JP2022112127A - Print film, processing method thereof, printed matter and production method thereof - Google Patents

Abstract

To provide: printed matter capable of fully exerting an antibacterial and antiviral effect of metal particles or metal oxide particles (hereinafter, metal particles); and a production method thereof.SOLUTION: Printed matter includes a printed cured film 303 formed on a surface of a substrate 300 using a printing ink containing antibacterial and antiviral metal particles and a binder resin, where surface of the metal particles 301 contained in the printed cured film 303 are partially exposed. A production method of printed matter includes: a printing process of forming a coating film 302 of a printing ink on a surface of a substrate 300; a curing process of applying active energy rays to form a printed cured film 303; and an atmospheric pressure plasma treatment process of irradiating a surface of the printed cured film with an atmospheric pressure plasma and removing a binder resin 301a covering surfaces of the metal particles 301 to partially expose the surfaces of the metal particles 301.SELECTED DRAWING: Figure 3

Description

The present invention relates to a printed film formed using a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin. Alternatively, the present invention relates to a printed film in which a part of the metal oxide particle surface is exposed, a treatment method thereof, a printed matter and a production method thereof.

It has long been known that copper, silver, nickel, and zinc have antibacterial and antiviral effects. Among them, copper and silver have extremely high antibacterial and antiviral effects, and are used in daily necessities such as triangular corners of sinks, washbasins, and doorknobs. The antibacterial and antiviral effects are due to the active oxygen generated by the reaction between the metal and the surrounding moisture or the trace amount of metal ions dissolved in the moisture suppressing the growth of bacteria and inactivating the virus. It is believed that this is due to the contact of solid surfaces.

In particular, it has been demonstrated that the antibacterial and antiviral effects of copper-containing compounds are due to contact with a metal solid surface, and the US Environmental Protection Agency (EPC) approved the antibacterial effect of copper in 2008. Its antibacterial and antiviral effects are attracting more and more attention.

At present, in addition to products made by pressing wrought copper products, there are methods of coating the surface of products with copper or applying copper foil, methods of incorporating copper particles into fibers or films, or methods of incorporating copper particles into paper or cloth. It has a wide range of uses such as printing methods.

And, in Patent Document 1, a cuprous oxide particle dispersion containing cuprous oxide particles, a coating agent composition containing the dispersion and a binder resin, and a substrate and a coating provided on the substrate An antibacterial and antiviral member comprising a coating of the agent composition is disclosed.

International Publication No. 2014/132606 pamphlet (claims 1 to 3, see paragraph 0039)

By the way, the antibacterial/antiviral member described in Patent Document 1 is formed by forming a film of a coating agent composition containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin on a substrate. In this case, even if there are metal particles or metal oxide particles on or near the coating surface, the surfaces of these particles may be covered with the coating.

Therefore, the antibacterial and antiviral effects of the metal particles and metal oxide particles may be suppressed by the coating of the coating agent composition.

The present invention has been made with a focus on such problems, and the object thereof is to form using a printing ink containing antibacterial / antiviral metal particles or metal oxide particles and a binder resin. and a printed film in which the antibacterial and antiviral effects of the metal particles and metal oxide particles are sufficiently exhibited, a treatment method thereof, and a printed matter in which the printed film is formed on the surface of a base material and a method for producing the same. to do.

Therefore, in order to solve the above problems, the present inventors have found that atmospheric pressure plasma is applied to the surface of a printed film formed using a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin. When the effect was confirmed by irradiating with , the resin component of the printed film covering the surface of the metal particles and metal oxide particles existing on or near the printed film surface was uniformly removed, and the metal particles and metal oxide particles were uniformly removed. We have found that the antibacterial and antiviral effects of the oxide particles are sufficiently exhibited. The present invention has been completed through such technical discoveries.

That is, the first invention according to the present invention is
A printed film formed using a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin,
A part of the surface of the metal particles or metal oxide particles contained in the printed film is exposed on or near the surface of the printed film.

Moreover, the second invention according to the present invention is
In the printed film according to the first invention,
The film thickness of the printed film is 0.5 μm to 100 μm, and the median value of the particle size distribution of the metal particles or metal oxide particles is 1/3 or less of the film thickness,
The third invention is
In the printed film according to the first invention or the second invention,
The antibacterial/antiviral metal particles are composed of copper particles, silver particles, nickel particles, or zinc particles,
The fourth invention is
In the printed film according to the first invention or the second invention,
The antibacterial and antiviral metal oxide particles are composed of cuprous oxide particles,
The fifth invention is
in printed matter,
characterized in that the printed film according to any one of the first to fourth inventions is formed on the surface of a substrate,
The sixth invention is
In the printed matter according to the fifth invention,
The base material is characterized by being composed of any one of paper, wood bark, cloth, plastic plate, metal plate, ceramic plate, and glass plate.

