preferably 80 to 110.

The method for producing a urethane resin is not limited, and even if it is produced by a direct reaction between isocyanate and a polyol, it is produced by once producing an isocyanate group-terminated urethane prepolymer and then reacting the isocyanate group-terminated urethane prepolymer with a polyol. You may.

A specific example of the urethane resin manufacturing method is as follows. First, the polyol (a) (or polyamine (b)) is mixed with a urethanization catalyst, a defoaming agent, a desiccant, an additive, a foaming agent, a foam stabilizer, etc. in the case of foam, if necessary, and the polyol is added. Prepare a compounding solution (hereinafter, it shall also include a polyamine compounding solution). At the same time, an additive or the like is added to the isocyanate (c) as needed to prepare an isocyanate compounding solution. Then, using a mixing device or a foaming device, the polyol compounding solution and the polyisocyanate compounding solution are rapidly mixed. The obtained mixed solution is put into a predetermined container (mold), resinified, and then taken out to obtain a urethane resin.

As the urethanization catalyst, a normal urethanization catalyst that promotes the urethanization reaction can be used. For example, triethylenediamine, bis (N, N-dimethylamino-2-ethyl) ether, N, N, N', N' Tertiary amines such as PO adducts of −tetramethylhexamethylenediamine, N, N-dimethylaminopropylamine and their carboxylates, carboxylic acid metal salts such as potassium acetate, potassium octylate, stanas octoate, dibutyltin Examples include organic metal compounds such as dilaurate.

When the urethane resin is used as a foam, a foaming agent and a foam stabilizer are used, but conventionally known ones can be used.

Further, when producing a urethane resin in order to improve the hardness and texture of the urethane resin, various conventionally known softeners, inorganic and organic reinforcing agents, fillers, and aging due to sunlight or heat are used as additives. Anti-aging agents, various oils and lubricants for improving processability, colorants such as dyes and pigments, antibacterial agents, antifungal agents, surfactants, catalysts and the like may be added.

In the present invention, the minute hollow spheres (s) are dispersed in the soft resin, particularly the urethane resin. The amount of the micro hollow spheres (s) blended in the urethane resin is not particularly limited, but is preferably 1 to 20 parts by weight based on 100 parts by weight of the total raw materials of the urethane resin. The microhollow spheres (s) are preferably blended and dispersed in the polyol (a) and / or the polyamine (b). Since it takes time to uniformly mix the fine hollow spheres (s), it is preferable to use a stable raw material such as polyol (a) and / or polyamine (b). When the amount of the fine hollow spheres added is 1 part by weight or more, the anti-slip effect is recognized in the sheet, and when it is 20 parts by weight or less, the mixture with the urethane resin is easy and the sheet processability is also good.

Further, in order for the sheet obtained by processing the urethane resin to be reliably and stably submerged in water, it is necessary to increase the specific gravity of the urethane resin. A preferable specific density capable of quickly and stably settling in water is to adjust the specific density of the sheet to 1.1 or more and 2.4 or less. A sheet having a specific gravity in this range is also suitable as a bathtub mat.

The method for increasing the specific density of the sheet is not particularly limited, and examples thereof include addition of inorganic particles having a high specific density, and specific examples thereof include gold, silver, lead, tungsten, barium salt, calcium salt, and talc. In particular, barium salt, calcium salt, and talc are mixed with the above-mentioned soft resin and microhollow spheres (s) from the viewpoints of safety to the human body, price competitiveness, and high specific density. Is preferable. The blending amount of the inorganic particles having a high specific gravity is not particularly limited as long as the specific gravity of the sheet can be 1.1 or more and 2.4 or less. The amount is usually 1% by weight or more and 90% by weight, preferably 5% by weight or more and 70% by weight.

[Method of manufacturing a non-slip sheet using the soft resin in the present invention]
(Method of forming micropores (A) in soft resin)
The method for producing a non-slip sheet of the present invention is not particularly limited as long as the surface of the sheet has irregularities (B) of the soft resin itself not derived from the micropores (A) and the microhollow spheres (s). .. For example, if the soft resin is polished, the soft resin itself becomes uneven. When a large recess is formed, the outer shell of the micro hollow sphere (s) on the surface thereof is cut to form a micropore (A), so that the above state is exhibited.
Further, since the micropores (A) in the convex portion of the soft resin itself also exert a suction cup effect and contribute to anti-slip, it is preferable that the micropores (A) are located at both locations of the concave-convex convex portion of the uneven portion of the soft resin itself. .. As a manufacturing method in which micropores (A) are likely to be formed in both of the concave and convex portions of the soft resin itself, the soft resin in which the fine hollow spheres (s) are dispersed is sliced, and then the soft resin is sliced. It is preferable to polish the surface of the surface because these can be surely performed.

