JP2011236703A - Antibacterial and antifouling film for wall covering material and wall covering material formed by laminating the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antibacterial and antifouling film for a wall covering material, which has fast-acting antibacterial performance, flaw resistance and antifouling properties, and is suitably used for the wall covering material, and to provide a wall covering material formed by laminating the antibacterial and antifouling film for the wall covering material.SOLUTION: The antibacterial and antifouling film for the wall covering material comprises: an upper layer containing at least 1.5-10 pts.wt. of an inorganic antibacterial agent containing silver, 1-50 pts.wt. of an ethylene-based copolymer, and 1-60 pts.wt. of an inorganic filler, with respect to 100 pts.wt. of a polypropylene resin; an lower layer containing a polypropylene resin; and an adhesion layer containing a base compound of a polyvinyl chloride-vinyl acetate copolymer and an isocyanate-based curing agent.

Description

The present invention relates to an antibacterial and antifouling film for wall coverings, which has immediate antibacterial performance, scratch resistance and antifouling performance, and can be suitably used for wall coverings, and the antibacterial and antifouling film for wall coverings. It is related with the wall covering material which laminates | stacks.

Molded articles mainly composed of polyvinyl chloride resin or the like are frequently used as interior materials for buildings. Among these, the wall covering material (hereinafter referred to as polyvinyl chloride wall covering material) including a polyvinyl chloride resin layer is inexpensive and excellent in various physical properties, and can be further imparted with design by embossing to form fine irregularities on the surface. Therefore, it is widely used in general households, hospitals, clinics, schools, stores, etc. However, there is a problem of being easily damaged by meals, cigarettes, hand dust, graffiti, etc., and pets or accidental contact. Recently, vigilance is increasing for diseases caused by microorganisms such as nosocomial infections and insect venoms.
Therefore, conventionally, a technique for laminating films for the purpose of imparting scratch resistance and stain resistance to polyvinyl chloride wall covering materials is known. For example, a saponified ethylene / vinyl acetate copolymer film is disclosed in Patent Document 1. Has been. However, the wall covering material in which such films are laminated sometimes has difficulty in forming fine irregularities when the film is hard. On the other hand, for example, Patent Document 2 discloses that a polypropylene film is used for the purpose of easily forming fine irregularities and improving the embossing followability.

JP 2006-282834 A JP 2006-096021 A

However, in recent years, higher antibacterial performance has been demanded due to growing concerns about microorganisms, and as one of the main countermeasures, it has been required to provide the ability to kill microorganisms more quickly, that is, to provide immediate antibacterial performance. . However, the prior art cannot achieve an immediate antibacterial performance.

In view of the present situation, the present invention has an antibacterial and antifouling film for wall coverings that has an immediate antibacterial performance, scratch resistance and antifouling performance and can be suitably used for wall coverings, and the wall covering. It aims at providing the wall covering material which laminates | stacks the antibacterial antifouling film for materials.

The present invention comprises at least 1.5 to 10 parts by weight of an inorganic antibacterial agent containing silver, 1 to 50 parts by weight of an ethylene copolymer, and 1 to 60 parts by weight of an inorganic filler with respect to 100 parts by weight of a polypropylene resin. An antibacterial antifouling film for wall covering, comprising: an upper layer containing; a lower layer containing a polypropylene resin; and an adhesive layer containing a vinyl chloride / vinyl acetate copolymer main component and an isocyanate curing agent. (Claim 1).
Furthermore, it is more preferable that the mass reduction rate of the inorganic antibacterial agent containing silver when heated at 100 ° C. for 24 hours is 0.10% or less (Claim 2), and the thickness of the upper layer is 4 to 15 μm (Claim 3).
According to the present invention, the antibacterial activity value against S. aureus and Escherichia coli after 3 hours of contact with the bacterial solution in a test according to JIS Z 2801 can be achieved to be 4.0 or more (claim 4).
In addition, a wall covering material in which such films are laminated and embossed is a preferred embodiment of the present invention (claim 5).

By using the film of the present invention, an antibacterial and antifouling film for wall coverings that has immediate antibacterial properties, scratch resistance and antifouling properties and can be suitably used for wall coverings, and the wall coverings It becomes possible to provide the wall covering material which laminates | stacks the antibacterial antifouling film for materials.
In addition, when the mass reduction rate of the inorganic antibacterial agent containing silver when heated at 100 ° C. for 24 hours is 0.10% or less, the effect of excellent workability is achieved.
Furthermore, the antibacterial antifouling film for wall coverings of the present invention is laminated and embossed to provide excellent scratch resistance and antifouling properties, and can easily impart a design with fine irregularities, and also has immediate antibacterial properties Can be obtained.

