JP3055844B2 - Compositions and uses thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition having both an antibacterial property and an antifouling function, and a laminate having the composition layer.

[0002]

2. Description of the Related Art Heretofore, there has been known a wallpaper containing a polyvinyl chloride resin layer. However, wallpaper containing these polyvinyl chloride resin layers, decorative panels used for ceiling materials, wall materials, floor materials, etc. of general households, hospitals, clinics, restaurants, factories, ships, trains, automobiles, etc. (hereinafter collectively referred to as wallpaper) Is easily contaminated with tobacco smoke, scale, graffiti, and pigments in various foods. Also, a plasticizer for the polyvinyl chloride resin bleeds on the surface of the wallpaper. Dust adheres to the bleeding plasticizer, and the PVC wallpaper becomes more easily soiled. In addition, there is also a problem that there is no effect of preventing nosocomial infection, which is a problem in hospitals and clinics, and the effect of suppressing the growth of bacteria.

As shown in Japanese Patent Application Laid-Open No. 58-23973, a stain-resistant wallpaper in which an acrylic resin film is laminated on a PVC wallpaper is known. However, although these wallpapers have excellent stain resistance compared to non-laminated PVC wallpaper, they are not perfect, and there is a problem that the tendency becomes large especially when a long period of time has passed after lamination. Further, the acrylic resin film is inferior in chemical resistance and particularly easily susceptible to esters, ketones, aromatic compounds and the like, so that it is necessary to pay attention to dirt wiping, which is not satisfactory.

As disclosed in Japanese Utility Model Application Laid-Open No. 59-172797, a stain-resistant wallpaper obtained by laminating a film of a saponified ethylene-vinyl ester copolymer (hereinafter referred to as EVOH) on a PVC wallpaper is known. I have. This wallpaper has excellent chemical resistance and plasticizer barrier properties, and is more excellent in stain resistance than non-laminated PVC wallpaper. Further EVO
The H film has an advantage that dust is less likely to adhere to the surface of the wallpaper because the H film has a relatively small electric resistance and is hardly charged with static electricity. However, there is no description about the antibacterial effect in the above-mentioned actual opening.

JP-A-60-224542, JP-A-60-224
JP-A-239233, JP-A-60-24205 and JP-A-62-15265 also show that EVOH is excellent in barrier properties of a plasticizer for a polyvinyl chloride resin, and EVOH is a plasticizer for a polyvinyl chloride resin. It is described that the contamination resistance can be improved by using it for the blocking of water. However, there is no description about the antibacterial effect in the above-mentioned Japanese Patent Application Laid-Open No. Sho.

On the other hand, Japanese Patent Application Laid-Open No. 4-173244 describes a multi-layered antibacterial plastic film characterized in that the outermost layer and / or the innermost layer of the multi-layer plastic film is a film layer containing an inorganic antibacterial substance. is there. However, the above-mentioned Japanese Patent Application Laid-Open No. HEI 9 does not describe mixing a specific antibacterial agent with EVOH, and further does not describe anything about an instrument or a building material.

[0007]

As described above, there is a strong demand for laminates having both antibacterial properties and antifouling functions, especially for wallpaper or decorative boards.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and has an antibacterial function, a barrier property of a plasticizer for polyvinyl chloride resin, an antifouling function, and the like. It is intended to obtain a laminate having the same, particularly a wallpaper or a decorative board.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a plasticizer for polyvinyl chloride resin which has an EVO having barrier properties and stain resistance.
Inorganic oxo acid salts having specific antibacterial metal ions in H
And providing a composition containing a carboxylic acid-modified polyethylene resin , and laminating the composition layer on at least one surface of a substrate, especially a polyvinyl chloride resin layer containing a plasticizer, particularly on the outermost layer Achieved by providing the body.

