JPH10337814A - Antibacterial synthetic resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide antibacterial ability while maintaining thermoforming characteristics after thermoforming such as vacuum molding with excellent external appearance by constituting by a transparent resin film obtained by adding matting agent and antibacterial agent to synthetic resin and opaque synthetic resin plate. SOLUTION: A matting agent does not remarkably lower transparency of a transparent vinyl chloride resin film to be laminated so that glossiness of a laminate obtained by laminating the film on an opaque synthetic resin plate becomes 15% or less. For example, fine powder-like silica particles, crosslinked acrylic resin, or crosslinked vinyl chloride resin can be used. And, an antibacterial agent scarcely discolors the film at the time of molding or laminating the film. For example, an agent obtained by carrying silver ion to acid point of phosphate ceramics by mechanochemical reaction of the phosphate ceramics added with silver nitrate is suitable. And, zeolite antibacterial agent is used as well.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin laminate having a matte effect and having an antibacterial property.

[0002]

2. Description of the Related Art Products such as covers and housing members of various devices are suitable for thermoforming such as vacuum forming, and are made of vinyl chloride resin or acrylonitrile butadiene-styrene, which is excellent in shape retention of formed molded products. Many are made of synthetic resins such as polymer resins.

[0003] On the surface of these synthetic resins, microorganisms are relatively difficult to proliferate. However, various types of relations such as hospital relations and barber / beauty relations that dislike the reproduction of microorganisms, as well as residence relations such as baths, toiletries, and rooms. When used in the environment, it is required to actively kill or reduce microorganisms.

[0004] Therefore, as means for imparting bactericidal or antibacterial properties for the purpose of use in various environments, there have hitherto been used an ultraviolet irradiation method using an ultraviolet lamp, an ozone oxidation method, a washing method using a sodium hypochlorite solution, and a molded article. The antibacterial agent or the antibacterial property is imparted by kneading an antibacterial agent into the synthetic resin constituting the above or coating the surface of the synthetic resin.

[0005]

However, the ultraviolet irradiation method, the ozone oxidation method, and the cleaning method using a solution require an apparatus for generating ultraviolet light, generating ozone, and cleaning, and constitute a molded object to be sterilized. The surface of the synthetic resin may be discolored or deteriorated.

When kneading an antibacterial agent into the entire constituent resin, a large amount of the antibacterial agent is inevitably required.
When applying an antibacterial agent, the strength of the obtained film becomes a problem.

[0007] Therefore, a film in which an antibacterial agent is contained is laminated on a synthetic resin as a base material. In this case, however, the antibacterial agent is exposed from the surface of the film in order to exhibit antibacterial or sterilizing ability. As a result, the surface of the laminate may lack smoothness, and if a glossy surface is desired, appearance may be difficult.

[0008] Further, when the laminate is subjected to thermoforming or the like, glossy unevenness may occur on the surface of the molded article after thermoforming, which may make appearance difficult.

[0009]

SUMMARY OF THE INVENTION The present invention provides a synthetic resin laminate having an excellent appearance, maintaining its properties even after thermoforming such as vacuum forming, and having an antibacterial activity. The gist thereof is that a transparent resin film having a matting agent and an antibacterial agent added to a synthetic resin, preferably having a thickness of 30 μm or more and 150 μm or less and / or having an irregular pattern on the outer surface, and an opaque synthetic resin An antibacterial synthetic resin laminate comprising a plate.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The synthetic resin constituting the transparent film of the present invention includes a thermoplastic resin such as a vinyl chloride resin, an acrylic resin, and a polystyrene resin. Among them, the material cost is low, and the processability into a film and the obtained resin are obtained. A vinyl chloride resin having excellent film strength is preferred.

The synthetic resin constituting the opaque synthetic resin plate includes vinyl chloride resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as ABS resin), acrylic resin, A mixture of a thermoplastic resin such as a polystyrene resin and a filler or a coloring agent can be used. Among them, a vinyl chloride resin or an ABS resin which is excellent in thermoformability such as vacuum molding and has relatively low material cost is preferable. . In particular, a vinyl chloride resin is excellent in flame retardancy, and an ABS resin is excellent in impact resistance. Further, it is preferable because the molded article can be reduced in weight at a low specific gravity at a low specific gravity.