First, the soft resin is sliced to a desired thickness, and then cut to a desired size to obtain an intermediate sliced sheet (hereinafter, simply referred to as an intermediate sheet), but the slicing and cutting methods are particularly limited. It's not something.
For example, a device for slicing rubber or the like can be applied to the slice. It can be manufactured by placing a soft resin on a moving table or conveyor and cutting it horizontally with a horizontally rotating blade (band knife / saw).

The thickness of the intermediate sheet is also determined by the application and is not limited, but is preferably 1 mm or more and 50 mm or less. Since the sliced surface has micropores (A), it is less slippery. Even if the thickness is matte, the same effect can be obtained, so it should be included in the intermediate sheet.

That is, the outer shell of the micro hollow sphere is cut by the knife of the slicer by slicing to form a recess, which becomes a micro hole (A). Further, the minute hollow spheres dispersed in the soft resin are separated from the slice surface to generate recesses due to holes, but these minute holes are mainly single holes and may exist because they have a suction cup structure.

The diameter of the micropores (A) thus obtained is preferably 5 μm or more and 200 μm or less, which is the same as that of the microhollow sphere (s). When it is 5 μm or more, a non-slip effect is exhibited on the sheet surface, and when it is 200 μm or less, the tactile sensation to the human body is good. It is more preferable that the diameter of the micropores (A) is 10 μm or more and 150 μm or less.

FIG. 1 is an enlarged cross-sectional view of an intermediate sheet according to an embodiment. FIG. 2 is an enlarged plan view of an intermediate sheet according to an embodiment of the present invention. These were measured using Keyence's digital ink oscilloscope VHX-500.
This intermediate sheet is obtained by dispersing "Matsumoto Microsphere MFL-HD60CA" (complex of AN-based copolymer and calcium carbonate, average particle size of 50 μm) in urethane resin, slicing it as a micro hollow sphere, and expanding it with a microscope. It is what I observed. In FIG. 1, S indicates the surface of the intermediate sheet. When combined with the plan view of FIG. 2, in addition to the micropores (A) 1 in which the outer shell of the microhollow sphere (s) is destroyed, the microhollow sphere dispersed in the soft resin is removed from the slice surface. Micropores 2 due to holes are also observed. Such micropores 1 and 2 have a non-slip effect due to the suction cup effect.

(Method of forming irregularities on the soft resin itself)
Next, a method of making unevenness on the soft resin itself will be described.
If the method is to make the soft resin itself uneven, sandpaper may be used for manual polishing, but there is no particular limitation, and a polishing device is preferably used. The polishing device is usually equipped with a polishing pad. Sandpaper is usually used as the polishing pad. The material of the abrasive grains used for sandpaper is not particularly limited, and specific examples thereof include alumina, white alumina, alumina zirconia, silicon carbide, diamond, garnet, emery, and flint.

The sandpaper count is preferably in the range of 40 or more and 2000 or less specified by JIS. More preferably, the number is 240 or more and 2000 or less, and particularly preferably 1000 or more and 2000 or less. When the number is 40 or more and 2000 or less, the anti-slip effect is improved.

The polishing method and polishing conditions are not particularly limited, and as described above, sandpaper may be used for manual polishing, or a polishing device may be used for industrial polishing. The material and count of the abrasive grains to be used are determined by the application and the degree of anti-slip effect.
By this polishing, unevenness (B) of the soft resin itself, which is not derived from the fine hollow particles (s), can be formed on the soft resin.

In the soft resin polished as described above, irregularities (B) on the surface of the soft resin not derived from the micro hollow spheres (s) occur. The width of the concave portion formed in the unevenness (B) is preferably 10 μm or more and 500 μm or less. With this size, the micropores (A) in which the outer shell of the microhollow sphere (s) is destroyed can be included in the surface of the concave portion of the unevenness (B). Double large and small sucker effects occur, which can synergize to improve the anti-slip effect.

