JP2001277453A - Antibacterial decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet, in which harmful and corrosive hydrogen chloride gas or the like generated at time of combustion are not accompanied and volatilization of a plasticizer or the like becoming a cause of hypersensitivity for a chemical substance is not produced and lapping workability, overlay workability such as vacuum moldability, V-cut workability and antibacterial properties are excellent. SOLUTION: The antibacterial decorative sheet is a decorative sheet 6 not less than two-layer structures, in which an olefinic resin layer 1 is made to a base sheet and at least one layer selected from a primer layer 3 and an ink layer 4 is laminated on one side or both sides thereof. The olefinic resin layer 1 is a propylene base block copolymer consisting of both a propylene-α-olefin random copolymer component (A) having >=90 wt.% content of propylene and a propylene-α-olefin random copolymer component (B) having 55-90 wt.% content of propylene and is constituted of a propylene base block copolymer (X) having specific limiting viscosity. The outermost layer 3 as the decorative sheet 6 is constituted of a layer, in which polylysine or polylysine salt is added as an antibacterial agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet made of polypropylene which is adhered to a plywood, a steel plate, a backer or the like to form a decorative material. More specifically, the present invention relates to a polypropylene-based decorative sheet excellent in overlay processing such as lapping processing and vacuum forming and V-cut processing properties and having an antibacterial action.

[0002]

2. Description of the Related Art Conventionally, decorative sheets adhered to plywood, steel sheets, etc. and used as decorative materials have excellent printability, embossability, wrapping properties, overlay formability such as vacuum formability, etc. and are economical. For that reason, vinyl chloride resins have been widely used.

However, the use of these vinyl chloride resins is being restricted due to the increasing environmental problems in recent years. Among them, the emergence of environmentally friendly alternative resins is expected.

[0004] On the other hand, it is desired to add an antibacterial function to home interior materials around homes such as kitchens and washrooms, home electric appliances, hospital materials and the like in order to lead a sanitary and comfortable life.

[0005]

The object of the present invention is to eliminate the harmful and corrosive hydrogen chloride gas generated during combustion,
Overlay workability such as lapping property and vacuum formability and V
An object of the present invention is to provide a decorative sheet which is excellent in cut workability and has an antibacterial function.

[0006]

Means for Solving the Problems The present inventors have intensively studied to achieve the above object. As a result, a propylene-α-olefin random copolymer component (A) and a propylene-α-olefin random copolymer component (B) having a different α-olefin content from the random copolymer component (A) A propylene-based block copolymer comprising: the intrinsic viscosity of the propylene-α-olefin random copolymer component (B), the intrinsic viscosity ratio of both random copolymer components, and the intrinsic viscosity ratio and both random copolymer weights. A decorative sheet using a propylene-based block copolymer (X) whose product with the weight ratio of the united product is within a certain range, wherein the outermost layer is a layer to which polylysine or a polylysine salt is added as an antibacterial agent. As a result, the present inventors have found that a cosmetic sheet having excellent secondary workability and an antibacterial function is obtained, and based on this finding, the present invention has been completed.

The present invention is described below. (1) Using an olefin-based resin layer as a base sheet,
Select from primer layer and ink layer on one or both sides
Of a two-layer structure or more in which at least one layer is laminated
Wherein the olefin-based resin layer is
Made of a len-based block copolymer (X),
The outermost layer of the decorative sheet may be made of polylysine as an antibacterial agent.
Or a layer to which polylysine salt is added
An antibacterial cosmetic sheet characterized by the following. The above propylene-based blow
The block copolymer (X) has a propylene content of 90% by weight.
Propylene-α-olefin random copolymer as described above
When the body component (A) and the propylene content are 55 to 90% by weight,
Certain propylene-α-olefin random copolymer components
(B) a propylene-based block copolymer
The propylene-α-olefin random copolymer composition
Intrinsic viscosity [η] of minute (B)_BIs 1.3 to 3.5 dl / g
[Η]_BAnd propylene-α-olefin random
Intrinsic viscosity [η] of copolymer component (A)_AIntrinsic viscosity ratio with
[η]_B/ [Η]_AIs 0.5 to 1.3, and propylene-
The weight of the α-olefin copolymer component (A) is_Aage,
Weight of propylene-α-olefin copolymer component (B)
To W_BAnd these weight ratios W_A/ W_BAnd the ultimate viscosity
Degree ratio [η]_B/ [Η]_A([Η]_B/ [Η]_A) ×
(W _A/ W_B) Is in the range of 1.0 to 4.5
It is a system block copolymer (X).

