JPH04275142A - Highly transparent antimicrobial multilayer sheet article and preparaiton thereof - Google Patents

Abstract

PURPOSE:To develop an antimicrobial crystalline thermoplastic resin sheet article having transparency equal to or more than that of a highly transparent sheet like article composed of a non-crystalline thermoplastic resin and extremely excellent mechanical strength. CONSTITUTION:A laminated sheet for rolling obtained by welding and laminating a layer consisting of a crystalline thermoplastic resin (A) and an antimicrobial agent and a layer composed of a crystalline thermoplastic resin (B) or laminating both solidified layers through an adhesive layer, is rolled under a specific draft at temp. equal to or lower than the lowest m.p. of all of the resins to obtain a highly transparent antimicrobial multilayer sheet. Or, the layer composed of the resin (A) and the antimicrobial agent is laminated to the highly transparent sheet obtained by rolling the layer of the resin (B) at the same temp. under the same draft to prepare the highly transparent antimicrobial multilayer sheet.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent antibacterial sheet that is relatively inexpensive, has excellent transparency, and has antibacterial properties, but does not have any harmful effects on living organisms.

0002

[Prior Art] Conventionally, antibacterial sheet materials made of plastic have been used mainly in food packaging, food processing, daily necessities, environmental equipment and materials, medical care and pharmaceuticals, and electronics and engineering. It is used to prevent microbial disasters such as spoilage and product deterioration. The following methods are already known for imparting antibacterial properties to these sheet materials: ・Incorporation of antibacterial organic compounds; ・Incorporation of heavy metal powders, fibers, or knitted fabrics that exhibit antibacterial properties.・Blending antibacterial heavy metal compound powder or particles; ・Modifying the resin to impart antibacterial properties.

[0003] Among these, compositions containing organic compounds are likely to be accompanied by a decrease in antibacterial properties due to elution, volatilization or sublimation of the compound. Furthermore, the blending of antibacterial heavy metal powders, etc. is not only difficult to achieve uniformly due to the large density difference with the resin, but also often results in a decrease in transparency due to the low affinity of the resin to the surface of the metal powder, etc. . Similar problems are often associated with formulations such as antimicrobial heavy metal compound powders. Furthermore, the means for modifying resins may impair the advantages of the raw material resin, and the range of application is extremely limited.

0004

[Problems to be Solved by the Invention] In most of the above-mentioned conventional technologies, a sheet-like product is manufactured by kneading an antibacterial substance into a crystalline thermoplastic resin, but the lack of transparency due to crystallinity. However, depending on the intended use, this becomes a major obstacle in the development of new uses for the sheet-like material. Further, there are also problems such as a decrease in transparency due to the antibacterial substance and an increase in the price of sheet-like products due to the high price of the substance.

[0005] The present inventors have conducted extensive research into ways to obtain a sheet-like material that has antibacterial properties, is relatively inexpensive, and has excellent transparency even though it is a crystalline thermoplastic resin.

[0006]

[Means for Solving the Problems] As a result, the present inventors discovered that the objects of the present invention could be achieved in the following various embodiments, and based on this knowledge, completed the present invention: Zeolite Rolling a laminated sheet-like product of a film of a crystalline thermoplastic resin (A) containing a specific proportion of an antibacterial agent and a resin layer of a crystalline thermoplastic resin (B), or
After the resin layer of the crystalline thermoplastic resin (B) is rolled, a film of the crystalline thermoplastic resin (A) containing the zeolite antibacterial agent in a specific proportion is laminated on the rolled resin layer. In this lamination, it is important to include an adhesive layer.

As is clear from the above description, an object of the present invention is to provide an inexpensive transparent antibacterial sheet material having excellent transparency and sufficient antibacterial properties, and a method for producing the same.