FIG. 3 is a schematic view showing the surface of a cross section measured by enlarging an intermediate sheet before polishing, which is one embodiment, with a digital ink oscilloscope VHX-500 manufactured by Keyence Corporation as a line. In FIG. 3, three micropores (A) 1 due to the microhollow sphere (s) can be confirmed. The soft resin 3 is cut by slicing, and the soft resin 3 itself is substantially flat.

FIG. 4 is a schematic view showing the surface of a cross section measured by enlarging the intermediate sheet after polishing, which is one embodiment, with a digital ink oscilloscope VHX-500 manufactured by Keyence Corporation as a line. In FIG. 4, there is a large unevenness, and a minute hole (A) 1 is further present in the concave portion 4. The outer shell of the micro hollow sphere (s) inside is cut into micropores (A) 1 by polishing.

As described above, the outer shell of the micro hollow sphere (s) is destroyed in the recess 4 during polishing, and the micro hole (A) 1 is formed in the recess 4. Further, even in the convex portion 5, the micropores (A) 1 generated when sliced remain as they are. As a result, in the recess 4, a suction cup effect due to the minute hole (A) 1 and a suction cup effect due to the recess 4 itself also occur. Further, there is a non-slip effect due to the unevenness 4 and 5 of the soft resin itself. Therefore, it exhibits an anti-slip effect superior to the anti-slip effect caused by the micropores (A) 1 alone, and has sufficient anti-slip performance not only in a dry environment but also in a water-wet environment.
Further, since the micropores (A) 1 and the irregularities (B) 4 and 5 on the surface are minute, a good feel to the body can be obtained. At the same time, the anti-slip effect is improved, and it has sufficient anti-slip performance not only in a dry environment but also in a wet environment.

The non-slip sheet of the present invention includes a bathroom mat, a kitchen mat, an automobile seat, a packing sheet for preventing bulk collapse, a part of a hook with a magnet, golf gloves and table tennis, a tennis racket, and a golf club. Grips, stamping mats, hanger mounting edge collapse prevention materials, skirt and trouser hanger linings, staircase non-slip materials, finger cot substitutes, sheets and carpet slip prevention materials, silicon wafer polishing material parts, etc. It is used for various purposes, but is not limited to these.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. The part indicates the weight part.

The polyurethane resin raw materials used in Examples and Comparative Examples are as follows.
(1) Polyol (a): A PO adduct of glycerin having an average functional group number of 3.0, a number average molecular weight of 3000, and a hydroxyl value of 56.
(2) Castor oil 3 (ko): Refined castor oil with an average number of functional groups of 2.7, a number average molecular weight of 950, and a hydroxyl value of about 160 [Castor oil SL manufactured by Itoh Oil Chemicals, Inc.]
(3) Urethane catalyst (E): "Neostan U-600" manufactured by Nitto Kasei Co., Ltd.
(4) Micro hollow sphere (s): Microballoon (Matsumoto Microsphere MFL-110CAL manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) in which the surface of an acrylic resin hollow sphere having an average particle size of 110 μm is coated with calcium carbonate.
(5) Inorganic powder (H): Talc "Soapstone A" with a median diameter of 4 μm [manufactured by Mistron Japan]
(6) Dehydrating agent: "Molecular Sheave 3A-B Powder" manufactured by Union Showa
(7) Isophorone diisocyanate (b): isophorone diisocyanate ["VESTANAT IPDI", manufactured by EVONIC, isocyanate group content 37.6% by weight, specific density 1.06]

(Examples 1 and 2, Comparative Examples 1 and 4)
Using a vacuum hard mixer (UVR-20L, manufactured by Nippon Sosei Kogyo Co., Ltd.), prepare the polyol compounding solution shown in Table 1, add the isocyanate compounding solution shown in Table 1 into it, and mix under reduced pressure for 15 minutes. Then, the resulting urethane resin reaction solution was put into a metal mold having a size of 300 mm in length × 300 mm in width × 10 mm in thickness and cured for 60 minutes, and then demolded to obtain a urethane resin.

With respect to the urethane resins of Examples 1 and 2 and Comparative Examples 1 and 2, the obtained urethane resins were sliced to a thickness of 2 mm with a slicer (AN400D manufactured by FOTUNA of Germany). Comparative Example 3 was not sliced.