Next, the seventh invention is
In the method for manufacturing printed matter,
a printing step of printing a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin on the surface of a substrate to form a coating of the printing ink;
A curing step of applying an active energy ray to the coating to cure it to form a printed cured film;
The surface of the printed cured film is irradiated with atmospheric pressure plasma to remove the binder resin covering the surface of the metal particles or metal oxide particles present on or near the surface of the printed cured film, thereby removing the metal particles or metal oxides. an atmospheric pressure plasma treatment step that exposes a portion of the particle surface;
characterized by having
The eighth invention is
In the method for manufacturing printed matter according to the seventh invention,
The process gas used in the atmospheric pressure plasma treatment step contains nitrogen, argon gas, or helium as a main component, and one or more species selected from oxygen, nitrogen, hydrogen, water, and ammonia are added as active species to the process gas. characterized by
The ninth invention is
In the printed matter manufacturing method according to the seventh invention or the eighth invention,
In the atmospheric pressure plasma treatment step, the surface of the printed cured film is irradiated with activated active species using a remote type atmospheric pressure plasma generator,
A tenth invention is
In the method for producing printed matter according to any one of the seventh to ninth inventions,
The antibacterial/antiviral metal particles used in the printing process are composed of copper particles, silver particles, nickel particles, or zinc particles,
The eleventh invention is
In the method for producing printed matter according to any one of the seventh to tenth inventions,
The binder resin used in the printing step is composed of a rosin-modified phenol resin, the antibacterial and antiviral metal particles are composed of copper particles, and the process gas used in the atmospheric pressure plasma treatment step is argon gas, and A mixed gas of 10% oxygen and 4% hydrogen is added to the above process gas, and a power of 50 W to 100 W is applied from a high frequency power supply to the atmospheric pressure plasma head of the remote atmospheric pressure plasma generator, and the speed is 30 m / min to 60 m. / minute, characterized by irradiating the printed cured film of the substrate conveyed with atmospheric pressure plasma,
A twelfth invention is
In the method for producing printed matter according to any one of the seventh to ninth inventions,
The antibacterial and antiviral metal oxide particles used in the printing process are characterized by being composed of cuprous oxide particles,
A thirteenth invention is
In the method for producing printed matter according to any one of the seventh to twelfth inventions,
The substrate is made of paper, wood bark, cloth, plastic plate, metal plate, ceramic plate, or glass plate,
Moreover, the fourteenth invention is
A printed film formed using a printing ink containing antibacterial and antiviral cuprous oxide particles and a binder resin, wherein the surface of a part of the cuprous oxide particles is exposed from the printed film surface In the processing method of
The surface of the cuprous oxide particles exposed from the printed film surface is irradiated with atmospheric pressure plasma to reduce some of the oxidized cuprous oxide to cuprous oxide, and the antibacterial and antiviral properties of the cuprous oxide particles are activated. It is characterized by

According to the printed film according to the present invention, which is formed using a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin,
On or near the surface of the printed film, since part of the surface of the metal particles or metal oxide particles contained in the printed film is exposed, the metal particles and metal oxide particles are antibacterial and antiviral. It is possible to make full use of the effect.

Further, according to the method for producing a printed matter according to the present invention, in which a printed film is formed on the surface of a base material,
In the atmospheric pressure plasma treatment step, the surface of the printed cured film is irradiated with atmospheric pressure plasma to remove the binder resin covering the surface of the metal particles or metal oxide particles present on or near the surface of the printed cured film, thereby removing the metal particles. Alternatively, since part of the surface of the metal oxide particles is exposed, it is possible to produce a printed material in which the antibacterial and antiviral effects of the metal particles and metal oxide particles are sufficiently exhibited.

Furthermore, according to the method for treating a printed film according to the present invention, in which the metal oxide particles are composed of cuprous oxide particles, and the surfaces of some of the cuprous oxide particles are exposed from the surface of the printed film,
The surface of the cuprous oxide particles exposed from the surface of the printed film is irradiated with atmospheric pressure plasma to reduce part of the oxidized cuprous oxide to cuprous oxide, so the antibacterial and antiviral properties of the cuprous oxide particles are activated. It is possible to convert

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory diagram of an apparatus according to a first embodiment used in a printed matter manufacturing method according to the present invention; FIG. 4 is an explanatory diagram of an apparatus according to a second embodiment used in the printed matter manufacturing method according to the present invention; 3(A) is a cross-sectional explanatory view of the coating immediately after printing the printing ink according to the present invention on the surface of the substrate, and FIG. 3(B) is the coating after drying. is a cross-sectional explanatory view of the printed cured film formed by curing, and FIG. FIG. 4 is a cross-sectional explanatory view showing a state in which the surfaces of metal oxide particles are exposed.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[Print film]
(1) Printed film The printed film according to the present invention, which is formed using a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin,
A part of the surface of the metal particles or metal oxide particles contained in the printed film is exposed on or near the surface of the printed film.

As mentioned above, the antibacterial and antiviral effects of metal particles and metal oxide particles are due to the active oxygen generated by the reaction between the metal and the surrounding moisture, or the trace amount of metal ions dissolved in the moisture. This is thought to be due to the suppression of viral infections and the inactivation of viruses, or due to contact with solid metal surfaces.

However, in a printed film (printed cured film) formed using a printing ink containing metal particles or metal oxide particles and a binder resin, the printed film (printed cured film) contains metal particles or metal oxide particles. If the surface of these particles is covered with the binder resin, metal ions are less likely to be eluted from the metal particles and the antibacterial and antiviral effects are less likely to be exhibited.

Therefore, in the present invention, the surface of the printed cured film is irradiated with atmospheric pressure plasma to remove the binder resin covering the surface of the metal particles or metal oxide particles present on or near the surface of the printed cured film, and the metal particles It is characterized in that the antibacterial and antiviral effects of the metal oxide particles are sufficiently exhibited.

That is, metal particles and metal oxide particles whose surfaces are partly exposed to the atmosphere generate a small amount of metal ions, and can sufficiently exhibit antibacterial and antiviral effects.

In any mechanism related to the antibacterial/antiviral action described above, it is clearly desirable that the metal surface be exposed to the atmosphere in order to effectively exhibit the antibacterial/antiviral effect.

(2) Metal particles, metal oxide particles, and film thickness of printed film (2-1) Metal particles to be applied may be composed of copper particles, silver particles, nickel particles, or zinc particles. preferable. These metal particles have antibacterial and antiviral effects and are available at low cost. These metal foils, plates, and plating films have antibacterial and antiviral effects. Moreover, it is desirable that the metal oxide particles to be applied are composed of cuprous oxide particles.

For example, when copper particles are used as the metal particles, the copper turns into copper ions, suppressing the growth of bacteria and inactivating viruses. In addition, when cuprous oxide particles are applied as metal oxide particles, the disproportionation reaction between cuprous oxide (Cu ₂ O) and cupric oxide (CuO) suppresses the growth of bacteria and kills viruses. inactivate.

(2-2) The film thickness of the printed film is preferably 0.5 μm to 100 μm, more preferably 1 μm to 50 μm. If the film thickness exceeds 100 μm, a large amount of printing ink containing metal particles or metal oxide particles and a binder resin is used, which is not economical. Further, when the film thickness is less than 0.5 μm, adhesion of metal particles and metal oxide particles in the printed film may be insufficient.