That is, the present invention provides crystalline thermoplastic resin 1
A laminated sheet of a thermoplastic resin sheet and a film mainly composed of 0.00 parts by weight and 0.05 to 3 parts by weight of zeolite solid particles holding metal ions exhibiting antibacterial activity is made transparent by rolling. It consists of a transparent antibacterial sheet-like material (a concept that encompasses sheets and films) that is characterized by:

[0009] As the zeolite in the present invention, both natural zeolite and synthetic zeolite can be used. Zeolite is a general term for aluminosilicates that generally have a three-dimensional skeleton structure, and is expressed by one of the following general formulas depending on the valence of the metal "M" contained:mM
2 O・Al2 O3 ・pSiO2 ・qH2 O
(M is a monovalent metal) mMO・Al2 O3 ・pSiO2 ・qH2 O
(M is a divalent metal) mM2 O3 ・Al2 O3 ・pSiO2 ・qH
2 O (M is a trivalent metal) (Here, M represents an ion exchangeable ion, and is usually a monovalent or divalent metal ion. m and p are coefficients of metal oxide and silica, respectively; (q represents the number of water of crystallization.) Specific examples of zeolites include A-type zeolite, Examples include lolite, chabasite, orionite, but are not limited to these.

[0010] The zeolite-based solid particles holding metal ions exhibiting antibacterial action of the present invention refer to ion-exchangeable metal ions in the zeolite, such as sodium ions,
Some or all of calcium ions, potassium ions, magnesium ions, iron ions, etc. are replaced with antibacterial metal ions. Examples of antibacterial metal ions include:
Ions of silver, copper, lead, tin, chromium, cadmium, zinc, bismuth or thallium, preferably silver, copper or zinc ions.

The content ratio of each metal exhibiting a bactericidal effect to the total amount of zeolite (based on the weight of anhydrous zeolite) is as follows: silver: 30% by weight or less, preferably 0.001 to 5% by weight; copper; or 35 for zinc
% by weight or less, preferably from 0.01 to 15% by weight; when two or more of silver, copper and zinc ions are used together, the sum of these ions is preferably in the range from 0.001 to 15% by weight.

There is no problem if metal ions other than silver, copper or zinc ions, such as sodium, potassium, calcium ions, or ammonium ions, coexist in amounts that do not impede the bactericidal effect.

The content of the antibacterial zeolite solid particles holding antibacterial metal ions in the transparent antibacterial sheet of the present invention (based on anhydrous zeolite) is 0.05% by weight based on the weight of the crystalline resin. ~3 parts by weight, preferably 0.1 ~
The amount is set at 2 parts by weight, more preferably in the range of 0.2 to 1 part by weight.

If the amount of antibacterial zeolite solid particles holding antibacterial metal ions is less than 0.05 parts by weight, sufficient antibacterial properties will not be exhibited, and if the amount exceeds 3 parts by weight, It becomes difficult to obtain a transparent sheet because the tendency of the sheet to whiten, become perforated or cut during rolling becomes difficult to ignore.

Examples of the crystalline thermoplastic resin used in the present invention include the following: high-density polyethylene (HDPE), medium-density polyethylene (MDPE),
) or linear low-density polyethylene (L-LDPE) or ultra-high molecular weight polyethylene (UHMW-PE); homopolymerized polypropylene or copolymerized polypropylene; in addition to poly-1-butene, ethylene or propylene is the main component,
Polyolefin resins such as copolymers of this and other α-olefins or polar monomers; Polyamide resins such as nylon-6, nylon-6,6, nylon-11, and nylon-12; polyethylene terephthalate, polybutylene terephthalate Polyester resins such as polyester resins, polyacetal resins, and mixtures of two or more of these resins may be used as long as they are thermoplastic resins having crystallinity, and there are no restrictions on the type of raw material resin. Among these, crystalline polyolefin resins are preferred from the standpoint of practicality, ease of processing, and the like. In addition, modified resins obtained by copolymerizing or grafting unsaturated carboxylic acids such as maleic acid, acrylic acid, and fumaric acid, and derivatives such as their acid anhydrides or esters to the above resins, or treating the above resins with ionizing radiation, Modified resins crosslinked with a crosslinking agent can also be used depending on the application.

The adhesive layer in the present invention is not particularly limited and may be any known adhesive or adhesive film layer for bonding the crystalline thermoplastic resin (A) and the crystalline thermoplastic resin (B). Adhesives used in the present invention include urea resin, melamine resin, phenol resin, epoxy resin, vinyl acetate resin solution, and emulsion (vinyl acetate resin emulsion, ethylene vinyl acetate emulsion, vinyl acetate emulsion, etc.). (acrylic copolymer emulsion, etc.)
, hot melt type, cyanoacrylate type, polyurethane type, synthetic rubber type, etc. When using the above adhesive, it is also possible to perform surface treatment to increase adhesive strength.