The matting agent of the present invention does not greatly reduce the transparency of the transparent vinyl chloride resin film to be laminated, and furthermore, the glossiness of the laminated plate obtained by laminating this on an opaque synthetic resin plate Is not particularly limited as long as it is 15% or less, for example, fine powdery silica particles, a crosslinked acrylic resin, a crosslinked vinyl chloride resin and the like can be used.

Particularly, the addition of the crosslinked vinyl chloride resin in the range of 15% by weight or more and 50% by weight or less of the whole composition is preferred.
It is preferable in terms of matting properties, tensile strength, and material cost.

The amount of the crosslinked vinyl chloride resin added is 15
If the content is less than 10% by weight, after laminating a transparent vinyl chloride resin film on an opaque resin molded plate and then thermoforming the same, gloss is developed on the surface of the laminated plate and the matte feeling is easily reduced. Not preferred.

On the other hand, if it exceeds 50% by weight, the tensile strength of the resin film decreases, and the resin film is easily cut when the resin film is laminated on an opaque synthetic resin plate, which is not preferable.

The antibacterial agent used in the present invention is not particularly limited as long as it does not discolor the film at the time of forming or laminating the film. For example, a phosphate ceramic obtained by adding silver nitrate to a phosphate ceramic is subjected to a phosphorylation by a mechanochemical reaction. Antibacterial agents in which silver ions are supported at acid sites of phosphate ceramics (hereinafter referred to as silver / apatite antibacterial agents) are preferable, and antibacterial synthetic zeolites supporting silver, copper, zinc, etc. , A zeolite-based antibacterial agent).

The addition of these antibacterial agents to the synthetic resin may be carried out by kneading the resin film together with various additives into a synthetic resin when forming a transparent resin film.

The method of evaluating antibacterial activity will be described in detail later. After applying a bacterial solution to a sample, this is cultured for 24 hours, and the number of bacteria on the surface of the sample is reduced to one hundredth or less of the initially added number. It is judged to be effective if possible. The addition amount of the antibacterial agent on this basis depends on the type of the antibacterial agent, but is preferably in the range of about 0.5 to 3% by weight.

The transparent synthetic resin film may further contain an impact modifier, a heat stabilizer, if necessary, in addition to the matting agent and the antibacterial agent.
Additives such as plasticizers, lubricants and colorants may be added.

The transparent synthetic resin film is formed by molding a composition in which a synthetic resin is blended with predetermined additives such as a matting agent and an antibacterial agent by a molding method such as a calendering method or an extrusion method using a T-die.

Then, on the surface of the transparent synthetic resin film, for example, a transparent film immediately after molding is passed through an embossing roll and laminated on the surface of the transparent synthetic resin film on a matte or embossed pattern or an opaque synthetic resin plate. In this case, a matte roll having fine matte-like irregularities on the surface may be used to form a concavo-convex pattern to impart a matte feeling and a good appearance.

The thickness of the synthetic resin film is set to 30 μm because, when laminating on an opaque synthetic resin plate, the film may be broken by the bonding tension or the heat of the bonded portion.
m or more.

When the thickness of the synthetic resin film is unnecessarily large, the color tone of the opaque synthetic resin plate, which substantially becomes the base of the formed synthetic resin laminate, is difficult to clearly appear. Preferably, it is a film.

An opaque synthetic resin plate on which a transparent synthetic resin film is laminated is provided with a coloring agent so that a molded product obtained by thermoforming such as vacuum forming has a concealing property such that the other side cannot be seen through. Alternatively, a filler, and if necessary, an impact modifier, a heat stabilizer, a plasticizer, a lubricant and the like are added.

Then, the composition to which the predetermined additive has been added is melt-mixed using an extruder, and cooled by a die.
And an opaque synthetic resin plate having a thickness of 0.5 to 10 mm obtained by extruding between the screws.

The transparent synthetic resin film is laminated on the surface of the opaque synthetic resin molded plate by a hot press method, a co-extrusion method, an extrusion lamination method or the like. While unwinding the transparent rolled film obtained by the above through a guide roll, the film is superimposed on the surface of the opaque yet molten plate-like body formed by the T-die extrusion method, and these are laminated with a plurality of films. A method is adopted in which a film is melt-integrated on the surface of a molten plate-like body while passing through a gap between cooling rolls to form a synthetic resin laminate. In this case, using a mat roll provided with a matte-like matte-like uneven pattern on the roll in contact with the film, the outer surface of the film may be provided with an uneven pattern, but all are plain rolls There may be no irregularities on the outer surface of the film.