In the present invention, an inorganic oxo acid salt and a carboxylic acid-modified polyether having an antibacterial metal ion in EVOH having a stain resistance and a barrier property against a polyvinyl chloride plasticizer.
By including a Tylene resin , the barrier property of the plasticizer,
Without impairing the stain resistance, the antibacterial effect is higher than when it is blended with polyethylene or the like, and it is an excellent material that is extremely practical as PVC wallpaper, decorative board and the like.

In the present invention, a typical example of the inorganic oxo acid salt having a specific antibacterial metal ion is one obtained by ion-exchanging a metal ion of an inorganic oxo acid salt with a metal ion having antibacterial property. Here, examples of the inorganic oxo acid salt include silicate, phosphate, titanate, antimonate and the like. Examples of the silicate include magnesium metasilicate, calcium silicate, magnesium silicate, and phosphorus. As the acid salt, calcium phosphate and zirconium phosphate, and as the titanate, compounds such as potassium titanate and calcium titanate, and as the antimonate, compounds such as sodium antimonate are preferable.In particular, magnesium aluminate metasilicate and calcium phosphate are mainly used. Apatite as a component is also preferable from the viewpoint of safety.
Apatite is also called apatite, and is a general term for fluorapatite, chlorapatite, and hydroxyapatite.

The oxo acid salt may be preformed or granular. The particle size is 2μm in order to make the antibacterial property, especially the antibacterial property of the wallpaper uniform.
The thickness is particularly preferably 0.5 μm or less.

As the metal ion having antibacterial property to be ion-exchanged, a metal ion usually used as an antibacterial agent and a bactericide, for example, silver, copper, zinc, tin, mercury, lead, cadmium and the like can be applied. In particular, metal ions of silver, copper, zinc, and tin are desirable in terms of safety to the human body.

These metal ions are ion-exchanged with the metal ions of the oxo acid salt in a usual manner.

For example, ion exchange of silver, copper, zinc, tin and the like is carried out in a region lower than the pH value at which hydroxide is formed and in which the oxo acid salt is not dissolved. That is, pH 9-4 for silver, pH 6-4 for copper, and pH for zinc.
A temperature range of 9 to 4 and a temperature range of 60 ° C. or higher is preferable. The ratio of the antibacterial metal ions to be ion-exchanged is preferably 0.1 to 90 mol% of the ion exchange capacity of the oxoacid salt, and the ion-exchanged ions in the antibacterial agent are Is preferably 0.01 to 40% by weight. If the metal ion is less than the above minimum value, the antibacterial property is not sufficient, and if the metal ion exceeds the maximum value, the metal ion becomes unstable and the stability and sustainability of the antibacterial effect are lacking.

The antibacterial agent used in the present invention is different from silver zeolite (in which the ion of a hydrated alkali metal salt or alkaline earth metal salt of aluminosilicate is ion-exchanged with a metal ion such as silver), It is possible to use other antibacterial agents such as silver zeolite in combination.

In the present invention, the EVOH has an ethylene content of 20 to 65 mol%, preferably 25 to 60 mol%.
Those having a molar percentage of at least 90 mol%, preferably at least 95 mol%, of a vinyl ester component are suitably used. If the ethylene content is less than 20 mol%, the water resistance is poor, and if it exceeds 65 mol%, the oil resistance is poor, and the oily contaminants easily penetrate, and the stain resistance is poor, which is not preferable.
Even if the degree of saponification of the vinyl ester component is less than 90 mol%, the oil resistance becomes poor, so that oily contaminants easily penetrate, and the stain resistance is also poor, which is not preferable. As a vinyl ester used as a raw material for EVOH, vinyl acetate is desirable from the viewpoint of economy. Comonomer components other than ethylene and vinyl ester can be used in this EVOH as long as the object of the present invention is not impaired.