(2) At least one layer selected from a primer layer and an ink layer is laminated on one or both sides of an olefin resin layer as a base sheet, and an olefin resin layer as a top sheet is laminated on one surface thereof. 3. A decorative sheet having a three-layer structure or more, wherein the olefin-based resin layer as the base sheet and the top sheet has the same propylene-based block copolymer as the propylene-based block copolymer (X) according to the above item 1. An antibacterial decorative sheet, which is made of united (X), wherein the outermost layer of the decorative sheet is composed of a layer to which polylysine or a polylysine salt is added as an antibacterial agent.

(3) The above item (1) or (2), wherein the propylene-based block copolymer (X) contains 10 to 50% by weight of a propylene-α-olefin random copolymer component (B). Antibacterial cosmetic sheet.

(4) The antibacterial cosmetic sheet according to any one of (1) to (3) above, wherein the polylysine or polylysine salt is ε-polylysine or ε-polylysine salt.

[0011]

Embodiments of the present invention will be described below. The antibacterial decorative sheet of the present invention has at least one layer selected from a primer layer and an ink layer laminated on one or both sides of an olefin-based resin layer as a base sheet, and polylysine or polylysine as an antibacterial agent is provided on the outermost layer of the decorative sheet. At least one layer selected from a primer layer and an ink layer is laminated on one or both sides of an olefin-based resin layer as a base sheet, and a decorative sheet having a structure of two or more layers to which a salt is added. A decorative sheet having a structure of three or more layers in which an olefin-based resin layer to which the above-mentioned antibacterial agent is added is laminated on one side of the olefin resin layer.

Preferably, a primer sheet is provided on both sides of an olefin-based resin layer as a base sheet, and further, an ink layer containing the antibacterial agent is laminated on one side thereof, and a decorative sheet having a structure of four or more layers, and a base sheet. A five-layer structure in which a primer layer is provided on both sides of an olefin-based resin layer as a sheet, an ink layer is further provided on one side thereof, and an olefin-based resin layer to which the antimicrobial agent is added is laminated on the surface of the ink layer as a top sheet. The above is a makeup sheet.

Particularly, a five-layer structure in which a primer layer is provided on both sides of an olefin-based resin layer as a base sheet, and an ink layer and a top coat layer containing the antibacterial agent on the ink layer on one side thereof is further laminated. A primer layer is provided on both surfaces of the above-mentioned decorative sheet and the olefin resin layer as a base sheet, and an ink layer is further provided on one surface of the primer sheet. The olefin resin layer as a top sheet is further provided on the surface of the ink layer. A decorative sheet having a six-layer structure or more in which a top coat layer to which the antibacterial agent is added is laminated on a top sheet layer is preferable.

The olefin resin layer serving as the top sheet can be subjected to any embossing or wiping such as a wood grain pattern by a known method.

The compositions of the olefin-based resin layer as the base sheet and the top sheet may be the same or different as long as they are within the composition ranges described below. The top sheet is colored by a coloring agent or the like, and is preferably transparent, but may be colored and transparent. Examples of the colorant for the base sheet include organic pigments, inorganic pigments, pearl pigments, etc., but inorganic pigments are preferred in view of concealing properties, heat resistance, economy and the like.

In the propylene-based block copolymer (X) used as a material of the olefin-based resin layer as the base sheet in the present invention, the propylene-α-olefin random copolymer component (A) And a random copolymer having a propylene content of 90% by weight or more, preferably 92% by weight or more, more preferably 94% by weight or more. When the propylene content is 90% by weight or more, the heat resistance is high and the propylene content can be suitably used as a decorative sheet.