Sectional drawing of the antibacterial antifouling film for wall coverings according to the present invention Sectional drawing of the antibacterial antifouling film for wall coverings according to the present invention Sectional drawing of wall covering laminated with antibacterial antifouling film for wall covering according to the present invention

The polypropylene resin used in the present invention is preferable in that it can impart scratch resistance and antifouling properties. Polypropylene resins include propylene homopolymers, random copolymers such as propylene / α-olefin random copolymers, propylene / α-olefin block copolymers, blocks such as propylene / ethylene / α-olefin copolymers Copolymers can be used. A plurality of these polypropylene resins may be used. In particular, a block copolymer such as a propylene / α-olefin block copolymer is preferable from the viewpoint of heat resistance and matting property.

Specific examples of the propylene / α-olefin block copolymer include propylene / ethylene block copolymer, propylene / 1-butene block copolymer, propylene / 1-pentene block copolymer, propylene / 1-hexene block copolymer. Examples thereof include a polymer, a propylene / 4-methyl-1-pentene block copolymer, a propylene / 1-heptene block copolymer, and a propylene / 1-octene block copolymer. Of these, propylene / ethylene block copolymers are preferred because of their good processability.

The polypropylene resin preferably has a melt flow rate of 1 to 10 g / 10 minutes. By using a polypropylene resin having a melt flow rate within this range, processability and scratch resistance are improved. In addition, the melt flow rate employ | adopted by this invention is the value measured based on JISK7210.

As the antibacterial agent used in the present invention, an inorganic antibacterial agent whose decomposition temperature is significantly higher than the processing temperature and high in safety is suitable. Among them, an inorganic antibacterial agent containing silver is preferable because it has an immediate antibacterial property.

The antibacterial agent containing silver may be one in which silver is supported on a carrier. Examples of the carrier include zeolite, zirconium phosphate, silica gel, apatite, soluble glass, thiosulfite and the like. The primary irritation index (P.I) in which zeolite is required for skin irritation in accordance with Federal Register (1972). .I.) Is less than 0.05, and is preferable because of excellent safety such as negative mutagenicity and acute toxicity. In this case, for example, a structure in which a part of the metal contained in the zeolite is replaced with silver or zinc is mentioned. The mass fraction of silver in the whole antibacterial agent composition is 1 to 5 wt%, and zinc is 7 to 12 wt%. Is preferred. In addition, the addition amount of the antibacterial agent in the present invention represents the mass of the whole antibacterial agent composition, and the mass of silver alone is not meant.

The inorganic antibacterial agent containing silver needs to be added in an amount of 1.5 to 10 parts by weight with respect to 100 parts by weight of the polypropylene resin. This can provide immediate antibacterial properties. If the added amount of the antibacterial agent is less than 1.5 parts by weight, an immediate antibacterial property cannot be expressed. If it is larger than 10 parts by weight, the antibacterial agent will bloom out and be detached, or melt fracture will occur and film processability will deteriorate.
Immediately effective antibacterial here refers to a performance that is effective for a shorter period of time, that is, immediately after the normal antibacterial activity is effective 24 hours after contamination with bacteria. The product of the present invention can exhibit efficacy in the same 3 hours.

In general, an inorganic antibacterial agent exerts an effect when it comes into contact with a bacterium. Therefore, when the antibacterial agent is buried in a resin layer, the antibacterial property is hardly exhibited. In other words, when the film surface is embossed after laminating the film on the base material, the antibacterial agent contained in the film is moved downward due to the embossing printing pressure, and the antibacterial property is reduced by reducing the antibacterial agent appearing on the film surface. May be reduced. Therefore, when applying to the wall covering material which performs embossing, if the addition amount of an antibacterial agent shall be 3-10 weight part, immediate effective antibacterial property can be provided more effectively.

Further, when zinc is further added to the antibacterial agent used in the present invention, not only a synergistic effect utilizing the antibacterial property of zinc is obtained, but also the weather resistance and heat resistance of the antibacterial agent containing silver are improved, and the resin made of silver This is effective in suppressing discoloration and deterioration of physical properties, thus improving the handleability.