[0028]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

The performance of the vinyl chloride resin and ABS resin laminate obtained in the following Examples and Comparative Examples was evaluated or measured by the following methods, and the results were displayed. "Film breakability" A roll of a transparent vinyl chloride resin film previously obtained by the T-die extrusion method is fed out from the unwinding shaft through a guide roll, and is an opaque molten plate formed by the T-die extrusion method. The film was inserted between the body and the cooling roll and melted and integrated while applying tension to prevent wrinkling of the film, and the state of the film was evaluated.

That is, a laminate that could be obtained without breaking due to tension and nearby heat was evaluated as (○),
A very small number of samples were broken, but a laminated plate could be obtained (△), and those frequently broken and a laminated plate could not be obtained were (X).

[Tone] The obtained vinyl chloride resin laminate and ABS resin laminate, an opaque vinyl chloride resin plate and ABS resin plate having the same surface condition as those of the laminate were prepared, and a 38-watt rod-shaped plate was prepared. Approximately 50c under two fluorescent lights
At m, both color tones were visually evaluated and compared, and this was regarded as the color tone.

That is, when there is no difference in the color tone between the opaque vinyl chloride resin plate and the ABS resin plate which are the bases due to the lamination of the transparent vinyl chloride resin film (、), the color is dull depending on the intensity of light and the angle. Those that can be seen are indicated by (△), those that have a distinctly dull color, or those that have a different gloss are indicated by (x).

"Matte" The resin film surface of the obtained vinyl chloride resin laminate and ABS resin laminate was measured according to JIS.
It was measured by K-7105, and this was taken as the matte property before molding.

That is, those having a glossiness of 15% or less (（), those having a glossiness of more than 15% and 20% or less (△), and those having a glossiness of more than 20% are (x). did.

The glossiness of the resin film surface of a product obtained by molding the obtained vinyl chloride resin laminate and ABS resin laminate by vacuum molding is measured according to JIS K-7105. Matted.

That is, those having a glossiness of 20% or less (（), those having a glossiness of more than 20% and 25% or less (△), and those having a glossiness of more than 25% are (x). did.

The vacuum forming method is described as follows: “The obtained vinyl chloride resin laminate and ABS resin laminate are 70 cm × 70 cm.
cm, which is clamped with the resin film surface facing upward and heated to a surface temperature of about 180 ° C. with an infrared heater, and then 50 cm wide, 50 cm deep and 25 cm high.
The laminated board softened with a box-shaped mold of m is pushed up and cooled by air while sucking air in the gap between the mold and the laminate into the mold side by vacuum, and the inner dimensions are width 50 cm, depth 50 cm, height. A 25 cm box-shaped product. ".

"Antibacterial activity" The antibacterial activity of an antibacterial product was evaluated in accordance with the method for testing the antibacterial activity of the product "Film adhesion method (Research Group for Inorganic Antibacterial Agents such as Silver; 1995 edition)".

That is, those in which the number of E. coli and Staphylococcus aureus both decreased to 1/100 or less in the initial stage were evaluated as (○), and those in which the numbers did not decrease to 1/100 or less were evaluated as (x).

The antibacterial activity test method is as follows: "A flat portion of a product obtained by a vacuum forming method is cut into 5 cm × 5 cm, and the resin film surface is wiped with ethanol, and then dried at 40 ° C. in a dryer.
After drying for 24 hours, a 0.5 ml inoculation solution containing 1.0 to 5.0 × 10 5 E. coli and Staphylococcus aureus was inoculated, and a polyethylene film cut into 45 × 45 mm was placed thereon. After covering, temperature 35 ° C, relative humidity 90
% For 24 hours, the number of Escherichia coli and Staphylococcus aureus on the surface of the sample was measured by a pour plating method and compared with the initial numbers of Escherichia coli and Staphylococcus aureus. ".

"Preparation of opaque vinyl chloride resin plate and ABS resin plate" Basic blend 100 parts by weight of vinyl chloride resin 15 parts by weight of acrylic impact modifier 5 parts by weight of acrylic moldability improver Maleate organotin heat stability 3 parts by weight Lubricant 1 part by weight Colorant (gray) 4 parts by weight Basic blend ABS resin 100 parts by weight 4 parts by weight Colorant (gray) 4 parts by weight Using a screw extruder, an opaque vinyl chloride resin plate and an ABS resin plate in a molten state having a thickness of about 3 mm were obtained.