(2-3) On the other hand, the median value of the particle size distribution of the metal particles and metal oxide particles is preferably 1/3 or less of the film thickness of the printed film, more preferably 1/3 of the film thickness. 3 or less and 0.05 μm or more and 10 μm or less. When metal particles or metal oxide particles with a median value of the particle size distribution exceeding 1/3 or 10 μm of the film thickness are applied, the smoothness of the printed film may be impaired. Further, if the median value of the particle size distribution is less than 0.05 μm, it may be difficult to disperse the metal particles or metal oxide particles when preparing the printing ink. The particle size distribution of the metal particles and metal oxide particles can be measured with a particle size distribution meter using laser diffraction.

[Print]
The printed matter according to the present invention is obtained by forming the above printed film on the surface of a base material. Paper, wood board, cloth, plastic plate, metal plate, ceramic plate, glass plate, and the like can be used as the base material. It may be a formula and is optional. Moreover, the thickness and size of the substrate are appropriately selected according to the intended use of the printed matter.

Applications of printed materials include a wide range of printed products such as banknotes, publications, packaging materials such as wrapping paper and bags, building materials such as decorative boards and decorative paper, electrical equipment, and sanitary ware.

In addition, when the surface of the metal particles or metal oxide particles exposed from the surface of the printed film is contaminated and the antibacterial and antiviral properties are lowered, the surface of the printed film is treated again with atmospheric pressure plasma. By doing so, it is also possible to revive the above antibacterial and antiviral properties.

[Manufacturing method of printed matter]
(1) Method for producing printed matter The method for producing printed matter according to the present invention comprises:
a printing step of printing a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin on the surface of a substrate to form a coating of the printing ink;
A curing step of applying an active energy ray to the coating to cure it to form a printed cured film;
The surface of the printed cured film is irradiated with atmospheric pressure plasma to remove the binder resin covering the surface of the metal particles or metal oxide particles present on or near the surface of the printed cured film, thereby removing the metal particles or metal oxides. an atmospheric pressure plasma treatment step that exposes a portion of the particle surface;
characterized by having

(2) Printing process (2-1) Configuration of printing ink The printing ink used in the printing process of the present invention contains antibacterial/antiviral metal particles or metal oxide particles and a binder resin as essential components, and is colored ink and In that case, inorganic pigments or organic pigments (dyes) are included as colorants. A printing ink that does not contain a colorant is sometimes called an OP varnish (overprint varnish).

Cellulose-based resins, rosin-modified resins, polyamide-based resins, urethane-based resins, vinyl-based resins, polyester-based resins, acrylic-based resins, alkyd-based resins, epoxy-based resins, ultraviolet-curable resins, and the like can be used as the binder resin. . Rosin-modified resins include rosin-modified phenolic resins, rosin esters such as rosin-modified pentaerythritol esters, and rosin-modified maleic acid resins. The ultraviolet curable resin includes an acrylic ultraviolet curable resin and a rosin-modified epoxy acrylate, and is used in combination with a photopolymerization initiator. Moreover, the said epoxy-type resin is used together with a polymerization initiator. These binder resins are appropriately selected in consideration of adhesion to the substrate.

In addition, the printing ink must have fluidity for printing, and may contain a solvent such as water or an organic solvent that imparts fluidity. As organic solvents, alcohol-based, ketone-based, hydrocarbon-based, glycol-based, ether-based, ester-based solvents, oils and fats, hydrocarbons, and the like can be used. When the epoxy resin is used, a reactive diluent that reacts with the epoxy resin to cure the resin may be used as a solvent. When an ultraviolet curable resin is used, a reactive diluent that reacts with the ultraviolet curable resin to harden the resin may be used as the solvent. In addition, it is necessary to select a solvent that does not corrode the substrate in the printing process.

Moreover, in order to uniformly disperse the antibacterial/antiviral metal particles or metal oxide particles in the printed film, it is necessary to uniformly disperse these particles in the printing ink. Therefore, a dispersant that has an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group and improves the dispersion stability of the metal particles or metal oxide particles may be used in combination.