Here, when an inorganic antibacterial agent containing silver is added to the polypropylene resin, the film becomes hard and the embossing followability decreases. Addition of an ethylene-based copolymer can suppress the curing of such a film. As the ethylene copolymer, for example, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, or the like can be used. Of these, low density polyethylene is preferable in consideration of processability when mixed with a polypropylene resin and the effect of softening the film.

The ethylene copolymer is preferably added in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the polypropylene resin. It is more preferable that the addition amount of the ethylene copolymer is 10 to 40 parts by weight because the flexibility of the film is improved and the matte property is increased. If it is smaller than 1 part by weight, the effect of reducing the film curing is small and the embossing followability is lowered. When it is larger than 50 parts by weight, the strength of the film is lowered and the scratch resistance is lowered or the antifouling property is lowered. Then, gelation due to deterioration of the ethylene component occurs, which increases the possibility of causing fish eyes in the film.

When the antibacterial agent used in the present invention is concentrated on the upper part of the film, the antibacterial performance can be efficiently expressed against the bacteria in contact with the film. On the other hand, the addition of a large amount of antibacterial agent may cure the film and reduce the embossability. From the above, the antibacterial antifouling film for wall coverings of the present invention is preferably a film in which an upper layer having an antibacterial agent-containing layer as an antibacterial layer and a layer not containing an antibacterial agent are laminated.

An inorganic filler is added to the upper layer of the antibacterial antifouling film for wall coverings of the present invention as a matting agent in order to further enhance the matting properties preferred as wall coverings. The inorganic filler is not particularly limited, and examples thereof include talc, silica, mica, alumina, calcium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and zinc oxide. In particular, talc and calcium carbonate are preferred because they have an excellent matting effect and good workability.

The inorganic filler is preferably added in an amount of 1 to 60 parts by weight with respect to 100 parts by weight of the polypropylene resin. The addition amount of the inorganic filler is preferably 3 to 25 parts by weight. If it is less than 1 part by weight, the matte property cannot be sufficiently provided. When it is larger than 60 parts by weight, the film is cured and the embossing followability is lowered or the transparency is lost. Also, scratch resistance is impaired.

The lower layer is preferably a polypropylene resin used for the upper layer according to the present invention because of its adhesiveness to the upper layer. Polypropylene resins include propylene homopolymers, random copolymers such as propylene / α-olefin random copolymers, propylene / α-olefin block copolymers, blocks such as propylene / ethylene / α-olefin copolymers Copolymers can be used. A plurality of these polypropylene resins may be used. In particular, a block copolymer such as a propylene / α-olefin block copolymer is preferable from the viewpoint of heat resistance and matting property.

Specific examples of the propylene / α-olefin block copolymer include propylene / ethylene block copolymer, propylene / 1-butene block copolymer, propylene / 1-pentene block copolymer, propylene / 1-hexene block copolymer. Examples thereof include a polymer, a propylene / 4-methyl-1-pentene block copolymer, a propylene / 1-heptene block copolymer, and a propylene 1-octene block copolymer. Of these, propylene / ethylene block copolymers are preferred because of their good processability.

The melt flow rate of the polypropylene resin used for the lower layer is preferably 1.0 to 20.0 g / 10 min. By using a polypropylene resin having a melt flow rate within this range, workability is improved.

If necessary, an inorganic filler may be added to the lower layer. The inorganic filler is not particularly limited, and examples thereof include talc, silica, mica, alumina, calcium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and zinc oxide.

The inorganic antibacterial agent containing silver is preferably such that the mass reduction rate when heated at 100 ° C. for 24 hours, that is, the mass of the decrease is 0.10% or less compared to the mass before heating. . Here, the mass reduction rate in the present invention is calculated by the following (formula 1) after heating the inorganic antibacterial agent for 24 hours in an oven set at 100 ° C.
Mass reduction rate of inorganic antibacterial agent = 100 × (mass of inorganic antibacterial agent before heating−mass of inorganic antibacterial agent after heating) / mass of inorganic antibacterial agent before heating ・ ・ ・ ・ ・ ・ ・ ・(Formula 1)
When a material with a mass reduction rate larger than 0.10% is used, when processed by a device not equipped with a deaeration device, the reduced amount, that is, volatile matter, causes gaps in the film, resulting in streak-like appearance defects and thickness unevenness. May occur. Inorganic antibacterial agents originally containing silver often contain moisture due to, for example, crystal water or moisture absorption. Such an antibacterial agent can be suitably used regardless of the processing apparatus if it is dried in advance so that the mass reduction rate when heated at 100 ° C. for 24 hours is 0.10% or less.