[Preparation of Transparent Vinyl Chloride Resin Film] Basic Formulation Vinyl Chloride Resin (TH-700, manufactured by Tosoh Corporation) 100 parts by weight Acrylic impact modifier 7 parts by weight Malate organic tin heat stabilizer 3 1 part by weight Fatty acid ester plasticizer 3 parts by weight Lubricant 1 part by weight Blue pigment (phthalocyanine blue) 0.002 parts by weight Impact modifier; methyl methacrylate butadiene-styrene copolymer Add and mix an antiseptic and an antibacterial agent, melt and knead them using a single screw extruder, extrude it onto a cooling roll from a T-die provided at the tip of the extruder, and wind it up on a paper tube. As a result, a transparent vinyl chloride resin film having the thickness shown in the table was obtained.

[Preparation of Vinyl Chloride Resin Laminated Board and ABS Resin Laminated Board] The T-die obtained above was wound out of the transparent vinyl chloride resin film having a smooth surface obtained above through a guide roll. A mat roll with fine matte tone unevenness in the center is placed on the upper surface of the more extruded molten opaque vinyl chloride resin plate and ABS resin plate, and plain rolls are arranged above and below it. In a gap between a lower plane roll and a center mat roll of a certain vertical three roll, continuously on a half circumference of the center mat roll, in a gap between the center mat roll and the upper plane roll, and on a half circumference of the upper plane roll, in order, it is transparent. Fusing and unifying the opaque vinyl chloride resin plate and ABS resin plate while forming a mat-like fine uneven pattern on the outer surface of the film,
A vinyl chloride resin laminate and an ABS resin laminate having a total thickness of 3 mm and having a matte-shaped fine irregular pattern on the outer surface were obtained.

However, in Example 7 and Example 18, the opaque vinyl chloride having no matte-like fine unevenness pattern formed on the outer surface of the transparent film using a center plain roll instead of the center mat roll. Resin laminate and A
A BS resin laminate was used.