Preferred specific examples of commercially available dispersants include:
日本ルーブリゾール（株）製 ＳＯＬＳＰＥＲＳＥ３０００、ＳＯＬＳＰＥＲＳＥ９０００、ＳＯＬＳＰＥＲＳＥ１１２００、ＳＯＬＳＰＥＲＳＥ１３０００、ＳＯＬＳＰＥＲＳＥ１３２４０、ＳＯＬＳＰＥＲＳＥ１３６５０、ＳＯＬＳＰＥＲＳＥ１３９４０、ＳＯＬＳＰＥＲＳＥ１６０００、ＳＯＬＳＰＥＲＳＥ１７０００、ＳＯＬＳＰＥＲＳＥ１８０００、ＳＯＬＳＰＥＲＳＥ２００００、ＳＯＬＳＰＥＲＳＥ２１０００、ＳＯＬＳＰＥＲＳＥ２４０００ＳＣ、ＳＯＬＳＰＥＲＳＥ２４０００ＧＲ、ＳＯＬＳＰＥＲＳＥ２６０００、ＳＯＬＳＰＥＲＳＥ２７０００、ＳＯＬＳＰＥＲＳＥ２８０００、ＳＯＬＳＰＥＲＳＥ３１８４５、ＳＯＬＳＰＥＲＳＥ３２０００、ＳＯＬＳＰＥＲＳＥ３２５００、ＳＯＬＳＰＥＲＳＥ３２５５０、ＳＯＬＳＰＥＲＳＥ３２６００ 、ＳＯＬＳＰＥＲＳＥ３３０００、ＳＯＬＳＰＥＲＳＥ３３５００、ＳＯＬＳＰＥＲＳＥ３４７５０、ＳＯＬＳＰＥＲＳＥ３５１００、ＳＯＬＳＰＥＲＳＥ３５２００、ＳＯＬＳＰＥＲＳＥ３６６００、ＳＯＬＳＰＥＲＳＥ３７５００、ＳＯＬＳＰＥＲＳＥ３８５００、ＳＯＬＳＰＥＲＳＥ３９０００、ＳＯＬＳＰＥＲＳＥ４１０００、ＳＯＬＳＰＥＲＳＥ４１０９０、ＳＯＬＳＰＥＲＳＥ５３０９５、ＳＯＬＳＰＥＲＳＥ５５０００、ＳＯＬＳＰＥＲＳＥ５６０００、ＳＯＬＳＰＥＲＳＥ７６５００等；
BYK-Chemie Japan Co., Ltd. Disperbyk-101, Disperbyk-103, Disperbyk-107, Disperbyk-108, Disperbyk-109, Disperbyk-110, Disperbyk-111, Disperbyk-112, Disperbyk-116, Disperbyk-130-140-perbyk 、Ｄｉｓｐｅｒｂｙｋ－１４２、Ｄｉｓｐｅｒｂｙｋ－１４５、Ｄｉｓｐｅｒｂｙｋ－１５４、Ｄｉｓｐｅｒｂｙｋ－１６１、Ｄｉｓｐｅｒｂｙｋ－１６２、Ｄｉｓｐｅｒｂｙｋ－１６３、Ｄｉｓｐｅｒｂｙｋ－１６４、Ｄｉｓｐｅｒｂｙｋ－１６５、Ｄｉｓｐｅｒｂｙｋ－１６６、Ｄｉｓｐｅｒｂｙｋ－１６７、Ｄｉｓｐｅｒｂｙｋ－１６８、Ｄｉｓｐｅｒｂｙｋ－１７０、Ｄｉｓｐｅｒｂｙｋ －１７１、Ｄｉｓｐｅｒｂｙｋ－１７４、Ｄｉｓｐｅｒｂｙｋ－１８０、Ｄｉｓｐｅｒｂｙｋ－１８１、Ｄｉｓｐｅｒｂｙｋ－１８２、Ｄｉｓｐｅｒｂｙｋ－１８３、Ｄｉｓｐｅｒｂｙｋ－１８４、Ｄｉｓｐｅｒｂｙｋ－１８５、Ｄｉｓｐｅｒｂｙｋ－１９０、Ｄｉｓｐｅｒｂｙｋ－２０００、Ｄｉｓｐｅｒｂｙｋ－２００１、Ｄｉｓｐｅｒｂｙｋ－２０２０、Ｄｉｓｐｅｒｂｙｋ－２０２５ , Disperbyk-2050, Disperbyk-2070, Disperbyk-2095, Disperbyk-2150, Disperbyk-2155, Anti-Terra-U, Anti-Terra-203, Anti-Terra-204, BYK-P104, BYK-P104S, BYK-220SYK , BYK-6919, etc.;
ＢＡＳＦジャパン（株）社製 ＥＦＫＡ４００８、ＥＦＫＡ４０４６、ＥＦＫＡ４０４７、ＥＦＫＡ４０１５、ＥＦＫＡ４０２０、ＥＦＫＡ４０５０、ＥＦＫＡ４０５５、ＥＦＫＡ４０６０、ＥＦＫＡ４０８０、ＥＦＫＡ４３００、ＥＦＫＡ４３３０、ＥＦＫＡ４４００、ＥＦＫＡ４４０１、ＥＦＫＡ４４０２、ＥＦＫＡ４４０３、ＥＦＫＡ４５００、ＥＦＫＡ４５１０、ＥＦＫＡ４５３０、ＥＦＫＡ４５５０、ＥＦＫＡ４５６０、ＥＦＫＡ４５８５、ＥＦＫＡ４８００ , EFKA5220, EFKA6230, JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL690, JONCRYL819, JONCRYL-JDX5050, etc.;
Ajinomoto Fine-Techno Co., Inc. Ajisper PB-711, Ajisper PB-821, Ajisper PB-822 and the like.

Furthermore, a known plasticizer may be added to the printing ink in order to impart flexibility to the printing film.

(2-2) Method for producing printing ink The printing ink according to the present invention containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin can be produced using a known dispersing method.

As a known dispersing method, a vehicle (also called varnish) composed of a resin and a solvent and a solvent are kneaded in a 3-roll mill to prepare a mill base, and an additional vehicle or solvent and the above metal particles or metal Add the oxide particles to the mill base and let down and disperse, or use medium media such as beads, balls, and Ottawa sand, and use a medium stirring mill such as a bead mill, ball mill, sand mill, and paint shaker to remove metal particles or metals. Examples include a method of pulverizing oxide particles and dispersing them in a solvent to prepare a dispersion, and adding a vehicle to the dispersion. Moreover, when dispersing the metal particles or the metal oxide particles, the above-described dispersant may be added as appropriate. Furthermore, the viscosity of the printing ink is appropriately adjusted in order to achieve printing suitability.

In addition, the content of the metal particles or metal oxide particles in the printing ink is preferably 0.1% by mass to 20% by mass with respect to the total of the binder resin and the metal particles or metal oxide particles. 0.1% to 15% by mass is more desirable, and 0.1% to 10% by mass is even more desirable. If the content is less than 0.1% by mass, the antibacterial and antiviral effects of the metal particles and metal oxide particles may be difficult to develop. Coloring of the same particles may occur, impairing the degree of freedom of coloring of the printed film. Moreover, when the content of these particles exceeds 20% by mass, the amount of the binder resin in the printed film decreases, and some of the metal particles and metal oxide particles may peel off from the printed film. In consideration of these factors, the content is appropriately set within the range of 0.1% by mass to 20% by mass based on the total amount of the binder resin and metal particles or metal oxide particles, taking into account the color of the printed film.

(2-3) Printing method As for the method of printing the printing ink containing antibacterial/antiviral metal particles or metal oxide particles and binder resin on the surface of the base material, known letterpress printing, intaglio printing, stencil printing A printing method, an inkjet method, or the like can be used. Further, the printing apparatus may be a sheet-fed printing press, or a continuous printing press such as a rotary press or a rotary screen.

(3) Curing process As the active energy ray for curing the printed printing ink film to form a printed cured film, electron beam (electron beam curing resin), ultraviolet ( For example, acrylic UV curable resin), infrared rays (eg, epoxy thermosetting resin), X-rays, α rays, β rays, γ rays, and the like are exemplified.