In order to obtain the immediate antibacterial property of the present invention, the inorganic antibacterial agent needs to be added in an amount of 1.5 parts by weight or more. By setting the rate to 0.10% or less, the thickness unevenness of the antibacterial and antifouling film for wall coverings can be more effectively suppressed and stably manufactured. Further, even when 3 parts by weight or more of the inorganic antibacterial agent is added, it is preferable in that the inorganic antibacterial agent within the above range can be used for more stable production.

Conventionally known methods can be used for mixing, melting, and kneading the resin, antibacterial agent, inorganic filler and the like. For example, a single or twin screw extruder, a Henschel mixer, a super mixer, a V blender, a tumbler mixer, a ribbon. Examples include a blender, a banbury mixer, and a kneader blender. Among them, it is preferable to sequentially laminate the upper layer and the lower layer by mixing or melt kneading with a uniaxial or biaxial extruder.

As the method for producing the film, any conventionally known method can be used, and examples thereof include a T-die casting method, an air-cooled inflation method, a water-cooled inflation method, and a calendar method. Among these, the T die casting method is excellent in thickness accuracy and transparency and is suitable.

As the adhesive layer used for the antibacterial and antifouling film for wall coverings, an adhesive layer containing a vinyl chloride / vinyl acetate copolymer main component and an isocyanate curing agent is suitable. By providing the adhesive layer, the lower layer made of the polypropylene resin and the wall covering substrate can be firmly bonded. In particular, when the wall covering base material is made of a polyvinyl chloride resin, it can be bonded more strongly, which is preferable.
Furthermore, when the antibacterial antifouling film for wall covering material provided with the adhesive layer is wound once and then laminated with the wall covering base material, the adhesive layer is formed on the upper layer of the antibacterial antifouling film for wall covering material. Is wound in the form of contact. For this reason, the adhesive layer according to the present invention requires that the upper layer and the adhesive layer are not blocked, but blocking with the upper layer according to the present invention without using an antiblocking agent by using an adhesive layer having the above-described configuration. Without blocking, and has excellent blocking properties.

It is important that the adhesive layer contains both a vinyl chloride / vinyl acetate copolymer main component and an isocyanate curing agent, and sufficient adhesion between the lower layer and the wall covering base material cannot be obtained with only one of them.

As a means for applying the adhesive layer to the lower layer side of the film, known means can be used. For example, as a method of obtaining by application by a solution coating method or the like, an adhesive dissolved in an organic solvent such as methyl ethyl ketone is a gravure printing machine or the like And a method of forming an adhesive layer after application and drying. In this case, in order to improve the affinity between the lower layer and the adhesive layer, the lower layer is preferably subjected to corona discharge treatment, plasma discharge treatment, primer treatment, and the like.

The thickness of the antibacterial and antifouling film for wall covering of the present invention is not particularly limited, but is 10 to 30 μm, more preferably 15 to 25 μm from the viewpoint of excellent embossing followability and transparency.

As for the thickness of the upper layer which concerns on the antibacterial antifouling film for wall coverings of this invention, 4-15 micrometers is suitable. By setting the thickness of the upper layer within the above range, workability and embossing followability are improved.

Although the thickness of the contact bonding layer which concerns on the antibacterial antifouling film for wall coverings of this invention is not specifically limited, Considering the hardness of a film and adhesiveness, it is 1-5 micrometers, More preferably, it is 2-4 micrometers.

The resin mass of the antibacterial and antifouling film for wall covering of the present invention is preferably 12 to ²⁰ g / m ² . By limiting the mass of the flammable resin within the above range, the fire performance required for the wall covering is improved, and it is not necessary to add a flame retardant or the like.

As the immediately effective antibacterial test method, a method in which the bacterial solution contact time was 3 hours in a test based on JIS Z 2801 was used. According to the present invention, the antibacterial activity value against either S. aureus or Escherichia coli satisfies 4.0 or more in the test, and the other satisfies 3.0 or more. The antibacterial activity value is the logarithm of the amount of bacteria reduced relative to a blank using an untreated product (here, polyethylene film), and 4.0 or more is the number of bacteria reduced to less than 1 / 10,000 of the blank. It means to do. That is, the antibacterial and antifouling film for wall coverings of the present invention shows an effective antibacterial effect by reducing the number of bacteria to less than 1 / 10,000 in 3 hours with respect to the blank polyethylene film.