The α-olefin used in the production of the propylene-α-olefin random copolymer component (A) includes ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1- Dodecene, 4-methyl-1-pentene, 3-methyl-1-pentene and the like can be mentioned. Of these, the use of ethylene is preferred in terms of production cost.

On the other hand, the propylene-α-olefin random copolymer component (B) is a random copolymer having a propylene content of 55 to 90% by weight, preferably 55 to 85% by weight. When the propylene content is in the range of 55% by weight or more and 90% by weight or less, impact resistance at low temperatures is sufficient and transparency is excellent.

The α-olefin used for producing the propylene-α-olefin random copolymer component (B) of the present invention includes ethylene, 1-butene, 1-pentene and 1-pentene.
Hexene, 1-octene, 1-decene, 1-dodecene,
4-methyl-1-pentene, 3-methyl-1-pentene and the like can be mentioned. Of these, the use of ethylene is preferred in terms of production cost.

The propylene-α-olefin random copolymer component (B) has an intrinsic viscosity [η] _B measured in tetralin at 135 ° C. of 1.3 to 3.5 dl / g, more preferably 1. 5~3.0dl / g is in the range of, and the intrinsic viscosity ratio between the intrinsic viscosity measured in a 135 ° C. in tetralin of the propylene -α- olefin random copolymer component _{(a) [η] a [} η ] _B / [η] _A is 0.5
To 1.3, preferably 0.6 to 1.2.

The intrinsic viscosity [η] _B of the propylene-α-olefin random copolymer component (B) affects the productivity and transparency of the decorative sheet, and the propylene-α-olefin random copolymer component (B) And intrinsic viscosity ratio [η] of propylene-α-olefin random copolymer component (A)
_B / [η] _A affects the dispersibility of the propylene-α-olefin random copolymer component (B) in the propylene-α-olefin random copolymer component (A). Intrinsic viscosity [η] of propylene-α-olefin random copolymer component (B) The productivity is improved as _B is smaller, and the intrinsic viscosity ratio [η] with propylene-α-olefin random copolymer component (A) is smaller. _{When B} / [η] _A is within the above range, a decorative sheet having excellent transparency and impact resistance at low temperature and having desired properties can be obtained.

In the propylene-based block copolymer (X) of the present invention, the weight (W _A ) of the propylene-α-olefin random copolymer component ( _A ) and the propylene-α-
Weight of olefin random copolymer component _(B) (W B)
The weight ratio W _A / W _B of the product of the intrinsic viscosity ratio of both copolymers ingredients _{[η] B / [η]} A, ([η] B /
_{[Η] A) × (W} A / W B) is in the range of 1.0 to 4.5.

The product of the weight ratio of the copolymer component and the intrinsic viscosity ratio is an index representing the whitening resistance of the decorative sheet (meaning that the folded portion when the sheet is folded is hardly whitened). If the value is within the above range, a copolymer having excellent whitening resistance, heat resistance and rigidity can be obtained. Due to these excellent whitening resistance, heat resistance, impact resistance and the like, overlay processing properties such as wrapping properties and vacuum forming properties as a decorative sheet and V-cut processing properties are greatly improved.

The specific composition of the propylene-based block copolymer (X) of the present invention is such that the propylene-α-olefin random copolymer component (B) is 10 parts by weight based on the weight of the composition.
５０50% by weight. If the composition of the propylene-based block copolymer (X) is within this range, transparency, whitening resistance,
A decorative sheet having excellent impact resistance, excellent overlay processing properties such as wrapping properties and vacuum forming properties, and excellent V-cut processing properties can be obtained.

The propylene-based block copolymer (X) of the present invention may be produced by any method as long as the above-mentioned various properties are satisfied. For example, a propylene-α-olefin random copolymer component (A) obtained by separately polymerizing each other
And the propylene-α-olefin random copolymer component (B) may be obtained by mixing by melt kneading or the like. Alternatively, it may be obtained by continuously polymerizing the propylene-α-olefin random copolymer component (A) and the propylene-α-olefin random copolymer component (B) by multistage polymerization. Specifically, in the presence of a stereocatalyst comprising a solid catalyst component comprising titanium tetrachloride supported on a large particle size magnesium chloride carrier and an organoaluminum compound and an organosilicon compound, propylene is used in the first stage in the gas phase. -Α-olefin random copolymer component (A) is produced (first polymerization step), and propylene-α-olefin random copolymer component (B) is produced continuously in the second stage (second polymerization step) Is more preferred. In this continuous polymerization method, the production cost is lower than in the above-mentioned melt mixing method, and the propylene-α-olefin random copolymer component (A) contains propylene-α-
It is preferable in that a propylene-based block copolymer (X) in which the olefin random copolymer component (B) is uniformly dispersed can be obtained and the quality can be stabilized.