(4) Atmospheric pressure plasma treatment step (4-1) Atmospheric pressure plasma apparatus The surface of the printed cured film is irradiated with atmospheric pressure plasma, and the surface of the metal particles or metal oxide particles existing on the surface or near the printed cured film is treated. The "atmospheric pressure plasma device" used in the atmospheric pressure plasma treatment process, which removes the binder resin covering the metal particles or metal oxide particles and exposes part of the surface of the metal particles or metal oxide particles, can irradiate plasma without the need for vacuum equipment. It is a device that is widely used for the purposes of surface modification, removal of surface contaminants, and surface roughening. As with the vacuum plasma apparatus, there are medium-frequency (MHz), high-frequency (MHz), and microwave (GHz) power sources, and the higher the frequency, the less surface roughness and uniform effect can be expected. Nitrogen, argon, helium, or the like is used as the main component (process gas) of the plasma gas, and a trace amount of additive gas (active species) is mixed depending on the purpose. In most cases, the process gas is determined in consideration of the gas cost depending on the size of the facility.

Further, since the effect of decomposing and removing organic substances differs depending on the additive gas (active species), it is preferable to add one or more species selected from oxygen, nitrogen, hydrogen, water, and ammonia as the active species to the process gas. When hydrogen is added as an active species, a reduction effect on the surface of metal oxide particles is expected. That is, when copper oxide (CuO) particles and cuprous oxide (Cu ₂ O) particles are compared as metal oxide particles, monovalent cuprous oxide (Cu ₂ O) is preferred to divalent copper oxide (CuO). is known to have superior antibacterial and antiviral effects. For this reason, atmospheric pressure plasma treatment in which hydrogen is added as an active species is performed on metal oxide particles that have been left in the atmosphere for a long time and oxidized from cuprous oxide (Cu ₂ O) to copper oxide (CuO). This makes it possible to return part of the particles to cuprous oxide (Cu ₂ O) and activate its antibacterial and antiviral properties.

Atmospheric pressure plasma apparatuses are roughly divided into "direct type" and "remote type". In the "direct type", the object to be irradiated with atmospheric pressure plasma is grounded, while in the "remote type", the atmospheric pressure plasma device has a ground inside, and only the plasma is irradiated to the object. If the surface of the object to be irradiated with atmospheric pressure plasma is not a uniform conductor or insulator, but a mixture of conductors and insulators, the plasma becomes unstable and a lightning-like arc is generated toward the object. In particular, since the arc is generated toward the conductor, it may damage the object. The above-mentioned "remote type" having a ground inside the atmospheric pressure plasma apparatus is extremely preferable because arcing is less likely to occur.

(4-2) Effect of Atmospheric Pressure Plasma Treatment Process FIG. 3 is a process explanatory drawing related to the above-described method for producing a printed matter, and FIG. FIG. 3(B) is a cross-sectional explanatory view of the printed cured film formed by curing the above-mentioned coated film after drying, FIG. 3(C) is a metal present on the surface of the printed cured film FIG. 3 is a cross-sectional explanatory view showing a state in which the surfaces of the metal particles or metal oxide particles are exposed by removing the binder resin covering the surfaces of the particles or metal oxide particles.

As can be seen from FIG. 3A, which shows the cross section of the coating immediately after the printing process, in the coating 302 of the printing ink before drying, the metal particles or metal oxide particles 301 are partially formed by the uncured binder resin, solvent, or the like. The part exists in a state of being separated from the base material 300 and floating.

In the printed cured film 303 after the curing step, the solvent is removed as shown in FIG. Alternatively, since the surface of the metal oxide particles 301 is covered with the hardened binder resin 301a, it is difficult for the metal particles or the metal oxide particles 301 to dissolve antibacterial and antiviral metal ions.

However, since the binder resin 301a is removed and the surfaces of the metal particles or metal oxide particles 301 after the atmospheric pressure plasma treatment are exposed as shown in FIG. It is possible to produce a printed matter in which the antibacterial and antiviral effects of the particles 301 are fully exhibited.

By the way, when the surface of metal particles or metal oxide particles is treated by irradiating atmospheric pressure plasma, the surface of the particles is modified by the gas of the active species contained in the process gas, resulting in the formation of metal particles or metal oxide particles. Activity may be improved. For example, when copper particles are applied as the metal particles, copper is oxidized to copper oxide (CuO) when left in the atmosphere, but as described above, monovalent cuprous oxide is used rather than divalent copper oxide (CuO). (Cu ₂ O) is superior in antibacterial and antiviral effects. Therefore, by irradiating the process gas with atmospheric pressure plasma containing active species, divalent copper oxide (CuO) is converted to monovalent cuprous oxide (Cu ₂ O), which has excellent antibacterial and antiviral effects. can be questioned.

[Apparatus used for manufacturing method of printed matter]
(1) Apparatus According to First Embodiment A apparatus according to the first embodiment relates to a gravure printing apparatus to which a long base material is applied.

That is, as shown in FIG. 1, this apparatus includes an unwinding core 101 for unwinding a long base material 100 such as paper or cloth, and a surface of the long base material 100 unwound from the unwinding core 101. A gravure roll 108 that prints a printing ink 111 containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin, and a film of the printed printing ink (see the film indicated by reference numeral 302 in FIG. 3A). A drying box 114 that dries and cures to form a printed cured film (see the printed cured film indicated by reference numeral 303 in FIG. 3B), and the printed cured film formed on the long substrate 100 carried out from the drying box 114. The atmospheric pressure plasma head 126 irradiates the surface with atmospheric pressure plasma, and the binder resin covering the surface of the metal particles or metal oxide particles is removed by the irradiated atmospheric pressure plasma, and the surface of the metal particles or metal oxide particles is removed. The main part is constituted by a winding core 127 for winding the long base material 100 with the exposed portion.

