JP2700855B2 - Antibacterial sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to chemical resistance, stain resistance,
Antimicrobial sheets with excellent abrasion resistance and excellent antibacterial properties, especially chairs, beds, etc. in facilities that dislike the propagation of bacteria, such as hospitals, medical facilities, food processing plants, and various research laboratories. It is suitably used as a surface material for furniture such as a consultation table, other furniture, electric appliances, vehicles, as an ornamental material such as apron, hats, footwear, and as an interior material such as a wallpaper and a floor material. It relates to an antibacterial sheet.

[0002]

2. Description of the Related Art Conventionally, sheets made of vinyl chloride resin have been
It is called a PVC sheet and has been widely used as a material as described above because it is easy to clean.

As is well known, a large amount of a plasticizer is used in a vinyl chloride resin for the purpose of imparting processability or cold resistance or changing hardness. Therefore, a large amount of a plasticizer is also incorporated in the vinyl chloride resin used for the above-mentioned PVC sheet.

[0004] The plasticizer gradually migrates to the surface of the sheet while using the PVC sheet, and the plasticizer leaches out of the sheet surface (this phenomenon is called bleeding). When the plasticizer bleeds, dirt easily adheres due to the oiliness of the plasticizer, causing a sticky feeling. In addition, there is a possibility that various kinds of bacteria may be propagated by using a plasticizer bleeding on the surface or a stabilizer accompanying the plasticizer as a nutrient source.

[0005] In addition, vinyl chloride resins and plasticizers have low resistance to highly polar chemicals, and when the surface of the sheet is disinfected with such a highly polar disinfectant, the material changes, and the surface changes. Because of deterioration, hardening, discoloration, etc., it is considered that the material cannot be practically disinfected.

In order to cope with the above-mentioned drawbacks, techniques for treating the surface of a sheet with a surface treating agent have been developed. According to this technique, since bleeding of the surface of the plasticizer (or various additives accompanying it) can be suppressed, dust and dirt are prevented from adhering, and even if they adhere, they are easily dropped and become sticky. A certain effect can be obtained, such as eliminating the feeling.

However, it is not a complete countermeasure against oily dirt, and it is not possible to prevent the adhesion itself, and once adhered, it is difficult to fall off and is not limited to the adhesion to the sheet surface. Instead, it penetrates into fine irregularities (referred to as embossments) formed in the vinyl chloride resin layer by embossing, and oozes into the vinyl chloride resin layer, making it impossible to remove. Moreover, the oily dirt may be a nutrient source for various bacteria.

Further, the conventional surface treating agent cannot be said to have excellent chemical resistance, especially resistance to highly polar agents, and is used as a surface treating agent for sheets used in places requiring frequent disinfection. Is not always suitable. in addition,
The surface treating agent also has a drawback that it is easy to flow out by a solvent or the like.

Therefore, in recent years, a technique of attaching a fluororesin film to a polyvinyl chloride sheet with an adhesive has been developed instead of the above-described treatment technique using a surface treating agent, and is being widely adopted. According to this technology, it has a good effect on oily dirt as described above, and has sufficient stain resistance and, consequently, sufficient anti-bacterial growth, and also has a chemical resistance due to a fluororesin film. In addition, it imparts properties such as suitability for disinfection, abrasion resistance, and durability. Therefore, a sheet having a fluororesin film adhered to its surface is expected to be used in a wide range as a so-called functional sheet having excellent stain resistance, chemical resistance, abrasion resistance, and durability.

[0010]

By the way, in the above-mentioned functional sheet, usually, it is manufactured as a long product, which is cut into an appropriate size in accordance with the size of the place of use and used. . When the cross section of the vinyl chloride resin layer is exposed from the cut cross section and bacteria enter the vinyl chloride resin layer from the cross section, the bacteria proliferate due to the plasticizer, the stabilizer, and the like mixed in the resin layer. It is concerned.

Further, the cut functional sheet is sometimes formed into a certain shape and then attached to a use location. This shaping is performed by various methods such as welding or sewing, but in the case of sewing, the thread passes through the inside of the sheet and connects both surfaces, and bacteria are transmitted inside this thread. They can enter and breed.

It is also conceivable that fine cracks may occur in the fluororesin film adhered to the surface during use of the functional sheet. In such a case, the cracks may be caused by the cracks. There is a risk that bacteria will enter and propagate.

Therefore, in the functional sheet as described above, not only various measures on the surface by the fluororesin film but also various measures on the inside (ie, the vinyl chloride resin layer) are required. Has occurred.

The present invention has been made to meet such a demand, and is a sheet having excellent antibacterial properties as well as excellent in chemical resistance, stain resistance, abrasion resistance, etc. (Referred to as "antibacterial sheet").