[0017] As the adhesive film layer in the present invention, polyamide type, polyester type, epoxy/phenolic type, ionomer type, modified epoxy type, emulsion type,
Phenol type, polyvinyl acetal type, acrylic type,
Polyolefin type etc.

In the present invention, various fillers (or reinforcing materials) may be added to the crystalline thermoplastic resin in an amount that does not substantially reduce its transparency. Fillers that can be used include fibrous reinforcing materials such as glass fiber, carbon fiber, and vinylon fiber, flake fillers such as mica and talc, spherical fillers such as glass beads, and amorphous fillers such as calcium carbonate, wood chips, and wood powder. can be mentioned.

[0019] The surface of these fillers (or reinforcing materials) is preferably treated to impart affinity to the resin to be blended. Examples of such treatment include addition of an unsaturated carboxylic acid or its acid anhydride, addition of an unsaturated amine, and rubber coating.

[0020] In addition to these fillers, moisture absorbers,
Bulking agents, colorants, flame retardants, deterioration inhibitors, antistatic agents, lubricants, etc. may also be added as necessary.

In the present invention, the crystalline thermoplastic resin (A)
and zeolite-based solid particles that hold metal ions exhibiting antibacterial activity are melt-kneaded, and an antibacterial film is formed by a known molding method such as the T-die method or the inflation method. The same or different crystalline thermoplastic resin (B) can be laminated on one or both sides of the formed resin layer, and the resulting laminated sheet for rolling can be rolled.

Alternatively, the crystalline thermoplastic resin (A
) and zeolite solid particles that retain metal ions exhibiting antibacterial activity, and a separately prepared melt of crystalline thermoplastic resin (B) are co-extruded or extruded. It is also possible to perform a rolling treatment on a laminated sheet material for rolling (multilayer sheet material) obtained by laminating by the Lusion tandem method.

[0023] Lamination in the present invention is a general term for laminating two or more films or sheets together using an adhesive, an adhesive film, or by a known method such as heat fusing. In addition, we use two or more extruders to combine two or more molten resin streams in a die and extrude them (eco-strusion), a lamination method, and two or more heat exchangers from two or more T-dams. The lamination of the present invention also includes a tandem enclusion method in which the plastic resin layer is fused while being extruded. The rolling in the present invention must be carried out between one or more pairs of rolls at a temperature below the melting point (defined later) of the crystalline thermoplastic resin. If an attempt is made to roll the sheet at a temperature higher than the melting point of the crystalline thermoplastic resin, the sheet will melt and rolling will not take place. This can cause problems such as adhesion to surfaces.

[0024] The melting point of the resin in the rolling process of the present invention refers to the temperature at which the maximum peak of the thermal behavior curve of the resin obtained using a DSC (differential scanning calorimeter) according to JIS K7121 is located. . If there are multiple peaks, the peak with the largest area among them is defined as the largest peak. Further, the rolling operation may be repeated or the sheet-like material may be preheated before rolling, if necessary. In order to improve the transparency of the sheet, the surface roughness of the rolling roll used to create the transparent antibacterial sheet of the present invention is usually less than IS, preferably less than 0.5 S, and more preferably 0. .2 Set to S or less.

[0025] In the present invention, the rolling reduction rate (
r:%) can be expressed by the following formula from the thickness of the material resin before rolling (h1) and the thickness of the sheet after rolling (h2). r=100・(h1 −h2)/h1 (%) The final rolling reduction ratio of the rolled film or sheet (sheet-like material) is 50
It is preferable to set it in the range of % or more and 90% or less,
More preferably, it is 60% or more and 85% or less.

[0026] The transparent antibacterial sheet material of the present invention has an ASTM
Haze measured according to D1003 is 5% or less,
Preferably it is 3% or less.

[0027]

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The zeolite-based solid particles holding metal ions exhibiting antibacterial activity (hereinafter referred to as "antibacterial agent") used in the examples are commercially available under the trade name "Bacterikiller BM103" (manufactured by Kanebo Co., Ltd.). It is. This is a powder containing 3.5% by weight of silver in A-type zeolite and has a particle size of approximately 2 μm.