The ink layer of the present invention can be formed by a method such as gravure printing, offset printing, screen printing, or transfer. Examples of the ink include inks using a urethane resin, chlorinated polyolefin, or the like as a vehicle. And an ink containing no halogen element such as chlorine. Further, it is preferable to provide a primer layer on one or both surfaces of the olefin resin layer in order to improve the adhesion between the olefin resin layer and the ink layer and the adhesion between the base material such as plywood and the decorative sheet.

The primer layer can be formed by a gravure coater, a roll coater or the like, and a known olefin primer can be used as the primer. Specifically, primers such as polyurethane-based, polyester-based, and chlorinated polyolefin-based primers can be exemplified, but primers containing no halogen element such as chlorine are preferable from the environmental viewpoint.

The outermost layer of the decorative sheet of the present invention may be provided with a top coat layer for the purpose of improving weather resistance, stain resistance, scratch resistance, and the like. Must be added to provide antibacterial properties. The top coat layer is a gravure coater,
It can be formed by a roll coater or the like, and a silicon resin, an acrylic resin, a urethane resin, a fluorine resin, a polyester resin, or the like can be used. Further, the top coat layer may be subjected to any embossing such as graining.

In the present invention, polylysine or a polylysine salt is used as an antibacterial agent. Α-polylysine or α in which an amino group at the α-position of L-lysine and a carboxyl group are bonded
-Polylysine salts and ε-polylysine or ε-polylysine salts in which an amino group and a carboxyl group at the ε-position are bonded can be used, but α-polylysine obtained by chemical synthesis is not permitted as a food additive Therefore, in the present invention, it is preferable to use ε-polylysine or ε-polylysine salt obtained by the following production method from the viewpoint of safety. As ε-polylysine, for example, Streptomyces alplus subsp. lysinopolymeras belonging to the genus Streptomyces, which is an ε-polylysine producing bacterium described in JP-A-59-20359, is obtained by culturing in a medium. Obtained by separating and collecting ε-polylysine from the cultured culture. Here, the ε-polylysine salt is an inorganic acid salt (inorganic acid: hydrochloric acid, sulfuric acid, phosphoric acid, etc.) or an organic acid salt (organic acid: acetic acid, propionic acid, fumaric acid, malic acid, citric acid, maleic acid) Acid, adipic acid, gluconic acid, caproic acid, lauric acid, stearic acid, oleic acid, linoleic acid, arachidonic acid, etc.). The amount of the antibacterial agent added to the outermost layer is 0.01 to 5% by weight, preferably 0.05 to 1% by weight. When the amount of addition is within the above range, a decorative sheet excellent in economy, secondary whitening resistance and antibacterial property can be obtained. The addition of the antibacterial agent can be performed by various known and publicly-known methods. Specifically, when adding to the propylene-based block copolymer (X), a so-called pelletizing or masterbatch blending method can be exemplified. For inks and the like, a method in which the antibacterial agent is dispersed in a solvent and then mixed with the ink When the polylysine is dispersed in a solvent, it is preferable to use an alcohol having good solubility as the solvent.

The base sheet and the top sheet constituting the olefin resin layer of the present invention can be produced by using the propylene block copolymer (X) by various known and publicly-known molding methods, ie, extrusion molding, calendering, and the like. Molding method,
Examples of the production method include a compression molding method and a casting molding method.

Among the known and used molding methods, the extrusion molding method and the calender molding method are preferred from the viewpoint of good productivity. Specifically, a T-die method using an apparatus (T-die sheet forming machine) including an extruder, a T-die, a cooling roll, a guide roll, a take-up roll, a trimming cutter, a fixed-size cutting cutter, a winding machine, and the like; A calendering method using a calender molding machine including a Banbury mixer, a mixing roll, a warming roll, an extruder, a calender roll, a cooling roll, a trimming cutter, a masking, a fixed-size cutting cutter, and a winding machine is more preferable.