[0015]

The antibacterial sheet of the present invention is a sheet formed by laminating a vinyl chloride resin layer and a fluorine resin layer via an adhesive layer. Contains an antimicrobial agent.

The soft vinyl chloride resin layer in the sheet of the present invention may be made of a sheet of this kind such as polyvinyl chloride, a copolymer of a vinyl chloride monomer with another monomer copolymerizable with the vinyl chloride monomer, or a blend of these resins. A layer made of a soft vinyl chloride resin which has been conventionally used can be used as a material for the above.

Other monomers copolymerizable with the above-mentioned vinyl chloride monomer include, for example, ethylene, propylene, vinyl acetate, vinylidene chloride, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, and the like.
Maleic acid, acrylonitrile fumarate and the like can be mentioned.

In such a vinyl chloride resin, as a plasticizer, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, didodecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, dihexyl phthalate, diisononyl phthalate, dioctyl adipate, diisodecyl adipate, dibutyl Other than sebacate, dioctyl sebacate, tributyl phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate, trioctyl phosphate, diphenylcresyl phosphate, etc., as well as trimellitate plasticizers and epoxies A plasticizer, a polyester plasticizer, or the like is used alone or in combination.

The mixing ratio of these plasticizers depends on the type of plasticizer, but in general, the greater the amount of plasticizer, the softer the vinyl chloride resin. An appropriate ratio is appropriately selected from the range of about 30 to 150 parts by weight with respect to 100 parts by weight of the vinyl chloride resin so that the required softness is obtained.

Along with these plasticizers, the vinyl chloride resin of the present invention contains an antibacterial agent. As this antibacterial agent, commonly used antibacterial agents such as silver-based, copper-based, zinc-based, chlorinated aromatic-based, organic nitrogen-sulfur compound-based, and organic nitrogen compound-based can be used. Two or more can be used in combination.

If the proportion of these antibacterial agents is too small, the desired antibacterial effect will not be exhibited. If the proportion is too large, this effect will not only be saturated and uneconomical, but will also be relatively expensive. If the compounding amount of the agent is too small, a high-quality product sheet cannot be produced at a high yield, or a product sheet having excellent properties that can be practically used in various fields is obtained. become unable. Therefore, in the present invention, it is preferable that the antibacterial agent is about 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin.

Further, in addition to the above-mentioned plasticizers and antibacterial agents, the vinyl chloride resin according to the present invention may further contain, if necessary, a coloring agent, a stabilizer, an antifouling agent, a fungicide, a lubricant, a flame retardant and the like. A suitable amount of the agent may be added.

In the present invention, the thickness of the layer made of the vinyl chloride resin is as follows:
It is preferable to set it to about 0.1 to 1.5 mm.

In the sheet of the present invention, the fluororesin layer laminated on the vinyl chloride resin layer via an adhesive layer includes ethylene tetrafluoride, ethylene trifluoride chloride, vinylidene fluoride, and the like. Homopolymers or copolymers of vinyl fluoride, propylene hexafluoride, perfluorovinyl ether, and other fluorine-containing monomers, or copolymers of these fluorine-containing monomers and monomers containing no fluorine, for example, ethylene-tetrafluoroethylene A layer made of a fluorinated ethylene copolymer, an ethylene-chlorofluoroethylene copolymer or the like is used.

Such a fluororesin layer is a layer to which additives such as an ultraviolet absorber, a colorant, a stabilizer, an antifouling agent, an antifungal agent, a lubricant, and a flame retardant are added as required. Is also good.

If the thickness of the fluorine-based resin layer is too thick, the surface of the sheet of the present invention becomes too hard to give a soft texture, and the surface of the layer is embossed or kneaded under moist heat conditions. (Japanese Patent Laid-Open No. 3-3 of the prior application filed by the present inventors)
No. 5849) and other fine irregularities (hereinafter referred to as
In the case of forming "textures", the formation of the textures becomes poor, and the material cost is significantly increased. On the other hand, if it is too thin, not only does the chemical resistance not improve, but also the surface strength decreases, and the wear resistance and durability do not improve. Therefore, in the present invention, about 1 to 50 μm, preferably 5 to 2 μm
It is suitable to be about 0 μm.

Since the fluorine resin layer and the vinyl chloride resin layer lack adhesiveness, an adhesive layer is interposed between the two layers. As the adhesive layer, any material having a property capable of firmly adhering a fluorine resin and a vinyl chloride resin can be used. For example, acrylic, acrylic epoxy, acrylic phenol modified vinyl,
A layer made of a vinylidene chloride-based or polyester-based temperature-sensitive adhesive is used.