Hereinafter, a method for producing printed matter according to the present invention using the apparatus according to the first embodiment will be described. As shown in FIG. 102, a tension sensor roll 103, a guide roll 104, a drive roll 105, and a tension sensor roll 106 are carried into a compression roll 107, and a tension sensor roll 112 and a drive roll 113 are carried out toward a drying box 114. be. The unwinding tension of the long substrate 100 unwound from the unwinding core 101 is feedback-controlled from the tension sensor roll 103 to the unwinding core 101, and the drag applied to the pressure roll 107 of the long substrate 100 is is feedback controlled from tension sensor roll 106 to drive roll 105 and from tension sensor roll 112 to drive roll 113 .

In addition, printing ink 111 containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin is printed on the surface of the long base material 100 conveyed on the pressure roll 107 by the gravure roll 108 . . The printing ink 111 is stored in the ink vat 110, adheres to the surface of the gravure roll 108 as shown in FIG.

Next, the long base material 100 with the coating of the printing ink 111 formed on the surface is carried into a drying box 114 in which drying heaters 120, 121, 122 are arranged, and guide rolls 115, 116 and a tension sensor roll 117 are carried in. , guide rolls 118 and drive rolls 119 , the elongated base material 100 having the printed and cured film on the surface thereof is carried out from the drying box 114 . Also, the tension during drying is feedback-controlled from the tension sensor roll 117 to the driving roll 119 .

In the first embodiment, since the printing ink that is cured by drying or heating is used, the drying heaters 120, 121, and 122 are arranged in the drying box 114. When printing ink that is cured by applying energy rays is used, it is possible to arrange an active energy ray irradiation device between the drying box 114 and the atmospheric pressure plasma head 126 to correspond.

The long base material 100 having the printed cured film formed on its surface is wound around the winding core 127 via the guide roll 123, the tension sensor roll 124, and the guide roll 125. The guide roll 123 and the tension Atmospheric pressure plasma is irradiated from the atmospheric pressure plasma head 126 incorporated between the sensor rolls 124 toward the print cured film surface of the long substrate 100 to remove the binder resin covering the metal particle or metal oxide particle surface. be done.

In addition, the distance between the atmospheric pressure plasma head 126 and the printed cured film on the long substrate 100 is set as narrow as about 1 to 5 mm in order to avoid disturbance, and the winding tension wound on the winding core 127 is Feedback control is performed from the sensor roll 124 to the winding core 127 .

In FIG. 1, a roll driven by a motor is denoted by M (motor), a tension sensor roll is denoted by TP (tension pickup), and a free roll is denoted by F (free).

(2) Apparatus According to Second Embodiment The apparatus according to the second embodiment also relates to a gravure printing apparatus to which a long base material is applied.

That is, as shown in FIG. 2, this device has an unwinding core 201 for unwinding a long base material 200, and an antibacterial/antiviral agent on the surface of the long base material 200 unwound from the unwinding core 201. A gravure roll 208 that prints a printing ink 211 containing metal particles or metal oxide particles and a binder resin, and a film of the printed printing ink (see the film indicated by reference numeral 302 in FIG. 3A) are dried and cured for printing. Drying box 214 for forming a cured film (see the printed cured film indicated by reference numeral 303 in FIG. 3B), and printing and curing of the long base material 200 disposed at a position facing the water-cooled driving roll 226 and carried out from the drying box 214. The atmospheric pressure plasma head 226 irradiates the film surface with atmospheric pressure plasma, and the binder resin covering the surface of the metal particles or metal oxide particles is removed by the applied atmospheric pressure plasma to form the metal particles or metal oxide particles. The main part is constituted by a winding core 227 for winding the long base material 200 whose surface is exposed.

Hereinafter, a method for manufacturing printed matter according to the present invention using the apparatus according to the second embodiment will be described. As shown in FIG. 202, a tension sensor roll 203, a guide roll 204, a drive roll 205, and a tension sensor roll 206 are carried into the compression roll 207, and the tension sensor roll 212 and the drive roll 213 are carried out toward the drying box 214. be. The unwinding tension of the long substrate 200 unwound from the unwinding core 201 is feedback-controlled from the tension sensor roll 203 to the unwinding core 201, and the drag applied to the pressure roll 207 of the long substrate 200 is is feedback controlled from tension sensor roll 206 to drive roll 205 and from tension sensor roll 212 to drive roll 213 .

In addition, printing ink 211 containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin is printed on the surface of the long base material 200 conveyed on the impression roll 207 by the gravure roll 208 . . The printing ink 211 is stored in the ink vat 210, adheres to the surface of the gravure roll 208 as shown in FIG.

Next, the long base material 200 with the coating of the printing ink 211 formed on the surface is carried into a drying box 214 in which drying heaters 220, 221 and 222 are arranged, and guide rolls 215 and 216 and a tension sensor roll 217 are carried in. , a guide roll 218 and a driving roll 219 , the long base material 200 having the printed cured film on the surface thereof, which is obtained by drying and curing the coating, is carried out from the drying box 114 . Also, the tension during drying is feedback-controlled from the tension sensor roll 217 to the drive roll 219 .

Also in the second embodiment, since printing ink that is cured by drying or heating is used, the drying heaters 220, 221, and 222 are arranged in the drying box 214. When a printing ink that cures by applying rays is used, it is possible to correspond by placing an active energy ray irradiation device between the drying box 214 and the atmospheric pressure plasma head 226 .

Then, the long base material 200 with the printed cured film formed on the surface passes through the tension sensor roll 228, the water-cooled driving roll 229, the guide roll 223, the tension sensor roll 224, and the guide roll 225, and the winding core 227. Atmospheric pressure plasma is applied from the atmospheric pressure plasma head 226 arranged at a position facing the water-cooled drive roll 229 to the printed cured film surface of the long substrate 200 to oxidize the metal particles or metal. The binder resin covering the particle surface is removed.

In addition, the distance between the atmospheric pressure plasma head 226 and the printed cured film on the long substrate 200 conveyed on the water-cooled drive roll 229 is set as narrow as about 1 to 5 mm to avoid disturbance. The winding tension to be wound is feedback-controlled from the tension sensor roll 224 to the winding core 227 .