According to the product of the present invention, in addition to the above two bacterial species, immediate antibacterial properties are satisfied against pathogenic E. coli O-157, methicillin-resistant Staphylococcus aureus (MRSA), Salmonella and Pseudomonas aeruginosa.

The antibacterial antifouling film (1) for wall covering of the present invention comprises an upper layer (2), a lower layer (3) and an adhesive layer (4) as shown in FIG. 1, but other layers may be laminated. For example, an intermediate layer (5) may be provided between the upper layer (2) and the lower layer (3) as shown in FIG. Moreover, it is good also as a structure which added the inorganic filler to the lower layer (3) containing a polypropylene resin, and laminated | stacked the upper layer (2) through the intermediate | middle layer (5) containing a polypropylene resin and an inorganic filler.

As a wall covering material which laminated | stacked the antibacterial antifouling film (1) for wall covering materials of this invention, an aspect like FIG. 3 is mentioned, for example. That is, the antibacterial antifouling film (1) for wall covering is laminated on the wall covering base material (8) in which the resin layer (8-2) and the printing layer (8-1) are laminated on the paper layer (8-3). The surface is embossed (6).

As a wall covering base material, it is not limited to the aspect of FIG. The resin layer can be laminated on the paper layer by calendaring, extrusion, coating, or the like. Moreover, the said printing layer can be provided on the resin layer laminated | stacked on the paper layer by gravure printing, flexographic printing, offset printing, silk screen printing, etc.

Although it does not specifically limit as paper used for the said paper layer, Normal pulp paper, a flame-retardant pulp paper, a calcium carbonate paper, aluminum hydroxide paper etc. are mentioned.

As the resin used for the resin layer, low-density polyethylene, linear low-density polyethylene, ethylene / propylene copolymer, styrene copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, Ethylene / methyl methacrylic acid copolymer, polyvinyl chloride resin, acrylic resin, polyester resin and the like can be mentioned, and polyvinyl chloride resin is particularly preferable from the viewpoint of cost and processability.

As the ink used for the printing layer, a printing ink containing a colorant, a binder resin, and a dispersion medium can be used.

When a foaming agent is added to the wall covering base material used in the present invention, the design and texture are improved. Examples of the foaming agent include azodicarbonamide, azobisformamide, oxybenzenesulfonyl hydrazide, and paratoluenesulfonyl hydrazide. From the viewpoint of design and texture, the expansion ratio is preferably about 2 to 7 times. From the viewpoint of the scratch resistance of the wall covering material, the anti-fouling antifouling film of the present invention is laminated on the wall covering material to improve the scratch resistance, but the effect is particularly effective when the expansion ratio is 3 to 4.5 times. It is suitable for playing.

The wall covering base material that can be used in the present invention is obtained by, for example, applying a paste sol composition containing a polyvinyl chloride resin and a foaming agent on ordinary pulp paper using a comma coater, and then drying and solidifying the paste sol composition. It is obtained by. Furthermore, the design property can be enhanced by applying acrylic resin ink on the polyvinyl chloride resin layer by gravure printing. It is possible to add a filler, a stabilizer, a flame retardant, a matting agent, a pigment, an antifungal agent, an antibacterial agent, etc. to the paste sol composition as long as the object of the present invention is not impaired. The blending amount is an appropriate amount.

The antibacterial / antifouling wall covering of the present invention is obtained by heat-pressing the wall covering base material so that the adhesive layer of the antibacterial / antifouling film for wall covering of the present invention is in contact with the wall covering base material. The antibacterial / antifouling film for covering material and the wall covering base material are laminated, and it can be produced by embossing the antibacterial / antifouling film surface for wall covering at the time of thermocompression bonding or in a separate process. The antibacterial and antifouling wall covering of the present invention is not limited to the above method. Thereby, the upper layer of the antibacterial / antifouling film for wall coverings is exposed on the surface, and an antibacterial / antifouling wall covering having immediate antibacterial properties, antifouling properties and scratch resistance can be obtained.

As long as the object of the present invention is not impaired, each layer relating to the antibacterial and antifouling film for wall coverings of the present invention includes a pigment, a colorant, an antioxidant, a light stabilizer, an ultraviolet absorber, an antistatic agent, and a slip. It is also possible to add an agent, an antiseptic, an antifungal agent, a filler, a fluorescent brightening agent, an antifogging agent, a flame retardant, and the like, and the blending amount thereof is an appropriate amount.