The speed of forming the base sheet and the top sheet constituting the olefin resin layer is 0.1 to 100 m / min from the viewpoint of productivity. The speed is 0.1m /
If it is more than minutes, the production amount of the base sheet and the top sheet per hour is large, the base sheet and the top sheet having a uniform thickness can be obtained, and the defective rate is reduced.
When the speed is not more than 00 m / min, the base sheet and the top sheet can be sufficiently cooled, and a linear pattern that occurs when the roll-shaped base sheet and the top sheet are unraveled cannot be obtained, and a good appearance can be obtained.

One or both surfaces of the base sheet and the top sheet of the present invention, that is, the olefin resin layer, have a wetting tension of 36 mN / m or more, preferably a wetting tension of 38 mN.
/ M or more, particularly preferably a corona treatment with a wetting tension of 40 mN / m or more. 36mN wet tension
/ M or more, the adhesion between the olefin-based resin layer and the ink layer or the primer layer becomes good.

The thicknesses of the base sheet and the top sheet constituting the olefin resin layer of the present invention are as follows.
0.02 mm to 0.5 mm, preferably 0.04 mm to 0.5 mm.
3 mm, particularly preferably 0.06 mm to 0.25 mm.

The propylene block copolymer (X) used in the olefin resin layer of the decorative sheet of the present invention includes:
Known antioxidants, neutralizing agents, antistatic agents, weathering agents, dispersants, slip agents, synthetic rubbers, synthetic resins, inorganic fillers (talc, calcium carbonate, Various additives such as silica and mica) and coloring agents can be added.

[0036]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The measuring methods used in the examples and comparative examples are as follows.

1) Intrinsic viscosity (unit: dl / g): using tetralin (tetrachloronaphthalene) as a solvent
The limit of the propylene-α-olefin random copolymer component (A) extracted from the middle of the polymerization process using an automatic viscosity meter (AVS2, manufactured by Mitsui Toatsu Chemicals, Inc.) under a temperature condition of 5 ° C. The viscosity [η] _A and then the intrinsic viscosity [η] _WHOLE of the propylene-based block copolymer (X) were directly measured. The intrinsic viscosity [η] _B of the propylene-α-olefin random copolymer component (B) is [η] _A and [η]
_It was calculated from the following equation using the value of _WHOLE . [Η] _B = ([η] _WHOLE / W _B ) − ([η] _A × W _A /
W _B) W _A: the amount of propylene -α- olefin random copolymer component (A) W _B: the amount of propylene -α- olefin random copolymer component (B) [η] _WHOLE: the propylene block copolymer Intrinsic viscosity of polymer (X)

2) Propylene content (unit% by weight):
It was measured by an infrared absorption spectrum method with a 1760X FT-IR device manufactured by Perkin-Elmer.

3) Random copolymers (A) and (B)
Weight of: The Mg content in the polymer obtained in the first and second polymerization steps was determined by high-frequency inductively coupled plasma emission spectroscopy (IC
P method), and the weights of the random copolymers (A) and (B) were calculated from the polymer yield per unit weight of the catalyst.

4) Suitability for secondary processing: width 5 mm, depth 3 mm
The product is made by wrapping a decorative sheet on a baseboard with a width of 60 mm and a thickness of 6 mm and a decorative sheet on a plywood with a width of 100 mm and a thickness of 3 mm. When there was no whitening or cracking, it was evaluated as ○, and when there was whitening or cracking, it was evaluated as ×.