In the apparatus according to the second embodiment, as described above, the long substrate 200 conveyed on the water-cooled driving roll 229 is irradiated with atmospheric pressure plasma, so that the floating state (in the air) shown in FIG. Compared with the apparatus according to the first embodiment, which irradiates the long substrate 100 with atmospheric pressure plasma, the cooling effect is higher, and the long substrate on which the printed cured film is formed is less likely to be damaged.

In FIG. 2, a roll driven by a motor is denoted by M (motor), a tension sensor roll is denoted by TP (tension pickup), and a free roll is denoted by F (free).

Examples of the present invention will be specifically described below.

[Manufacturing antibacterial and antiviral printed matter]
In this example, copper powder [UCP-030 manufactured by Sumitomo Metal Mining Co., Ltd.] with a median value in the particle size distribution of 0.5 μm was used as the antibacterial and antiviral metal particles, and rosin-modified phenol with a molecular weight of 100,000 was used as the binder resin. A resin was used, a solvent prepared by blending soybean oil, which is fat, and AF7 solvent (manufactured by ENEOS), which was a hydrocarbon, was used.

(Preparation of printing ink)
A vehicle composed of 50% by mass of rosin-modified phenolic resin and 50% by mass of the solvent was prepared, and the vehicle, copper powder, and solvent were kneaded in a 3-roll mill to prepare a mill base. A vehicle is added to the mill base so that the three compositions [copper particle content of 0% by weight, 10% by weight, and 20% by weight] described in the column "Content (% by weight)" are adjusted. went above At that time, the solvent was added to adjust the viscosity of the printing ink. A printing ink containing 0% by weight of copper particles was prepared by adding the solvent for viscosity adjustment to the vehicle. In addition, the viscosity of each printing ink is adjusted with a solvent so that the film thickness of the printed cured film after printing and drying is 3 μm.

(printing, curing, atmospheric pressure plasma treatment)
Using the prepared printing ink, on the surface of glossy paper, which is a long base material, printed matter is produced by forming a printed cured film with a thickness of 3 μm by the apparatus shown in FIG. 1, and the printed matter is cured under the following conditions. An antibacterial and antiviral printed material was produced by irradiating the membrane surface with atmospheric pressure plasma.

That is, a printed matter with a printed cured film having a copper particle content of 0% by weight, a printed matter with a printed cured film having a copper particle content of 10% by weight, and a printed matter with a copper particle content of 20% by weight. The printed article on which the cured film was formed was subjected to atmospheric pressure plasma treatment using an atmospheric pressure plasma head with a distance of 3 mm from the printed cured film.

In addition, argon is used as the process gas, and the mixed gas described in the "with/without hydrogen addition" column in Table 1 ("with hydrogen addition" is a mixed gas of 10% oxygen and 4% hydrogen, and "without hydrogen addition" is oxygen only) is added to the above process gas, and the high-frequency power supply (13.5 MHz) is added to the atmospheric pressure plasma head (head width is 100 mm) of the remote atmospheric pressure plasma generator. The power (0 W, 50 W, 100 W) described in is applied, and the printed matter is conveyed at the speed (30 m / min, 60 m / min) described in the "conveyance speed (m / min)" column of Table 1 The surface of the cured film was irradiated with atmospheric pressure plasma. In addition, in order to prevent each print from being damaged by the heat load caused by the continuous irradiation of atmospheric pressure plasma, the high frequency power supply is turned off when the printed material is not being transported, and the high frequency power supply is turned on only while the printed material is being transported. ing.

[Evaluation of antibacterial/antiviral printed matter]
(Evaluation sample)
A square of 50 mm square was cut out from each printed material manufactured under the conditions described in Table 1 to obtain evaluation samples with sample numbers 1 to 30.

(evaluation)
Evaluation samples of sample numbers 1 to 30 shown in Table 1 were evaluated for antibacterial and antiviral properties.

(1) Antibacterial evaluation Antibacterial evaluation was performed based on JIS Z 2801,
× when the antibacterial activity value is less than 2.0,
An antibacterial activity value of 2.0 or more was evaluated as ◯.

In addition, the non-processed test piece described in JIS Z 2801 was glossy paper that had not been printed.

(2) Evaluation of antiviral properties Evaluation of antiviral properties is performed based on ISO21702,
× when the antibacterial activity value is less than 2.0,
An antibacterial activity value of 2.0 or more was evaluated as ◯.

In addition, unprocessed test pieces described in ISO21702 were glossy papers that were not printed.

(Evaluation results)
Table 1 shows the evaluation results.

(1) Evaluation ○ Sample No. 11 [plasma power 50 (W), transport speed 30 (m / min), hydrogen addition, copper particle content 10 (% by weight)] and sample No. 12 [plasma power 50 (W ), transport speed 30 (m / min), hydrogen addition, copper particle content 20 (% by weight)] evaluation results,
Evaluation ○ Sample No. 23 [plasma power 100 (W), transport speed 30 (m / min), hydrogen addition, copper particle content 10 (% by weight)] and sample No. 24 [plasma power 100 (W), transport Speed 30 (m / min), hydrogen addition, copper particle content 20 (% by weight)] evaluation results,
Evaluation ○ Sample No. 29 [plasma power 100 (W), transport speed 60 (m / min), hydrogen addition, copper particle content 10 (% by weight)] and sample No. 30 [plasma power 100 (W), transport Speed 60 (m / min), hydrogen addition, copper particle content 20 (% by weight)] from the evaluation results,
Antibacterial and antiviral effects were confirmed under the conditions of plasma power of 50 W to 100 W, transport speed of 30 m/min to 60 (m/min), and hydrogen being added to the plasma gas (with hydrogen addition). .