The method of bonding the fluorine-based resin layer and the vinyl chloride-based resin layer includes a method of bonding the respective resin layers with the resin-based adhesive as described above, a method of bonding the fluorine-based resin and the resin for the adhesive as described above. (A method of simultaneously extruding a plurality of types of resins and simultaneously laminating a plurality of layers is referred to as "coextrusion"; therefore, in the present invention, this extrusion method is hereinafter referred to as "coextrusion." Extrusion ”) and bonding this co-extruded product to the vinyl chloride resin layer by thermal lamination, or co-extrusion of three layers of a fluorine resin, the adhesive resin and the vinyl chloride resin at the same time. Any suitable method such as a method of bonding by means of bonding can be adopted.

The thickness of the adhesive layer is not particularly limited, and it is sufficient that the adhesive layer has a thickness capable of firmly bonding the two resins.

The sheet of the present invention is based on a layer structure composed of the above three resins, but the basic structure can be modified as follows.

One is to use the above-mentioned vinyl chloride resin layer as a foam layer. The expansion ratio in this case is not particularly limited, and is, for example, 130% to 350%, preferably 15%.
0-200% is suitable.

Another one is to form the above-mentioned vinyl chloride resin layer into a plurality of layers. In this case, one of the layers
The layer may be a foam layer. In addition, each layer may have the same degree of softness, or the present inventors may use a “functional sheet”
Patent application (hereinafter, the "separate proposal" say) in and to 1993 June 28, dated as of the thing, the layers non
A foam layer may be used so that the degree of softness increases (that is, becomes flexible) sequentially from the adhesive layer side to the non-adhesive layer side.

In the latter case where the softness is gradually increased from the adhesive layer side to the non-adhesive layer side, the sheet of the present invention is imparted with excellent bending resistance and rubbing resistance. Cracks can not be generated on the seat surface due to the tension applied to the seat when attaching it to a chair or bed, or due to the frequent bending or kneading force applied to these during use after the seat is installed. Absent.

As a method of changing the softness of the vinyl chloride resin layer, there is a method of changing the blending amount of the above-described plasticizer as separately proposed. That is, the vinyl chloride resin layer having relatively high softness on the non-adhesive layer side contains a plasticizer in a higher blending ratio than the vinyl chloride resin layer having relatively low softness on the adhesive layer side. When a vinyl chloride-based resin layer is present, the amount of the plasticizer may be changed sequentially.

Specifically, the vinyl chloride resin layer on the non-adhesive layer side is about 60 to 150 parts by weight of the plasticizer per 100 parts by weight of the vinyl chloride resin, and the vinyl chloride resin layer on the side in contact with the adhesive layer. Is, based on 100 parts by weight of vinyl chloride resin,
The amount of the plasticizer is about 30 to 80 parts by weight, and the ratio of the plasticizer is gradually reduced from the non-adhesive layer side to the adhesive layer side.

The antimicrobial agent may be added to each layer at the above ratio, or the antimicrobial effect can be sufficiently obtained only by adding it to any one layer at the above ratio.

When a plurality of vinyl chloride resin layers are used, the thickness of each layer is not particularly limited.

Still another one is to laminate a foam layer and a base fabric in this order on the side surface of the non-adhesive layer of the vinyl chloride resin layer (that is, to form a leather structure). The base cloth may be woven or non-woven fabric made of natural or synthetic fibers,
A base fabric material usually used for this type of sheet, such as a knitted fabric, can be preferably used. The thickness of the base fabric is not particularly limited,
An appropriate thickness is selected according to the purpose of use of the sheet of the present invention.

The foam layer may be made of a general synthetic resin such as vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, acrylic resin, etc., which is used for such a sheet, a foaming agent, and the like. Plasticizers, colorants, stabilizers, antifouling agents, fungicides, lubricants,
A foam layer prepared by various additives such as a flame retardant is exemplified. The foaming ratio of this foam layer is also not particularly limited, but if it is too low, it does not give a good texture, and if it is too high, it causes poor foaming or lamination failure or lowers mechanical strength.
In the present invention, 130 to 350%, preferably 150 to 2%
50% is suitable.

Further, in the sheet of the present invention, the antibacterial agent is not limited to the vinyl chloride resin layer, and may be blended in the adhesive layer or the fluorine resin layer, or a base cloth containing the antibacterial agent may be used. It goes without saying that the foam layer may also contain an antibacterial agent.

The sheet of the present invention having the above constitution can be easily produced by a usual lamination technique using a vinyl chloride resin composition containing an antibacterial agent. Further, as described above, a grain may be formed on the sheet surface of the present invention by embossing or kneading under moist heat conditions, or prior to providing a fluorine-based resin layer via an adhesive layer. On the vinyl chloride resin layer, a pattern such as a so-called cloud pattern approximated to the surface pattern of natural leather and other appropriate patterns can be printed in the same manner as in the case of ordinary PVC sheet or PVC leather.