The combination of the antibacterial agent containing silver of the present invention and the above-mentioned various additives can be directly added to the propylene-based resin of the present invention obtained by polymerization and melt kneaded for use. Or may be added directly after melt-kneading. Further, it can be added as a master batch.

Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

(Examples 1-14, Comparative Examples 1-9)
As shown in Tables 1 to 4, a polypropylene compound resin, an ethylene copolymer, an antibacterial agent, and an inorganic filler were mixed in a twin screw extruder and pelletized to obtain a full compound pellet. Subsequently, a film having a two-layer structure of an upper layer obtained by melt-kneading the above-mentioned full compound and a lower layer obtained by melt-kneading a polypropylene resin was obtained using a uniaxial multilayer extruder.
As shown in Tables 1 to 3, the adhesive obtained by uniformly dispersing the adhesive main agent and curing agent at room temperature is applied to the lower layer side of the film with a gravure printing machine and then dried to give an adhesive layer. Film was obtained. The thickness of the adhesive layer at this time was 2 μm.

As shown in Tables 1 to 4, the film provided with the adhesive layer was applied to a polyvinyl chloride wall covering base material composed of a printed layer, a polyvinyl chloride resin layer, and a paper layer at 200 ° C. and 1.5 MPa with an embossing roll. Thus, a wall covering material having an embossed film surface was obtained.

In Example 14, a wall covering material having no embossing on the film surface was obtained in the same manner as in Example 1, except that lamination was performed with a satin roll under the conditions of 200 ° C. and 1.5 MPa.

Comparative Example 8 is the same as Example 1 except that a saponified ethylene / vinyl acetate copolymer film (trade name: EVAL FILM HF-MW12 (manufactured by Kuraray Co., Ltd.)) was used. A wall covering with an embossed finish was obtained.

Comparative Example 9 is the same as Example 1 except that a polypropylene film (trade name: FUNCRARE ACB (manufactured by Gunze Co., Ltd.)) was used, and a wall covering material having an embossed film surface was obtained. It was.

The materials used in the examples and comparative examples are as follows.
(Polypropylene resin)
BPP: Propylene / ethylene block copolymer (MFR2.0, melting point 162 ° C.)
RPP: Propylene / ethylene random copolymer (MFR5.0, melting point 140 ° C.)
HPP: propylene homopolymer (MFR8.0, melting point 162 ° C.)
(Ethylene polymer)
LDPE: Low density polyethylene (MFR1.0)
HDPE: High density polyethylene (MFR1.0)
LLPE: Linear low density polyethylene (MFR1.0)
(Antimicrobial agent)
AA1a: Silver / zinc zeolite (mass reduction rate when heated at 100 ° C. for 24 hours is 0.15%)
Product Name: Bacter Killer (Fuji Chemical Co., Ltd.)
AA1b: Silver / zinc zeolite (0.05% mass reduction rate when heated at 100 ° C. for 24 hours)
Product Name: Bacter Killer (Fuji Chemical Co., Ltd.)
AA2: Silver zeolite Product name: Zeomic (manufactured by Sinanen Zeomic Co., Ltd.)
AA3: Silver zirconium phosphate Product name: Novalon (manufactured by Toagosei Co., Ltd.)
AA4: Silver apatite Product name: Apacider (manufactured by Sangi Co., Ltd.)
AA5: Silver glass Brand name: AEON PURE (manufactured by Ishizuka Glass Co., Ltd.)
(Inorganic filler)
M1: Talc (manufactured by Nitto Flour Industry Co., Ltd.)
M2: Calcium carbonate (Hitachi Crushed Stone Co., Ltd.)
(Adhesive main agent)
Ad1: Vinyl chloride-vinyl acetate copolymer Trade name: Dick Seal A-100Z (manufactured by DIC Corporation)
Ad2: Acrylic product Name: Dick Seal A-262 (manufactured by DIC Corporation)
Ad3: Polyester type Product name: Seika Bond E-295NT (manufactured by Dainichi Seika Kogyo Co., Ltd.)
(Adhesive curing agent)
H1: Isocyanate-based product name: KR-90 (manufactured by DIC Corporation)
H2: Isocyanate product name: Seika Bond E-75N-1.5 (manufactured by Dainichi Seika Kogyo Co., Ltd.)