5) Antibacterial test 1: "Study group on silver and other inorganic antibacterial agents" Antibacterial evaluation test method for silver and other inorganic antibacterial agents (1995)
The following antibacterial tests were performed according to the “film adhesion method”, which is a synthetic resin antibacterial test method specified in “1. First, the obtained decorative sheet was cut into a size of 50 × 50 mm, and the entire surface was lightly wiped twice or three times with a local gauze impregnated with ethanol, and dried at room temperature to obtain a test piece. On the other hand, E. coli (Escheric) was diluted with sterilized purified water 500-fold and the pH was adjusted to 7.0 ± 0.2 into “1/500 medium” using a sterilized pipette.
ia coli, IFO3972) to prepare a test bacterial solution such that the number of viable bacteria in the medium was 3.0 × 10 ⁵ cells / mL. Next, the test piece was placed in a sterile petri dish, the test surface was inoculated with 0.5 mL of the test bacterial solution, and further covered with a sterilized polyethylene film, covered with a lid, and then heated to a temperature of 35 ± 1 ° C. The culture was performed for 24 hours under the condition of 90% or more of relative humidity. After completion of the culture, the bacteria adhering to the test piece and the film are removed from the SCDLP medium (10 mL).
Was washed out sufficiently in a sterile petri dish, and the viable cell count in 1 mL of the washed out liquid was measured by a standard agar medium method. After the test was completed, the difference in increase or decrease was calculated by the following formula. Antibacterial unprocessed cosmetic sheet A: Number of viable bacteria immediately after inoculation B: Number of viable bacteria after fixed-time culture operation Antibacterial cosmetic sheet C: Number of viable bacteria after fixed-time culture operation Increase / decrease value = log ₁₀ (B / A) −log ₁₀ (C / A)

6) Antibacterial test 2: Staphylococcus aureu instead of E. coli
s, IFO12732) was used in the same manner as in the antibacterial test 1.

Production of Propylene Block Copolymer (X) As a first polymerization step, a horizontal polymerization vessel (L /
D = 6, internal volume 100 liters) and average particle size 115 μm
0.5 g / hr of a titanium-containing solid catalyst component using magnesium chloride as a carrier and triethylaluminum and diisopropyldimethoxysilane in an Al / Si molar ratio of 6
Were supplied continuously so that While continuously maintaining the conditions of a reaction temperature of 70 ° C., a reaction pressure of 2.5 MPa, and a stirring speed of 40 rpm, a propylene-ethylene mixed gas is continuously supplied,
Further, hydrogen gas was continuously supplied to adjust the molecular weight of the propylene-α-olefin random copolymer (A). Table 1 shows the ethylene / propylene molar ratio and the hydrogen / propylene molar ratio at this time.

The propylene-α-olefin random copolymer (A) obtained in the present polymerization reactor is continuously fed from the polymerization reactor in the first polymerization step so that the level of the retained polymer becomes 50% by volume of the reaction volume. Horizontal polymerization vessel (L / D = 6, inner volume 100 liter) having stirring blades in the second polymerization step
Supplied. At this time, a part of the propylene-α-olefin random copolymer (A) was intermittently extracted to prepare a sample for obtaining the ethylene content, the intrinsic viscosity and the polymer yield.

In the second polymerization step, the propylene-α-olefin random copolymer (A), the ethylene-propylene mixed gas and the hydrogen gas from the first polymerization step are continuously supplied to carry out the copolymerization of ethylene and propylene. went. The reaction conditions were a stirring speed of 40 rpm, a temperature of 60 ° C., and a pressure of 2.1 M.
Pa. In addition, oxygen was supplied as a polymerization activity inhibitor in order to adjust the polymerization amount of the propylene-α-olefin random copolymer (B). Table 1 shows the ethylene / propylene molar ratio, hydrogen / propylene molar ratio, and oxygen concentration at this time.

The propylene block copolymer produced in the copolymerization step has a polymer holding level of 50% of the reaction volume.
It was taken out from the polymerization vessel in the second polymerization step so that the volume% was obtained. The production rate of propylene-based block copolymer is 8 to 1
It was 2 kg / hr.

The composition, intrinsic viscosity and the like of the obtained propylene-based block copolymer (X) are shown in Examples and Comparative Examples in Table 1.