(2) On the other hand, sample number 8 [plasma power 50 (W), transport speed 30 (m/min), no hydrogen addition, copper Particle content 10 (% by weight)] and Sample No. 9 [plasma power 50 (W), transport speed 30 (m/min), no hydrogen addition, copper particle content 20 (% by weight)] were evaluated as ×. ,
Sample number 20 [Plasma power 100 (W), transport speed 30 (m / min), no hydrogen addition, copper particle content 10 ( % by weight)] and Sample No. 21 [plasma power 100 (W), transport speed 30 (m/min), no hydrogen addition, copper particle content 20 (% by weight)], the evaluation is x,
Sample No. 26 [plasma power 100 (W), transport speed 60 (m / min), no hydrogen addition, copper particle content 10 ( % by weight)] and Sample No. 27 [plasma power 100 (W), transport speed 60 (m / min), no hydrogen addition, copper particle content 20 (% by weight)].
When the plasma power is 50 W to 100 W and the transport speed is 30 m/min to 60 (m/min), the binder resin covering the surface of the copper particles near the surface of the printed cured film is removed, but the oxygen of the additive gas removes the copper. It is presumed that the surface of the particles is oxidized and the antibacterial and antiviral effects cannot be exhibited.

(3) In addition, for the mixed gas of oxygen and hydrogen added to the process gas (argon gas) as active species (“with hydrogen added” in Table 1 is a mixed gas of 10% oxygen and 4% hydrogen), copper particles The type of binder resin covering the surface of the printed matter, the thickness of the coating, and the irradiation conditions of the atmospheric pressure plasma may affect the ratio of oxygen and hydrogen in the mixed gas.・ It is considered that the antiviral effect should be confirmed and set accordingly.

According to the printed matter of the present invention, since a part of the surface of the antibacterial/antiviral metal particles or metal oxide particles contained in the printed film is partially exposed, the antibacterial/antiviral properties of these particles are It is possible to make full use of the effect. Therefore, printed products obtained by processing the printed matter have industrial potential for use in the medical field and the like.

100 long substrate 101 unwinding cores 102, 104, 115, 116, 118, 123, 125 guide rolls 103, 106, 112, 117, 124 tension sensor rolls 105, 113, 119, drive roll 107 pressure roll 108 gravure roll 109 doctor blade 110 ink vat 111 ink 114 drying box 120, 121, 122 drying heater 126 atmospheric pressure plasma head 127 winding core 200 long base material 201 unwinding core 202, 204, 215, 216, 218, 223, 225 guide Rolls 203, 206, 212, 217, 228, 224 Tension sensor rolls 205, 213, 219 Drive roll 229 Water-cooled drive roll 207 Impression roll 208 Gravure roll 209 Doctor blade 210 Ink vat 211 Ink 214 Drying box 220, 221, 222 Drying heater 226 Atmospheric pressure plasma head 227 Winding core 300 Base material 301 Antibacterial/antiviral metal particles or metal oxide particles 302 Print ink coating before drying 303 Printed cured film 301a Metal particles or metal oxide particle surface Binder resin to cover

Claims (14)

A printed film formed using a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin,
A printed film, wherein a part of the surfaces of metal particles or metal oxide particles contained in the printed film is exposed on or near the surface of the printed film. 2. The method according to claim 1, wherein the film thickness of the printed film is 0.5 μm to 100 μm, and the median value of the particle size distribution of the metal particles or metal oxide particles is ⅓ or less of the film thickness. printed film. 3. The printed film according to claim 1, wherein the antibacterial/antiviral metal particles are copper particles, silver particles, nickel particles, or zinc particles. 3. The printed film according to claim 1, wherein the antibacterial/antiviral metal oxide particles are composed of cuprous oxide particles. A printed matter comprising the printed film according to any one of claims 1 to 4 formed on the surface of a substrate. 6. The printed matter according to claim 5, wherein the substrate is any one of paper, wood bark, cloth, plastic plate, metal plate, ceramic plate and glass plate. a printing step of printing a printing ink containing antibacterial/antiviral metal particles or metal oxide particles and a binder resin on the surface of a substrate to form a coating of the printing ink;
A curing step of applying an active energy ray to the coating to cure it to form a printed cured film;
The surface of the printed cured film is irradiated with atmospheric pressure plasma to remove the binder resin covering the surface of the metal particles or metal oxide particles present on or near the surface of the printed cured film, thereby removing the metal particles or metal oxides. an atmospheric pressure plasma treatment step that exposes a portion of the particle surface;
A method for producing a printed matter, comprising: The process gas used in the atmospheric pressure plasma treatment step contains nitrogen, argon gas, or helium as a main component, and one or more species selected from oxygen, nitrogen, hydrogen, water, and ammonia are added as active species to the process gas. 8. The method of manufacturing a printed matter according to claim 7, wherein: 9. The printed material according to claim 7, wherein in the atmospheric pressure plasma treatment step, the surface of the printed cured film is irradiated with activated active species using a remote type atmospheric pressure plasma generator. Production method. The printed matter according to any one of claims 7 to 9, wherein the antibacterial/antiviral metal particles used in the printing step are composed of copper particles, silver particles, nickel particles, or zinc particles. manufacturing method. The binder resin used in the printing step is composed of a rosin-modified phenol resin, the antibacterial and antiviral metal particles are composed of copper particles, and the process gas used in the atmospheric pressure plasma treatment step is argon gas, and A mixed gas of 10% oxygen and 4% hydrogen is added to the above process gas, and a power of 50 W to 100 W is applied from a high frequency power supply to the atmospheric pressure plasma head of the remote atmospheric pressure plasma generator, and the speed is 30 m / min to 60 m. 11. The method for producing a printed matter according to any one of claims 7 to 10, wherein the printed cured film on the substrate conveyed at a speed of 1/min is irradiated with atmospheric pressure plasma. 10. The method for producing a printed matter according to any one of claims 7 to 9, wherein the antibacterial/antiviral metal oxide particles used in the printing step are composed of cuprous oxide particles. 13. The method for producing a printed matter according to any one of claims 7 to 12, wherein the substrate is made of any one of paper, wood bark, cloth, plastic plate, metal plate, ceramic plate, and glass plate. A printed film formed using a printing ink containing antibacterial and antiviral cuprous oxide particles and a binder resin, wherein the surface of some of the cuprous oxide particles is exposed from the surface of the printed film In the processing method of
The surface of the cuprous oxide particles exposed from the printed film surface is irradiated with atmospheric pressure plasma to reduce some of the oxidized cuprous oxide to cuprous oxide, and the antibacterial and antiviral properties of the cuprous oxide particles are activated. A method for treating a printed film, characterized in that

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