(Evaluation of film)
<Immediate antibacterial properties>
In the test based on JIS Z 2801, the bacterial solution contact time was evaluated as 3 hours. Judgment was made according to the following criteria. If it is (circle) and (triangle | delta), this invention is satisfied.
○: Antibacterial activity value of both S. aureus and E. coli is 4.0 or more. Δ: Antibacterial activity value of either S. aureus or E. coli is 4.0 or more, and the other is 3.0 or more. Glossiness>
HORIBA, Ltd. Using gloss checker IG-320, the incident angle and the light receiving angle were 60 ° from the normal direction of the film surface, and 20 arbitrary points on the upper layer side of the film were measured, and the average value was taken as the glossiness of each sample. Judgment was made according to the following criteria. If it is (circle) and (triangle | delta), this invention is satisfied.
○: Glossiness is less than 10% Δ: Glossiness is 10 or more and 20% or less ×: Glossiness is more than 20% <Processability>
The processability during film formation was determined according to the following criteria. If it is (circle) and (triangle | delta), this invention is satisfied.
○: No particular defects are confirmed on the surface Δ: Slight defects are confirmed on the surface ×: Remarkable defects are confirmed on the surface <Adhesiveness>
The film was laminated on a polyvinyl chloride wall covering base material with a satin roll under the conditions of 130 ° C. and 1 MPa, and the adhesion of the obtained laminate was evaluated and judged according to the following criteria. If it is (circle), this invention is satisfied.
○: Does not peel between the film surface and the vinyl chloride layer ×: There is a part that peels between the film surface and the vinyl chloride layer XX: Easy peeling between the film surface and the vinyl chloride layer <Blocking property>
After the adhesive was applied to the film and dried at 70 ° C., the presence or absence of blocking on the upper surface of the film and the surface of the adhesive layer was evaluated and judged according to the following criteria. If it is (circle), this invention is satisfied.
○: Blocking is not confirmed, and it can be used without problems. X: Blocking is confirmed, causing problems in use.

(Evaluation of wall covering)
<Antimicrobial properties>
In the test based on JIS Z 2801, the bacterial solution contact time was evaluated as 3 hours. Judgment was made according to the following criteria. If it is (circle) and (triangle | delta), this invention is satisfied.
○: Antibacterial activity value of both S. aureus and E. coli is 4.0 or more. Δ: Antibacterial activity value of either S. aureus or E. coli is 4.0 or more, and the other is 3.0 or more. Scratch resistance>
The evaluation was made in accordance with a test based on the Japan Wall Association's surface-enhanced wallpaper performance regulations, and the following criteria were used. If it is (circle) and (triangle | delta), this invention is satisfied.
○: No change on the surface Δ: Some change on the surface is observed but there is no problem in use ×: The surface is broken and there is a problem in use <Anti-fouling>
The pollutant was evaluated as a soy sauce based on a test based on the anti-smudge wallpaper performance regulations of the Japan Wallcovering Association. Judgment was made according to the following criteria. If it is (circle), this invention is satisfied.
○: Dirt does not remain ×: Dirt remains <embossing followability>
The clarity of the embossed pattern (depth of carving) in the wall covering was evaluated by visual observation and judged according to the following criteria. If it is (circle) and (triangle | delta), this invention is satisfied.
○: The embossed pattern is clear △: The embossed pattern is hardly blurred ×: The embossed pattern is blurred .

As is clear from the results of Tables 1 to 3, the antibacterial and antifouling film for wall covering of the present invention has an immediate antibacterial property, satisfies the performance required as a film, and is laminated. It can be seen that the wall covering material has good antibacterial properties, scratch resistance, antifouling properties and embossing followability (Examples 1 to 14).

An upper layer obtained by melt-kneading an ethylene copolymer, an antibacterial agent and an inorganic filler within a specific range with respect to 100 parts by weight of a polypropylene resin, a lower layer obtained by melt-kneading a polypropylene resin, and vinyl chloride / vinyl acetate. A film composed of an adhesive layer containing a main copolymer copolymer and an isocyanate curing agent has immediate antibacterial properties and good gloss, processability, adhesiveness, and blocking properties (Examples 1-6, 8). ~ 14). The above performance can be satisfied even when an inorganic filler is added to the lower layer (Example 7). When the film is laminated on the wall covering and then embossed on the film side, the antibacterial property is slightly reduced, but the added amount of the antibacterial agent is 3 parts by weight or more with respect to 100 parts by weight of the polypropylene resin. Thus, high antibacterial properties can be maintained (Examples 3 to 13). In addition, when laminating | stacking on the wall covering material which does not give embossing, high antimicrobial property can be exhibited with the same density | concentration as a film (Example 14).