The EVOH may be a composition of two or more EVOHs having different ethylene contents, saponification degrees, and polymerization degrees. Boric acid, an antioxidant,
Slip agents, coloring agents, deodorants, and thermoplastic resins such as polyamides and polyolefins may be blended. EVO
H and the specific antibacterial agent are mixed in EVOH 90 to 9
9.9% by weight and antimicrobial agent 10 to 0.1% by weight, preferably E
95-99.8% by weight of VOH and 5-0.2% by weight of antibacterial agent
It is.

In the present invention, the method of incorporating the antimicrobial agent into the resin may be a method of previously blending the resin with a twin screw extruder, a Brabender plastograph, or the like, or a method of directly supplying the resin to various molding machines. There is a method of molding while kneading with a molding machine, but once a high-concentration master pellet is prepared with an extruder, and 1/1 to 1/30
A method in which a material diluted to a certain extent is subjected to melt extrusion molding is preferred. When an antimicrobial agent is contained in the above resin, a metal soap such as sodium stearate, magnesium stearate and zinc stearate, and a dispersing aid such as ethylenebisfatty acid amide and polyethylene wax may be added. Further, the content of the antibacterial agent is 10 to 0.1% by weight, preferably 5 to 0.2% by weight based on the composition. When the amount of the antibacterial agent is less than 0.1% by weight, the antibacterial function is not sufficient. These resins have antibacterial agents, deodorants,
The compounding of an antioxidant, an ultraviolet absorber, a lubricant, various resins and the like is free as long as the object of the present invention is not impaired.

Further, by blending a carboxylic acid-modified polyethylene with EVOH, a composition having excellent matting can be obtained, but a change in melt viscosity is observed. However, surprisingly, by blending the specific antibacterial agent used in the present invention, it is possible to suppress the change in melt viscosity, the antibacterial property is maintained for a long time, and the composition is excellent in matting. Can be obtained. That is, an embodiment of the present invention is a composition in which the above specific antibacterial agent is blended with a composition comprising 95 to 50% by weight of EVOH and 5 to 50% by weight of a carboxylic acid-modified polyethylene resin. By using this composition, the surface gloss of at least one surface of the composition layer can be made to be matte of 40% or less. The matte layer not only gives the PVC wallpaper a sense of quality but also makes it possible to mix the chemicals that are difficult to mix with EVOH into the carboxylic acid-modified polyethylene resin, thereby expanding the range of options for adding functions. Become. The mixing ratio of EVOH and carboxylic acid-modified polyethylene resin is EVO
H95 to 50% by weight, carboxylic acid-modified polyethylene resin 5 to 50% by weight, preferably EVOH 92 to 55% by weight, and carboxylic acid-modified polyethylene resin 8 to 45% by weight. Carboxylic acid-modified polyethylene resin content of 5% by weight
If it is less than 50%, the glossiness is not satisfied, and if it exceeds 50% by weight, the plasticizer barrier properties are inferior, the film-forming properties are deteriorated, and defects such as the formation of holes in the film appear. Further, the melt index (hereinafter referred to as MI) of EVOH and the carboxylic acid-modified polyethylene resin measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238 is MIa and M, respectively.
When Ib is satisfied, a good matte layer is obtained when 3 ≦ MIa / MIb ≦ 80.

Here, the carboxylic acid-modified polyethylene resin is obtained by graft polymerization of an α, β-unsaturated carboxylic acid or the carboxylic anhydride to a polyethylene resin.
The content of α, β-unsaturated carboxylic acid or the carboxylic anhydride (graft amount) is 0.0005 to 0.5 mol%;
Preferably it is 0.001-0.4 mol%. 0.00
If it is less than 05 mol%, the dispersibility becomes poor when blended with EVOH, and the matting effect of the film is poor.
If it exceeds mol%, the viscosity increases during the blending operation, and the film-forming property deteriorates. It is desirable that all the polyethylene resins are graft-modified with an α, β-unsaturated carboxylic acid or the carboxylic anhydride, but a blend of a high-concentration carboxylic acid-modified seed polymer and an unmodified polymer, The graft amount may be within the above range. Examples of the α, β-unsaturated carboxylic acid or the carboxylic anhydride include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride, with maleic anhydride being preferred. Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, with high-density polyethylene being preferred.