[0029] When performing melt-kneading and film forming by rolling, 1 part of the crystalline thermoplastic resin containing the antibacterial agent is added in advance.
The sample was heated in a heating oven at 20° C. for 8 hours or more before being subjected to treatment.

[0030] The rolling suitability was evaluated as × when whitening, holes, breakage, etc. occurred in the sheet material during the rolling process, and as ○ when a uniform transparent sheet was obtained.

[0031] Antibacterial properties were evaluated from the killing rate of viable bacteria measured by the method shown below. Results with a mortality rate of 90% or higher are marked with “○”
”, and results of less than 90% were expressed as “×”. The sample bacterial solution contains Escherichia coli as a test bacterial strain.
coil IF03301) or Staphylococcus aureus (S
taphylococcus aureusIFO
13276), cultured overnight at 37°C in ordinary bouillon medium, and then cultured for 1 m using sterile physiological saline.
Dilute and prepare so that the number of bacteria per liter is about 105 to 106. A fixed amount of the bacterial solution is sprayed onto the film surface of the laminated sheet, and the surface of the sample sheet is wiped with sterile gauze immediately after spraying and after being left at 35° C. for 18 hours. The test bacteria attached to this gauze are extracted with SCDLP bouillon medium to make a test solution, and the number of viable bacteria in this test solution is determined by SCDL.
Measurement is performed using the usual pour plate culture method (cultured at 37°C for 2 days) using P agar medium, and the mortality rate is calculated from the number of viable bacteria adhering to the sample surface immediately after spraying and after 18 hours.

Mortality rate = 100 x {Number of viable bacteria after 1-18 hours/Number of viable bacteria immediately after spraying} (%) Examples 1 to 3 and Comparative Examples 1 to 3 Polypropylene homopolymer [abbreviated as PP, melt Flow rate 1.0 g/10 min, density 0.90 g/cc,
melting point 162°C] and 0.5 part, 1 part by weight, or 2.5 parts by weight of the antibacterial agent were melt-kneaded in a granulator and the resin was mixed into two pieces. Laminated using the tandem method of extrusion using a T-die, the layer containing antibacterial agent is 30μ and the total thickness of the sheet is 1.5 mm.
Three types of rolling sheets each having a width of 250 mm and having different antibacterial agent concentrations on one side were prepared.

The above-mentioned rolling sheet was supplied to a pair of upper and lower rolling rolls each having a roll diameter of 300 mm and a width of 400 mm, and rolled at a roll temperature of 110° C. to a thickness of 0.40 mm and three types of sheets with different antibacterial agent concentrations. A rolled sheet was obtained (rolling ratio 73
%).

Table 1 shows the transparency (haze) and antibacterial properties of each sheet.

In addition, as Comparative Examples 1, 2, and 3, the case of laminating films containing no antibacterial agent, the case of laminating films containing 0.02 parts by weight of antibacterial agent, or the case of laminating films containing 10 parts by weight of antibacterial agent. The results are shown in Table 1.

Examples 4 to 6 and Comparative Examples 4 and 5 Ethylene-propylene random copolymer [abbreviated as "R-PP"]. Melt flow rate 2.2 g/10 min, density 0.
90g/cc, melting point 142℃, ethylene content 4mol%
and propylene content 96 mol%] and 0.5 parts by weight, 1 part by weight, or 1.5 parts by weight of the antibacterial agent, and a composition obtained by melt-kneading each composition in a granulator, and the resin. are laminated by the extrusion tandem method using two T-dies, and the antibacterial agent-containing layer is 30 μm, the total sheet thickness is 1.5 mm, and the width is 250 mm. Three types of rolling sheets with different antibacterial agent concentrations on one side are produced. It was created.

[0037] Each of the above sheets was supplied to a rolling roll with a roll diameter of 300 mm and a width of 400 mm, and rolled at a roll temperature of 90°C to a thickness of 0.42 mm with different antibacterial agent concentrations.
A type of rolled sheet (transparent sheet) was obtained (rolling ratio 72
%).

Table 1 shows the transparency and antibacterial properties of each sheet. Further, as Comparative Examples 4 and 5, the results are shown in Table 1 in the case of laminating films containing no antibacterial agent and in the case of laminating films containing 0.02 parts by weight of antibacterial agent.