Table 1 “In the case of a vinyl chloride resin laminate” Additives account for% by weight of the total formulation. Example 1 Example 2 Example 3 Example 4 Additive to film Delustering agent Crosslinked vinyl chloride resin 30 % 30% 30% 30% Antibacterial agent Silver / Apatite 1% 1% 1% Silver / Zeolite 1% Film properties Thickness 30μm 75μm 150μm 75μm Breakability 〇 〇 〇 特性 Laminate properties Film thickness about 27μm About 72μm About 145μm About 72μm Thickness of laminated board 3mm 3mm 3mm 3mm Color tone 〇 〇 〇 Matting property Before molding 〇 〇 〇 〇 Matting property After molding 〇 〇 〇 抗菌 Antibacterial 〇 〇 性 〇 Table 2 In the case of a resin laminate "The additive accounts for% by weight of the total composition. Example 5 Example 6 Example 7 Additive to film Delustering agent Crosslinked vinyl chloride resin 30% 30% 30% Antibacterial agent Silver / apatite system% 1% 1% Film properties Thickness 35μm 140μm 30μm Breakability 〇 〇 特性 Properties of laminated board Film thickness about 32μm about 136μm about 27μm Laminated board thickness 3mm 3mm 3mm Color tone 〇 〇 艶 Matting Before molding 〇 〇 〇 Matting property After molding 〇 〇 〇 Antibacterial property 〇 〇 〇 Table 3 “In the case of vinyl chloride resin laminate” Additives are% by weight of the total formulation Example 8 Example 9 Example 10 Example 11 Additive to film Matting agent Crosslinked vinyl chloride resin 10% 45% 30% 30% Antibacterial agent Silver / apatite 1% 1% 1% 1% Film properties Thickness 75μm 75μm 25μm 200μm Breakability 〇 △ △ Board properties Film thickness Approx. 72μm Approx. 72μm Approx. 22μm Approx. 194μm Thickness of laminated board 3mm 3mm 3mm 3mm Color tone 〇 〇 〇 △ Matting property Before molding 〇 〇 〇 艶 Matting property After molding △ 〇 〇 抗菌 Antibacterial ４ 〇 〇 〇 Table 4 “In the case of vinyl chloride resin laminate” Additives are% by weight of the total formulation Comparative Example 1 Comparative Example 2 Additives to films Delustering agent Crosslinked vinyl chloride resin 0 30% Antibacterial agent Silver / Apatite 1% 0% Film characteristics Thickness 75μm 75μm Breakability 〇 特性 Laminate characteristics Film thickness Approx. 72μm Approx. 72μm Laminate thickness 3mm 3mm Color tone × 〇 Matteness Before molding × 〇 Matte After molding × 抗菌 Antibacterial 〇 × Table 5 “In the case of ABS resin laminate” Additives are% by weight of the total formulation. Example 12 Example 13 Example 14 Example 15 Additive to film Matting agent Crosslinked vinyl chloride resin 30% 30% 30% 30% Antibacterial agent Silver / Apatite 1% 1% 1% Silver / Zeolite 1% Film properties Thickness 30μm 75μm 150μm 75μm Breakability 〇 〇 〇 〇 Film thickness Approx. 27 μm Approx. 72 μm Approx. 145 μm Approx. 72 μm Laminate thickness 3 mm 3 mm 3 mm 3 mm Color tone 〇 〇 艶 Matting Before molding 〇 〇 〇 艶 Matting After molding 〇 〇 〇 抗菌 Antibacterial 〇 〇 〇 〇 Table 6 “In the case of ABS resin laminate” Additives are% by weight of the total formulation. Example 16 Example 17 Example 18 Additive to film Delustering agent Crosslinked vinyl chloride resin 30% 30% 30% Antibacterial Agent Silver / Apatite 1% 1% 1% Film properties Thickness 35μm 140μm 30μm Breakability 〇 〇 特性 Laminate properties Film thickness Approx. 32μm 136μm Approx. 27μm Laminate thickness 3mm 3mm 3mm Color tone 〇艶 Matting property Before molding 〇 〇 〇 Matting property After molding 〇 〇 抗菌 Antibacterial property 〇 〇 〇 Table 7 “In the case of ABS resin laminate” Additives are% by weight of the total formulation Example 19 Example 20 Example Example 21 Example 2 Additive to film Delustering agent Crosslinked vinyl chloride resin 10% 45% 30% 30% Antibacterial agent Silver / apatite 1% 1% 1% 1% Film properties Thickness 75μm 75μm 25μm 200μm Breakability 〇 △ △ Laminate properties Film thickness Approx. 72μm Approx. 72μm Approx. 22μm Approx. 194μm Laminate thickness 3mm 3mm 3mm 3mm Color tone 〇 〇 〇 △ Matting property Before molding 〇 〇 〇 艶 Matting property After molding △ 〇 〇 抗菌 Antibacterial Properties 〇 〇 〇 〇 Table 8 “In the case of ABS resin laminate” Additives are% by weight of the total formulation Comparative Example 3 Comparative Example 4 Additive to film Delustering agent Crosslinked vinyl chloride resin 0 30% Antibacterial agent Silver / Apatite 1% 0% Film characteristics Thickness 75μm 75μm Breakability 〇 特性 Laminate characteristics Film thickness Approx. 72μm Approx. 72μm Laminate thickness 3mm 3mm Color tone × 〇 Matteness Before molding × 〇 Matte sex After molding × 抗菌 Antibacterial 〇 ×

[0046]

The synthetic resin laminate of the present invention does not change its color tone due to dull surface or loss of calm matte due to glossiness. The predetermined glossiness can be maintained before and after the history.

Further, even after a heat history such as a vacuum forming method, good sterilization can be sufficiently ensured without being affected by heat.

The synthetic resin laminate of the present invention is to uniformly improve the color tone and mattness of the transparent film by adding a matting agent. A mat-like fine uneven pattern may be formed by a mat roll or the like.

Claims (5)

[Claims] 1. An antibacterial synthetic resin laminate comprising a transparent resin film obtained by adding a matting agent and an antibacterial agent to a synthetic resin, and an opaque synthetic resin plate. 2. The antibacterial synthetic resin laminate according to claim 1, wherein the transparent resin film is a vinyl chloride resin having a thickness of 30 μm or more and 150 μm or less. 3. The antibacterial synthetic resin laminate according to claim 1, wherein the transparent resin film has an uneven surface on its outer surface. 4. The antibacterial synthetic resin laminate according to claim 1, wherein the synthetic resin of the opaque synthetic resin plate is a vinyl chloride resin. 5. An antibacterial synthetic resin laminate according to claim 1, wherein the synthetic resin of the opaque synthetic resin plate is an acrylonitrile-butadiene-styrene copolymer resin.