In the present invention, the composition containing the antibacterial agent is effectively used as a laminate with another resin. Here, examples of the other resin layer include a polyvinyl chloride resin, in particular, a polyvinyl chloride resin containing a plasticizer, a polyolefin (eg, polyethylene, polypropylene), polystyrene, polyester, and polyamide. The thickness of the composition layer is not particularly limited, but is preferably from 10 to 30 μm. When the composition layer is laminated with the polyvinyl chloride resin layer, for example, when embossing, the composition layer containing the antibacterial agent hardly generates pinholes at 10 to 30 μm. It is preferable because the barrier property of the plasticizer is good. The composition layer of the present invention is formed into a film by a melt extrusion method such as a T-die method or an inflation method.
A laminate can be formed by heat lamination and polysand lamination. A laminate can also be obtained by extruding the composition of the present invention onto another resin film or by co-extruding the composition of the present invention and another resin.

In the present invention, a typical example is a laminate of the composition layer of the present invention on a wallpaper containing a polyvinyl chloride resin layer containing a plasticizer. Here, wallpaper containing a polyvinyl chloride resin layer containing a plasticizer is flame-retardant paper,
On a support made of nonwoven fabric, glass fiber, asbestos paper, etc., polyvinyl chloride resin, plasticizer, if necessary,
By laminating a composition containing pigments, fillers, stabilizers, etc. by calendering method, coating method, etc., further by printing on these laminates, or by compounding a foaming agent And a product obtained by foaming a polyvinyl chloride resin 1.5 to 15 times as the final product. In the present invention, as another example of the laminate, a decorative plate on which the composition layer of the present invention is laminated can be given. Here, the decorative board is a generic name of a printed decorative board, a decorative plaster board, a PVC decorative board, a PVC steel plate, a PVC incombustible board, and the like. The printed decorative board is a product obtained by printing on thin paper or the like and laminating it on a support made of plywood, particle board, or the like. Also, embossing may be applied to emphasize the three-dimensional effect. In addition, decorative plaster boards, PVC decorative boards, PVC steel sheets, PVC non-combustible boards, etc. are printed on sheets made of polyvinyl chloride resin containing a plasticizer, etc., and then printed on plaster boards, plywood, particle boards, steel sheets, concrete It is a product laminated on a support such as a plate. As in the case of printed decorative boards, to emphasize the three-dimensional effect,
Sometimes embossed.

In the present invention, the plasticizer for the polyvinyl chloride resin is liquid at 20 ° C.
It contains 5% by weight. Examples of the plasticizer which is liquid at 20 ° C. include dibutyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, diisodecyl phthalate, didecyl phthalate, dinonyl phthalate, butyl lauryl phthalate, dilauryl phthalate, and butyl phthalate. Examples include phthalate plasticizers such as benzyl, phosphate plasticizers such as tricresyl phosphate, tributyl phosphate and tri-2-ethylhexyl phosphate, and chlorine-containing plasticizers such as chlorinated paraffin. By laminating a layer of the composition of the present invention on at least one surface of the polyvinyl chloride resin layer containing these plasticizers, particularly on the outermost layer, a desired laminate can be obtained.

In the present invention, EVO containing an antibacterial agent
The H layer has a sufficient antifouling function, and bacteria adhering to the outermost layer do not multiply on the surface and do not penetrate the inner layer, and furthermore, the bleeding of the plasticizer in the inner layer polyvinyl chloride resin layer to the outer layer. It is preferable because it can be prevented.