Examples 7 and 8 and Comparative Example 6 Made of high-density polyethylene homopolymer (abbreviated as "PE", melt index (MI) 0.80 g/10 min, density 0.
A composition prepared by kneading 100 parts by weight (95 g/cc, melting point 130°C) and 1 part or 2 parts by weight of the antibacterial agent in a granulator and the resin were laminated by an extrusion tandem method using two T-dies. Two types of rolling sheets were prepared, each having a layer containing an antibacterial agent of 30 μm, a total sheet thickness of 2.2 mm, and a width of 250 mm, each having a different antibacterial agent concentration on one side.

[0040] Both sheets were rolled at a rolling temperature of 90°C in the same manner as in Example 1 to obtain a rolled sheet with a thickness of 0.45 mm (
Reduction rate: 80%).

Table 1 shows the transparency and antibacterial properties of both sheets.

Table 1 also shows the results of Comparative Example 6, in which films containing no antibacterial agent were laminated.

Example 9 Nylon-6 [abbreviated as "PA"]. Melt flow rate 2
．． 5 g/10 min, density 1.13 g/cc, melting point 225
Admer QF30, a resin layer obtained by melt-kneading a composition consisting of 100 parts by weight of the antibacterial agent and 1 part by weight of the antibacterial agent in a granulator.
5 (melt flow rate 1.5 g/10 min, density 0.
91g/cc, melting point 160°C, Mitsui Petrochemical Industries, Ltd.
] layer and the PP layer using a 60 mm coextrusion device, the PA layer containing 1 part by weight of antibacterial agent is 30 μm, and the ADM layer is 20 μm.
A multilayer rolled sheet having a total sheet thickness of 1.5 mm and a width of 250 mm was prepared using m, and rolling was performed in the same manner as in Example 1 to obtain a rolled sheet with a rolling reduction of 73%.

Examples 10 to 12 and Comparative Examples 7 to 9 Polypropylene homopolymer [abbreviated as PP, melt flow rate 1.0 g/10 min, density 0.90 g/cc, melting point 16
2° C.] and 0.5 parts by weight, 1 part by weight, or 2.5 parts by weight of the above-mentioned antibacterial agent, and a resin layer obtained by melt-kneading each composition with a granulator, and a layer of the resin to a thickness of 60 mm. Using a coextrusion apparatus, three types of multilayer rolling sheets with different antibacterial agent concentrations on one side were prepared, each having a layer containing an antibacterial agent with a thickness of 30 μm and a total sheet thickness of 1.5 mm x width of 250 mm.

The above-mentioned rolling sheet was supplied to a pair of upper and lower rolling rolls with a roll diameter of 300 mm and a width of 400 mm, and rolled at a roll temperature of 110° C. to a thickness of 0.40 mm, and three types of sheets with different antibacterial agent concentrations were prepared. A rolled sheet was obtained (rolling ratio 73
%). The transparency (haze) and antibacterial properties of each sheet are shown in "Table 3". In addition, as Comparative Examples 7, 8, and 9, a case where a film containing no antibacterial agent was multilayered and a case where a film containing an antibacterial agent of 0.0
Table 2 shows the results when a film containing 2 parts by weight was multilayered or a film containing 10 parts by weight was multilayered.

Examples 13 to 15 and Comparative Examples 10 and 1
1 Ethylene-propylene random copolymer [“R-PP
”. Melt flow rate 2.2 g/10 minutes, density 0.90 g/cc, melting point 142°C, ethylene content 4 mol%, propylene content 96 mol%] 100 parts by weight, 0.5 parts by weight of the above antibacterial agent, 1 weight or 1.5 parts by weight of each composition was melt-kneaded using a granulator, and the resin layer was melt-kneaded using a 60 mm coextrusion device to form a sheet with a layer containing an antibacterial agent having a thickness of 30 μm. Total thickness: 1.5mm x width: 2
Three types of 50 mm multilayer rolling sheets with different antibacterial agent concentrations on one side were prepared.

[0047] Each of the above sheets was supplied to a rolling roll with a roll diameter of 300 mm x width of 400 mm, and rolled at a roll temperature of 90°C to a thickness of 0.40 mm with different antibacterial agent concentrations.
A type of rolled sheet (transparent sheet) was obtained (rolling ratio 73
%). The transparency and antibacterial properties of each sheet are shown in "Table 2". Further, as Comparative Examples 10 and 11, the results are shown in "Table 2" for a multilayer film containing no antibacterial agent and a multilayer film containing 0.02 parts by weight of an antibacterial agent.