On the other hand, when the addition amount of the antibacterial agent is increased, the workability is slightly lowered, but by using an antibacterial agent with a limited mass reduction rate under specific heating conditions, good processability can be maintained (Example 5). -7, 11, 13).
In addition, various types of polypropylene resins, ethylene copolymers, antibacterial agents, and inorganic fillers can be used (Examples 8 to 13).

In contrast, as is clear from the results in Tables 4 to 6, various performances are reduced when the value is outside the specified range of the present invention (Comparative Examples 1 to 9). In addition, lamination | stacking to a wall covering material is not implemented about the thing in which adhesiveness is remarkably inferior or the blocking property is bad (Comparative Examples 1 and 7).

When the addition amount of the antibacterial agent is low, the immediate antibacterial property is not exhibited, and when the adhesive layer is composed only of the vinyl chloride / vinyl acetate copolymer main agent, the adhesiveness is low (Comparative Example 1). On the other hand, when the amount of the antibacterial agent added is too large, noticeable streak-like defects are caused on the film surface and the embossability is lowered (Comparative Example 2). If the upper layer is made thicker, streak-like defects are similarly generated and embossing followability is lowered. If the adhesive layer is made of an acrylic layer, sufficient adhesiveness cannot be obtained (Comparative Example 3).

On the other hand, when the amount of the ethylene copolymer added is too large, fish eyes are generated on the film, and the scratch resistance and antifouling properties, which are the characteristics of the polypropylene resin, are impaired (Comparative Example 4). Even if there are too many inorganic fillers, a surface will generate | occur | produce and scratch resistance and embossing followability will fall (comparative example 5).

If the ethylene copolymer is not added, the embossability is reduced (Comparative Example 6). If an inorganic filler is not added, the glossiness becomes too high, and when a polyester polyol-based main agent and an isocyanate-based curing agent are used for the adhesive layer, although strong adhesive force can be obtained, blocking occurs (Comparative Example 7).

When an ethylene / vinyl acetate copolymer saponified film or polypropylene film, which is an off-the-shelf product, is used, immediate antibacterial properties cannot be obtained (Comparative Examples 8 and 9).

According to the present invention, an antibacterial and antifouling film for wall coverings that has immediate antibacterial performance, scratch resistance and antifouling properties and can be suitably used for wall coverings, and antibacterial and antibacterial protection for the wall coverings. It is possible to provide a wall covering material in which dirty films are laminated. The wall covering material of the present invention is an interior material and can be used for a wall surface or a ceiling.

1 Antibacterial antifouling film for wall covering 2 Upper layer 3 Lower layer 4 Adhesive layer 5 Intermediate layer 6 Embossing 7 Wall covering 8 Wall covering base material
8-1 Printed layer of wall covering base material
8-2 Resin layer of wall covering base material
8-3 Paper layer of wall covering base material

Claims (5)

At least an upper layer containing 1.5 to 10 parts by weight of an inorganic antibacterial agent containing silver, 1 to 50 parts by weight of an ethylene copolymer, and 1 to 60 parts by weight of an inorganic filler with respect to 100 parts by weight of a polypropylene resin ,
A lower layer containing a polypropylene resin;
An antibacterial and antifouling film for wall covering, comprising: an adhesive layer comprising a vinyl chloride / vinyl acetate copolymer main component and an isocyanate curing agent. 2. The antibacterial and antifouling film for wall covering according to claim 1, wherein a mass reduction rate of the inorganic antibacterial agent containing silver when heated at 100 ° C. for 24 hours is 0.10% or less. The antibacterial antifouling film for wall covering according to claim 1 or 2, wherein the upper layer has a thickness of 4 to 15 µm. In the test according to JIS Z 2801, the antibacterial activity value against S. aureus and Escherichia coli after 3 hours of contact with the bacterial solution is 4.0 or more, according to any one of claims 1 to 3. The antibacterial antifouling film for wall covering described. An antibacterial and antifouling film for wall covering according to any one of claims 1 to 4, wherein the antibacterial and antifouling film for wall covering is laminated, and the antibacterial and antifouling film surface for wall covering is embossed. Wall covering.

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