[0042]

In the sheet of the present invention, the action of the antibacterial agent blended in the vinyl chloride resin layer exhibits an antibacterial action inside the sheet. Therefore, even if bacteria enter the vinyl chloride resin layer exposed on the cut surface of the sheet of the present invention,
In addition, even if bacteria enter the interior through the thread used for sewing or from fine cracks generated on the surface,
It does not breed.

In addition, a fluorine resin layer is present on the surface of the sheet of the present invention, and has excellent chemical resistance, stain resistance, and abrasion resistance derived from the resin. In addition to being sufficiently resistant to disinfection, there is no bleeding such as a plasticizer or a stabilizer that is a nutrient source of bacteria, so that the growth of bacteria can be suppressed as much as possible.

[0044]

【Example】

[Preparation Example of Sheet of the Present Invention] Example 1 A vinylidene fluoride resin (thickness: 10 μm) and polymethyl methacrylate (thickness: 10 μm) were coextruded to give a total thickness of 2
A film I having a two-layer structure of 0 μm was produced. Next, Table 1
Was used to prepare a film II having a thickness of 0.2 mm by a calendering method. The surface of the film II was heated to 150 ° C.
To obtain a sheet of the present invention. FIG. 1 shows a schematic diagram of a cross section of this sheet. In FIG. 1, 1 indicates a vinyl chloride resin layer containing an antibacterial agent of the film II, 2 indicates an adhesive layer made of polymethyl methacrylate of the film I, and 3 indicates a vinylidene fluoride resin layer of the film I. I have.

[0045]

[Table 1]

Example 2 A foam layer having a composition shown in Table 2 (thickness 0.3 mm, foaming ratio 200%) on a base cloth (knitted fabric having a thickness of 0.35 mm)
Are laminated by a calender method, and a vinyl chloride resin layer (thickness: 0.2 mm) containing an antibacterial agent and having the composition shown in Table 1 used in Example 1 is laminated thereon by a calender method. Heat for 1 minute, foam and laminate III
Was prepared. Next, the laminate I heated to 150 ° C.
The polymethyl methacrylate surface of the two-layer film I made of the polymethyl methacrylate (thickness 10 μm) and the vinylidene fluoride resin (thickness 10 μm) prepared in Example 1 is in contact with the vinyl chloride resin layer II. And the laminate III and the film I were firmly adhered to each other to obtain a sheet of the present invention.

[0047]

[Table 2]

[Example of Evaluation of Antibacterial Property of Sheet of the Present Invention] From the two kinds of sheets of the present invention obtained as described above, 3 × 3c was obtained.
m samples were sampled and subjected to an antibacterial test. The evaluation method was as follows: a sample was stuck on a bouillon agar medium to which test bacteria (Staphylococcus aureus, Escherichia coli) had been added by the inhibition circle method.
The measurement was performed by measuring the inhibition zone formed after culturing at 3 ° C. for 18 hours. Table 3 shows the results.

For comparison, a similar antibacterial test was also performed on a sample obtained by cutting a conventional commercially available PVC sheet (used for a chair surface material, etc.) into a similar size. . This result is also shown in Table 3.

[0050]

[Table 3]

From Table 3, it can be seen that the sheet of the present invention clearly shows antibacterial activity, but the conventional PVC sheet does not.

[0052]

As described above in detail, according to the sheet of the present invention, the vinyl chloride resin layer has an excellent antibacterial effect, and the fluorine resin layer has an excellent chemical resistance, stain resistance, and resistance to contamination. It has the effect of migrating (bleed resistance of plasticizers and stabilizers), abrasion resistance, and durability. Therefore, the sheet of the present invention is required to have antibacterial properties, such as chairs and examination tables in hospitals, and as a surface material that is required to have chemical resistance or durability that does not change even after frequent disinfection. Very suitable.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing one embodiment of a sheet of the present invention.

[Explanation of symbols]

 Reference Signs List 1 vinyl chloride resin layer containing antimicrobial agent 2 adhesive layer 3 fluorine resin layer

Claims (3)

(57) [Claims] 1. A sheet formed by laminating a vinyl chloride-based resin layer and a fluorine-based resin layer via an adhesive layer, wherein at least the vinyl chloride-based resin layer contains an antibacterial agent. Antibacterial sheet. 2. The antibacterial sheet according to claim 1, wherein the vinyl chloride resin layer has a plurality of layers, and at least one of the layers contains an antibacterial agent. 3. The non-foamed multi-layer vinyl chloride resin layer,
3. The antibacterial sheet according to claim 2, wherein the degree of softness gradually increases from the adhesive layer side to the non-adhesive layer side.