Example 1 Propylene block copolymer (X) 1 obtained above
0.1 part by weight of a phosphorus-based antioxidant to 00 parts by weight,
0.1 parts by weight of calcium stearate, 0.2 parts by weight of a lubricant, and 7 parts by weight of a coloring pigment are charged into a Banbury mixer and mixed by heating. Then, a mixing roll, a warming roll, a calender roll, and a cooling roll having a surface temperature of 60 ° C. Calender roll temperature 180 ° C, forming speed 60m by calendering method using a sheet forming machine equipped with
/ Min, a base sheet constituting a colored olefin-based resin layer having a thickness of 0.1 mm was produced. Further, both surfaces of the olefin-based resin layer are subjected to corona treatment (wetting tension 43 mN /
m).

The olefin-based resin layer 1 as a base sheet was coated on a gravure printing machine manufactured by Dainippon Kiko Co., Ltd. with polyurethane primer “NH Primer” manufactured by The Inktech Co., Ltd. on both sides. Several colors of polyurethane ink (trade name: Lamister) manufactured by Toyo Ink Mfg. Co., Ltd. were overlaid on the primer layer 2 and one surface thereof, and a woodgrain pattern was printed. Further, a mixture of a medium color (clear clear color) of the urethane-based ink and an ε-polylysine solution dissolved in an isopropyl alcohol solvent was applied to the outermost layer to form a woodgrain-like ink layer 3 as shown in FIG. The decorative sheet 6 was obtained. The concentration of ε-polylysine in the above-mentioned urethane-based ink-polylysine mixture was adjusted so that 0.1% by weight of ε-polylysine was contained with respect to the solid content of the dried ink layer 3.

When an antibacterial property test was performed using this decorative sheet 6, it was found that the antibacterial property was extremely excellent. Furthermore, using this decorative sheet 6, a wrapping product and a V-cut product were manufactured. There was no whitening or cracking in the parts bent at right angles to these products, and they were excellent in suitability for secondary processing. The results are shown in Table 1.

Example 2 The procedure of Example 1 was followed except that the concentration of ε-polylysine in the medium urethane-based ink-polylysine mixed solution was 0.5% by weight based on the solid content of the dried ink layer 3. Thus, the decorative sheet 6 shown in FIG. 1 was manufactured. This decorative sheet 6
Had excellent antibacterial properties and suitability for secondary processing. The results are shown in Table 1.

Example 3 First, 0.1 part by weight of a phenolic antioxidant, 0.05 part by weight of zinc stearate, and 0.1 part of ε-polylysine powder as an antibacterial agent were added to 100 parts by weight of a propylene block copolymer (X). After adding by weight and pelletizing, a top sheet having a thickness of 0.05 mm was manufactured using a T-die-air knife type film forming apparatus, and one side of this sheet was subjected to corona treatment (wetting tension 43 m / m) to obtain a transparent olefin. The base resin layer 5 was formed. Subsequently, the decorative sheet 6 shown in FIG. 1 in which the colored olefin-based resin layer 1, the primer layer 2, and the ink layer 3 were laminated was manufactured in accordance with the conditions of Example 1, but the ink layer 3 was different from Example 1. The wood-grain pattern printing was performed without applying the urethane-based ink-polylysine mixed solution. The corona-treated surface of the transparent olefin-based resin layer 5 and the surface of the ink layer 3 of the decorative sheet 6 were bonded via a polyester-based adhesive (adhesive layer 4) manufactured by Toyo Morton Co., Ltd., as shown in FIG. A decorative sheet 7 was obtained. This decorative sheet 7 was excellent in both antibacterial properties and suitability for secondary processing. Table 1 shows the results.
It was shown to.

Comparative Example 1 The decorative sheet 6 in which the colored polyolefin resin layer 1, the primer layer 2, and the ink layer 3 produced in Example 3 were laminated in this order.
Was used directly as an antibacterial test sample. This decorative sheet had no antibacterial property. The results are shown in Table 1.

Comparative Example 2 A decorative sheet 6 shown in FIG. 1 was produced according to Example 1 except that the composition of the propylene-based block copolymer (X) was changed to that shown in Table 1. This decorative sheet 6 was excellent in antibacterial properties. Furthermore, using this decorative sheet 6, a wrapping product and a V-cut product were manufactured. The portions of these products that were bent at right angles were whitened, and were poor in secondary processing suitability. The results are shown in Table 1.