Examples 16 and 17 and Comparative Example 12 Made of high-density polyethylene homopolymer (abbreviated as "PE", melt index (MI) 0.8 g/10 min, density 0.95 g/cc, melting point 130° C.) 100 A resin layer obtained by kneading parts by weight and 1 part by weight or 2 parts by weight of the above-mentioned antibacterial agent in a granulator and the resin layer were mixed in a 60 mm co-extrusion device so that the layer containing the antibacterial agent had a thickness of 30 μm and the entire sheet was coated. Thickness is 2.2mm
Two types of rolling sheets each having a width of 250 mm and having different antibacterial agent concentrations on one side were prepared.

Both sheets were rolled in the same manner as in Example 10 at a rolling temperature of 90° C. to obtain a rolled sheet with a thickness of 0.44 mm (reduction ratio of 80%). The transparency and antibacterial properties of both sheets are
Table 2 shows the results. Furthermore, as Comparative Example 12, the results of a multilayered film containing no antibacterial agent are also shown in "Table 2".

Examples 18 to 20 and Comparative Examples 13 to 15 100 parts by weight of polypropylene homopolymer (abbreviated as PP, melt flow rate 1.0 g/10 minutes, density 0.90 g/cc, melting point 162°C) and the above antibacterial agent. 0.5 parts by weight, 1
Each composition consisting of parts by weight or 2.5 parts by weight was melt-kneaded using a granulator, and three types of films having different antibacterial agent concentrations and having a thickness of 30 μm and a width of 250 mm were prepared using a T-die method. Further, the crystalline resin was similarly kneaded using a granulator, and a sheet for rolling having a thickness of 1.5 mm and a width of 250 mm was prepared using the T-die method. The rolling sheet was supplied to a pair of upper and lower rolling rolls each having a roll diameter of 300 mm and a width of 400 mm, and the roll temperature was set to 1.
A rolled sheet with a thickness of 0.40 mm was obtained at 10° C. (rolling reduction ratio of 73%).

[0051] The antibacterial film and the rolled sheet were laminated using a dry lamination method (adhesive: Seikabond A-
120S, adhesive application amount: 1.5g/m2 ・Dry,
Laminated at a drying temperature of 80°C) and with different antibacterial agent concentrations 3
A transparent sheet-like material of various types was obtained. The transparency (haze) and antibacterial properties of each sheet are shown in "Table 3". Also, Comparative Example 13
, 14 and 15, Table 3 shows the results of laminating a film containing no antibacterial agent, laminating a film containing 0.02 parts by weight of an antibacterial agent, or laminating a film containing 15 parts by weight of an antibacterial agent. Shown below.

Examples 21 to 23 and Comparative Examples 16 and 1
7 Ethylene-propylene random copolymer (“R-PP
”. Melt flow rate 2.2 g/10 min, density 0.90 g/cc, melting point 142°C, ethylene component content 4 mol% and propylene component content 96 mol%) 100
parts by weight and 0.5 parts by weight, 1 part by weight or 1.5 parts by weight of the antibacterial agent.
Parts by weight of each composition were melt-kneaded using a granulator, and three types of films with different antibacterial agent concentrations each having a thickness of 30 μm and a width of 250 mm were created using a T-die method. Further, the crystalline resin was similarly kneaded using a granulator, and a sheet for rolling having a thickness of 1.5 mm and a width of 250 mm was prepared using the T-die method. Roll diameter 300
The above rolling sheet was supplied to a pair of upper and lower rolling rolls of mm x width 400 mm, and the rolling sheet was rolled to a thickness of 0.40 mm at a roll temperature of 90°C.
A rolled sheet of mm was obtained (rolling reduction ratio: 73%).

[0053] The antibacterial film and the rolled sheet were laminated using a dry lamination method (adhesive: Seikabond A-
120S, adhesive application amount: 1.5g/m2 ・Dry,
Laminated at a drying temperature of 80°C) and with different antibacterial agent concentrations 3
A transparent sheet-like material of various types was obtained. The transparency and antibacterial properties of each sheet are shown in "Table 3". Further, as Comparative Examples 16 and 17, the results are shown in Table 3 when a film containing no antibacterial agent was laminated and a film containing 0.02 parts by weight of an antibacterial agent was laminated.