In the present invention, layers other than the EVOH layer,
For example, each layer or a specific layer of the PVC wallpaper may contain an antibacterial agent. By doing so, in addition to the antibacterial property from the surface side, the generation of mold from the wall side, and the antibacterial property at the end portion and the joint portion of the PVC wallpaper can be secured. In this case, the antibacterial agent may be the antibacterial agent according to the present invention or a known arsenic-based antibacterial agent.

In the present invention, there is no particular limitation on the method of laminating a layer obtained by kneading an antibacterial agent into EVOH and a PVC wallpaper. As shown in JP-A-59-172797, an urethane-based adhesive may be laminated on a PVC wallpaper, and an EVOH film containing an antibacterial agent may be laminated thereon. JP 6
As described in JP-A-224542, JP-A-60-239233 and JP-A-60-242053, an urethane-based adhesive alone is laminated on an EVOH film into which an antibacterial agent has been kneaded, or polyester or A mixture of a modified product of a copolymer of vinyl acetate and vinyl chloride and a urethane-based adhesive is laminated, or a urethane-based adhesive is laminated first, followed by polyester or a copolymer of vinyl acetate and vinyl chloride. A modified polymer may be laminated, and a vinyl chloride wallpaper may be attached thereto. Alternatively, a thermoplastic resin that can be bonded to both EVOH and PVC may be coextruded with EVOH, and the resulting film may be laminated with PVC.

The antibacterial laminate of the present invention obtained in this manner has no change in laminating strength even after long-term use, and further maintains the antifouling function and the antibacterial function. Very useful as a decorative board. As described above, the composition of the present invention is particularly effective as a wallpaper or decorative board, but can also be effectively used as a laminate laminated on another substrate.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0030]

EXAMPLES Example 1 3.2 g of silver nitrate and 5.7 g of copper sulfate were dissolved in 5 l of pure water, and the pH was adjusted to 5. In this aqueous solution, magnesium aluminate metasilicate (Al ↓ 2O ↓ 3 ・ MgO ・ 2SiO
↓ 2.7H ↓ 2O, average particle size 0.02μm, water content 20
125% by weight), adjust the pH to 5 again, and add
Stirred at 0 ° C. for 1 hour. Then, it was washed with 5 equivalents of warm water, dried at 100 ° C. for 4 hours, and baked at 600 ° C. for 2 hours to obtain an antibacterial agent.

Next, 75 parts by weight of EVOH having an ethylene content of 44 mol% and a saponification degree of the vinyl acetate component of 99.5 mol%, 25 parts by weight of carboxylic acid-modified high-density polyethylene, and 1 part by weight of the above antibacterial agent were added. The mixture was pelletized at 220 ° C. using a twin screw extruder. In order to examine the thermal stability of the blended pellets, the MI after heating the blended pellets at 120 ° C. for 1 hour in air was 1.0 g / 10 minutes, and the MI after heating in air for further 24 hours. The MI was 0.15 g / 10 minutes, and the change in melt viscosity was relatively small. An antibacterial EVOH film having a thickness of 15 μm was obtained from the blended pellets at 220 ° C. by using a single screw extruder. Using a gravure coater, a urethane-based adhesive Adcoat AD-335A having a solid content concentration of 20% by weight and a curing agent Cat-10 (manufactured by Toyo Morton Co., Ltd., mixing ratio: 17: 1) were applied to the film at a coating amount of 2 g / g.
m ↑ 2 (solid content basis)
After drying for minutes, MPR-TM (manufactured by Nissin Chemical Industry Co., Ltd.), which is a modified product of a copolymer of vinyl acetate and vinyl chloride dissolved at a solid concentration of 18% by weight, was applied again using a gravure coater. It was coated so as to have an amount of 2 g / m ↑ 2 (based on solid content), and dried at 70 ° C. for 1 minute.