[0055]

The antibacterial decorative sheet of the present invention has no harmful and corrosive hydrogen chloride gas generated during combustion, has no volatilization of plasticizers and the like which cause chemical sensitivity, and has good wrapping processability. It is a decorative sheet excellent in overlay workability such as vacuum moldability, V-cut workability and antibacterial property.

[0056]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a sectional view of a decorative sheet according to Example 1 of the present invention.

FIG. 2 is a sectional view of a decorative sheet according to a third embodiment of the present invention.

[Description of Signs] 1 ... Colored olefin resin layer (base sheet) 2 ... Primer layer 3 ... Ink layer 4 ... Adhesive layer 5 ... Transparent olefin resin layer (top sheet) 6, 7 ... Decorative sheet

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08F 297/08 C08F 297/08 4J026 C08J 7/04 CES C08J 7/04 CESSZ C08L 23/16 C08L 23/16 53/00 53/00 // A01N 37/46 A01N 37/46 F-term (reference) 2B002 AA03 DA02 DA04 4F006 AA12 AA14 AB35 AB37 AB55 AB65 BA17 4F100 AK03A AK03D AK03E AK07A AK41G AK51 AK66A AK66D AK66E02A03 AL02A02 AL02A02 AL02A02 AL02A03 AL02A03 AL02A03 AL02A02 AL02A BA04 BA05 BA06 BA07 BA10B BA10C BA10D BA10E EJ40 EJ402 EJ55 EJ552 GB08 HB00B HB00C HB01 JA06A JC00D JC00E JL01 JL10B JL10C YY00A 4H011 AA02 HA01 HA19 HA12 HA19 HA12 HA01 HAB27 BC06 BC18 BC1 DA07 DC10 DD07 DH4 HB02 HB03 HB04 HB20 HB39 HB42

Claims (4)

[Claims] 1. An olefin-based resin layer comprising: a base sheet;
And primer layer and ink on one or both sides
A two-layer structure in which at least one layer selected from layers is laminated
The upper decorative sheet, wherein the olefin-based resin layer is
Made from the propylene-based block copolymer (X)
The outermost layer of the decorative sheet is made of
Consists of a layer to which lysine or polylysine salt is added
An antibacterial cosmetic sheet characterized by the fact that: Above
The propylene-based block copolymer (X) has a propylene content of
90% by weight or more of propylene-α-olefin run
Dam copolymer component (A) and propylene content is 55-9
0% by weight of propylene-α-olefin random copolymer
Propylene block copolymer with polymer component (B)
The propylene-α-olefin random
Intrinsic viscosity [η] of copolymer component (B)_BIs 1.3 to 3.5
In dl / g, the [η]_BAnd propylene-α-olefin
Intrinsic viscosity [η] of random copolymer component (A)_ALimit with
Viscosity ratio [η]_B/ [Η]_AIs 0.5 to 1.3, and
The weight of the len-α-olefin copolymer component (A) is_A
And a propylene-α-olefin copolymer component (B)
Weight of W_BAnd these weight ratios W_A/ W_BAnd said
Intrinsic viscosity ratio [η]_B/ [Η]_A([Η]_B/
[Η]_A) × (W _A/ W_B) Is in the range of 1.0 to 4.5
Propylene-based block copolymer (X). 2. An olefin-based resin layer as a base sheet, wherein at least one layer selected from a primer layer and an ink layer is laminated on one or both sides of the olefin-based resin layer, and an olefin-based resin layer as a top sheet is laminated on one side thereof.
A decorative sheet having a layer structure or more, wherein the olefin-based resin layer as the base sheet and the top sheet is provided.
And the outermost layer of the decorative sheet is a layer to which polylysine or a polylysine salt is added as an antibacterial agent. An antibacterial cosmetic sheet characterized by being constituted. 3. A propylene-based block copolymer (X)
Contains 10 to 50% by weight of a propylene-α-olefin random copolymer component (B).
Or the antibacterial cosmetic sheet according to claim 2. 4. The method according to claim 1, wherein the polylysine or the polylysine salt is ε.
The antibacterial cosmetic sheet according to any one of claims 1 to 3, which is a polylysine or ε-polylysine salt.