Examples 24 and 25 and Comparative Example 18 Made of high-density polyethylene homopolymer (abbreviated as "PE"). 100 parts by weight of melt index (MI) 0.8 g/10 minutes, density 0.95 g/cc, melting point 130°C] and 1 part by weight or 2 parts by weight of the above antibacterial agent were kneaded in a granulator, and then mixed by a T-die method. Two types of films with different antibacterial agent concentrations were created, each having a thickness of 30 μm and a width of 250 mm. Further, the crystalline resin was similarly kneaded using a granulator, and a sheet for rolling having a thickness of 2.2 mm and a width of 250 mm was prepared using the T-die method. Roll diameter 300
The above-mentioned rolling sheet was supplied to a pair of upper and lower rolling rolls measuring 400 mm in width and 0.45 mm in thickness at a roll temperature of 90°C.
A rolled sheet of mm was obtained (rolling ratio: 80%).

[0055] The antibacterial film and the rolled sheet were bonded together using a dry lamination method (adhesive: Seikabond A-
120S, adhesive application amount: 1.5g/m2 ・Dry,
Laminated at a drying temperature of 80°C) with different antibacterial agent concentrations 2
A transparent sheet-like material of various types was obtained. Both sheets were rolled at a rolling temperature of 90°C in the same manner as in Example 18 to a thickness of 0.45 m.
A rolled sheet of m was obtained (rolling ratio: 80%). The transparency and antibacterial properties of both sheets are shown in Table 3. Also, Comparative Example 18
"Table 3" also shows the results when a film containing no antibacterial agent was laminated. In Tables 1 to 3, the words or symbols in the tables have the following meanings: A: Product name "Bactekiller BM103"; AD: Product name "Admer" (manufactured by Mitsui Petrochemicals); PA/AD/PP: It is a three-layer laminate consisting of a PA layer, an adhesive resin layer, and a PP layer, and the melting points of the resins in each layer are 225°C, 160°C, and 162°C, respectively.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Effects of the Invention] According to the present invention, it is possible to provide a sheet-like material that is highly transparent and effectively inhibits the growth of microorganisms such as Escherichia coli and cocci, even though it is made of a crystalline thermoplastic resin. Can be done.

Furthermore, the sheet material of the present invention has excellent mechanical strength and has sufficient durability against tension, impact, high temperature sterilization, etc.

Claims (24)