On the other hand, a backing flame-retardant paper impregnated with 24 parts by weight of a guanidine sulfamate-based flame retardant per 100 parts by weight of paper was added with 100 parts by weight of polyvinyl chloride resin and 5 parts by weight of filler 5.
0 parts by weight, plasticizer (di-2-ethylhexyl phthalate) 55 parts by weight, pigment 20 parts by weight, flame retardant 3 parts by weight, stabilizer 2 parts by weight, blowing agent 2 parts by weight, and binazine (organic arsenic antibacterial agent) ) After laminating 2 parts by weight of the compound, PVC was foamed to obtain a PVC wallpaper.

An adhesive surface applied to the EVOH film;
Combine the surfaces of the polyvinyl chloride resin laminated on paper,
And embossed at the same time to obtain a wallpaper having the desired antibacterial properties and anti-smudge function.

In order to check the stain prevention function, the wallpaper E
Oily red ink (Mitsubishi Marker manufactured by Mitsubishi Pencil Co., Ltd.) and soy sauce (Kikkoman Co., Ltd., Kikkoman dark mouth) were applied to the VOH surface in a size of 2 cm × 2 cm, and after 24 hours, they were wiped off with gauze with benzine. But no trace was left. In addition, even when wiped with gauze moistened with a neutral detergent, no trace remains in the case of soy sauce, and it was confirmed that the surface was not damaged by water and had sufficient water resistance. As shown in FIG. 1, the stain prevention function was perfect.

In order to examine the antibacterial function, E. coli (Esc
hericia coli) 3.0 × 10 ↑ 4 pieces /
5 ml of physiological saline having a concentration of
1 g of an H film was put therein, and the viable cell count was measured after shaking at 28 ° C. for 24 times. As shown in Table 2, 1.0 × 10 2 /
The ml was very good. Separately, the antibacterial EVOH film was stored at 20 ° C. for half a year and its antibacterial function was examined. As a result, there was no deterioration with time and the antibacterial function was maintained for a long period of time.

Comparative Example 1 The procedure of Example 1 was repeated except that no antibacterial agent was added. Blend pellets at 120 ° C, 2
The MI after heating in air for 4 hours is 0.03 g / 10
Min, and the heat deterioration was more severe than that to which an antibacterial agent was added. A film was obtained from the blended pellets, and the antifouling function and the antibacterial function were tested in the same manner as in Example 1. The results are shown in Tables 1 and 2, respectively. The stain preventing function was perfect, but no antibacterial function.

Comparative Example 2 The procedure of Example 1 was repeated, except that polyethylene was used in place of EVOH, and the stain prevention function and the antibacterial function were similarly tested. The results are shown in Tables 1 and 2, respectively. The stain prevention function is incomplete and has an antibacterial function.
It was inferior to VOH type.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

Industrial Applicability The composition of the present invention has an excellent stain-preventing function, a high antibacterial property, and can suppress a change in melt viscosity.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁷ Identification code FI C08L 29/04 C08L 29/04 S // (C08L 23/08 23:26) (C08L 29/04 23:26) (56) JP-A-63-179934 (JP, A) JP-A-60-224542 (JP, A) JP-A-3-43457 (JP, A) JP-A-3-83906 (JP, A) JP-A-3 −68642 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/08 C08L 29/04 C08K 3/00-3/40 B32B 27/00-27/42

Claims (4)

(57) [Claims] An ethylene content of 20 to 65 mol%, vinyl
Ethylene-vinyl ester having a degree of saponification of ester component of 90 mol% or more
95 to 50% by weight of saponified ester copolymer
Tree comprising 5 to 50% by weight of a boronic acid-modified polyethylene resin
Fat composition 90 to 99.9% by weight, and an antibacterial metal
From 10 to 0.1% by weight of an inorganic oxo acid salt having
Composition. 2. The composition according to claim 1, which comprises at least one layer.
Having a laminate. 3. The composition layer according to claim 1, which contains a plasticizer.
Product on at least one surface of the polyvinyl chloride resin layer
Layer body. 4. A wall comprising the laminate according to claim 2 or 3.
Paper or decorative board.