Next, the surfaces of the urethane resins of Examples 1 and 2 and Comparative Examples 3 and 4 were uniformly polished with sandpaper No. 1500. Polishing was done manually at room temperature, but under similar pressure. The urethane resin of Comparative Example 3 was not sliced and only the above polishing treatment was performed.

(Comparative Example 5)
A commercially available non-slip sheet (made of acrylic resin) was purchased and evaluated.
For the above Examples and Comparative Examples, the foam physical characteristics were measured by the measuring method shown below. The measurement results are shown in Table 1.

(Measuring method of resin physical properties)
Magnitude of micropores (A): Measured at a magnification of 300 times using a digital microscope VHX-500 manufactured by Keyence Corporation.
Size of unevenness of the resin itself: Measured in the same manner as above.
Recess size: Measured in the same manner as above. The concave portion refers to a concave portion in the unevenness of the resin itself.

C hardness: Using an automatic hardness tester (PX-100 manufactured by Kogaku Keiki Co., Ltd., weighting 1 kg), the hardness after 5 minutes of weighting was measured.
Friction during drying: After slicing into the prepared urethane resin sheet, place ^{a 2 kg cubic weight with a bottom area of 100 cm 2} on the obtained sheet, push the weight with a push-pull gauge, and the weight starts to move. Friction force during wetting, where the force applied to the friction force is the friction force: The frictional force during drying was performed according to the above method. That is, after slicing into the prepared urethane resin sheet, the obtained sheet is immersed in water and taken out, and a 2 kg cubic weight having a ^{bottom area of 100 cm 2 is placed on the sheet with a wet surface and pushed.} Feeling that the force applied to push the weight with a pull gauge and the weight starts to move is used as frictional force: Place the sheet on the floor and have 10 evaluators place it on it with bare feet to evaluate the feel of the sheet surface. I was asked to.
◯: The surface is smooth without any unevenness, and the feel is good.
×: The surface feels rugged and feels bad.

In Table 1, it can be seen that Example 1 is a sheet of Comparative Example 1 and Example 2 is a sheet of Comparative Example 2 subjected to a polishing treatment, and the frictional force during drying or wetting is improved. .. In particular, the frictional force during drying is greatly improved. Comparative Example 3 was obtained by polishing the surface of the produced urethane resin without slicing, and although it was not worse than that of Comparative Examples 1 and 2, the effect as in Examples 1 and 2 did not occur. rice field. In Comparative Example 4, since the minute hollow sphere (s) is not inserted, the frictional force is not improved. Comparative Example 5 is a commercially available product, but the frictional force is not good and the surface feel is poor. On the other hand, since the non-slip sheet of the present invention is made of urethane resin, the surface feel is good. From the above, it was confirmed that the anti-slip sheet of the present invention has an excellent anti-slip effect and a surface feel.

1 Micropores (A) in which the outer shell of the microhollow sphere (s) is cut
2 Micropores due to holes caused by the microhollow spheres coming off the sliced surface 3 Soft resin 4 Concave 5 Convex S Surface of intermediate sheet

Claims (5)

A method for manufacturing a non-slip sheet formed of a soft resin in which micro hollow spheres (s) are dispersed.
A non-slip sheet comprising slicing a soft resin in which the micro hollow spheres (s) are dispersed to cut the micro hollow spheres (s) and then polishing the sliced surface of the soft resin. Manufacturing method . A non-slip sheet manufactured by the method for manufacturing a non-slip sheet according to claim 1.
The surface of the anti-slip sheet has micropores (A) in which the outer shell of the microhollow sphere (s) is cut, and irregularities (B) of the soft resin itself not derived from the microhollow sphere (s). A non-slip sheet featuring . The non-slip sheet according to claim 2, wherein the micropores (A) are present at both locations of the concave and convex portions of the unevenness (B) of the soft resin itself. The non-slip sheet according to claim 2 or 3, wherein the soft resin is a thermosetting urethane resin. The diameter of the micropores (A) from which the outer shell of the microhollow sphere (s) has been cut is 5 μm or more and 200 μm or less, and the concave and convex recesses on the surface of the soft resin not derived from the microhollow sphere (s). The non-slip sheet according to any one of claims 2 to 4, wherein the width is 10 μm or more and 500 μm or less.

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