[Claims] Claim 1: A resin layer containing 100 parts by weight of a crystalline thermoplastic resin (A) and 0.05 to 5 parts by weight of zeolite solid particles holding metal ions having an antibacterial effect is made of a crystalline thermoplastic resin (B). 1.) A highly transparent antibacterial multilayer sheet material, which is laminated on at least one side of a resin layer consisting of a resin layer having a haze of 5% or less. 2. The highly transparent antibacterial multilayer sheet material according to claim 1, wherein the crystalline thermoplastic resin (A) is a crystalline polypropylene resin. [Claim 3]Claim 1, wherein the crystalline thermoplastic resin (A) is a crystalline propylene-1-olefin copolymer resin.
The highly transparent antibacterial multilayer sheet material described in . 4. The highly transparent antibacterial multilayer sheet material according to claim 1, wherein the crystalline thermoplastic resin (A) is a crystalline random copolymerized polypropylene resin. 5. The highly transparent antibacterial multilayer sheet material according to claim 1, wherein the crystalline thermoplastic resin (A) is a crystalline propylene-ethylene random copolymer resin. 6. The highly transparent antibacterial multilayer sheet material according to claim 1, wherein the crystalline thermoplastic resin (A) is a crystalline block copolymerized polypropylene resin. 7. The highly transparent antibacterial multilayer sheet material according to claim 1, wherein the crystalline thermoplastic resin (A) is a crystalline propylene-ethylene block copolymer resin. 8. The highly transparent antibacterial multilayer sheet material according to claim 1, wherein the crystalline thermoplastic resin (A) is a crystalline polyethylene resin. 9. The highly transparent antibacterial multilayer sheet material according to claim 1, wherein the crystalline thermoplastic resin (A) is a crystalline ethylene copolymer resin. 10. The highly transparent antibacterial multilayer sheet material according to claim 1, wherein the crystalline thermoplastic resin (B) is the same as the crystalline thermoplastic resin (A). 11. A resin layer containing 100 parts by weight of the crystalline thermoplastic resin (A) and 0.05 to 5 parts by weight of zeolite solid particles holding metal ions having an antibacterial effect is added to the crystalline thermoplastic resin (B). A highly transparent antibacterial multilayer sheet material, characterized in that it is laminated on at least one side of a resin layer consisting of the following: and is rolled at a temperature below the lower melting point of both thermoplastic resins (A) and (B) manufacturing method. 12. A melt of a resin composition containing 100 parts by weight of a crystalline thermoplastic resin (A) and 0.05 to 5 parts by weight of zeolite solid particles holding metal ions having an antibacterial effect, and crystallization heat. The melted plastic resin (B) is coextruded and laminated to form a resin layer (
A) is laminated, and the resulting laminate is laminated with both thermoplastic resins (A).
A method for producing a highly transparent antibacterial multilayer sheet material, which comprises rolling at a rolling reduction of 50 to 90% below the lower of the melting points of (B) and (B). 13. A melt of a resin composition containing 100 parts by weight of a crystalline thermoplastic resin (A) and 0.05 to 5 parts by weight of zeolite solid particles holding metal ions having an antibacterial effect is heated to crystallization heat. A highly transparent antibacterial multilayer sheet, which is a rolled sheet made of a plastic resin (B), characterized in that the resin (B) is laminated on at least one side of the rolled sheet within a rolling reduction ratio of 50 to 90%. A method for manufacturing a shaped article. 14. A sheet-like material made of a resin composition containing 100 parts by weight of a crystalline thermoplastic resin (A) and 0.05 to 5 parts by weight of zeolite solid particles holding metal ions having an antibacterial effect is crystallized. A rolled sheet made of a thermoplastic resin (B) with a rolling reduction ratio of 50 to 90%.
1. A method for producing a highly transparent antibacterial multilayer sheet material, which comprises laminating on at least one side of a sheet material rolled within the range of . 15. The laminate obtained in any one of claims 12 to 14 is subjected to an overall rolling reduction of 50 to 50 at a temperature below the lower melting point of both thermoplastic resins (A) and (B).
A method for producing a highly transparent antibacterial multilayer sheet material, characterized by further rolling it with rolls so as to keep the antimicrobial resistance within a range of 90%. 16. The method for producing a highly transparent antibacterial multilayer sheet material according to claim 11, wherein the crystalline thermoplastic resin (A) is a crystalline polypropylene resin. 17. The method for producing a highly transparent antibacterial multilayer sheet according to claim 11, wherein the crystalline thermoplastic resin (A) is a crystalline propylene-1-olefin copolymer resin. 18. Claims 11 to 12, wherein the crystalline thermoplastic resin (A) is a crystalline random copolymerized polypropylene resin.
16. The method for producing a highly transparent antibacterial multilayer sheet material according to any one of 15. 19. The method for producing a highly transparent antibacterial multilayer sheet according to claim 11, wherein the crystalline thermoplastic resin (A) is a crystalline propylene-ethylene random copolymer resin. 20. Claims 11 to 20, wherein the crystalline thermoplastic resin (A) is a crystalline block copolymerized polypropylene resin.
16. The method for producing a highly transparent antibacterial multilayer sheet material according to any one of 15. 21. The method for producing a highly transparent antibacterial multilayer sheet according to claim 11, wherein the crystalline thermoplastic resin (A) is a crystalline propylene-ethylene block copolymer resin. 22. The method for producing a highly transparent antibacterial multilayer sheet according to any one of claims 11 to 15, wherein the crystalline thermoplastic resin (A) is a crystalline polyethylene resin. 23. The method for producing a highly transparent antibacterial multilayer sheet material according to claim 11, wherein the crystalline thermoplastic resin (A) is a crystalline ethylene copolymer resin. 24. The method for producing a highly transparent antibacterial multilayer sheet according to claim 11, wherein the crystalline thermoplastic resin (B) is the same as the crystalline thermoplastic resin (A).