JPH0453741A - Sheet for printing and printed matter using same - Google Patents

Abstract

PURPOSE:To obtain a printing sheet imparting printed matter excellent in light fastness by providing a surface layer based on an n-butyl methacrylate to the single surface of a transparent film and providing ultraviolet-absorbing properties to the transparent film and/or the surface layer. CONSTITUTION:A surface layer based on an n-butyl methacrylate resin is provided to the single surface of a transparent film and the transparent film and/or the surface layer is a printing sheet having ultraviolet-absorbing properties. Further, a printing layer 9 to which printing is applied and an ultraviolet protective layer 10 are successively laminated to the surface layer of the printing sheet. Ultraviolet-absorbing properties are imparted to the transparent film and/or the surface layer by one of two methods, that is, a method using the transparent film 1 having ultraviolet-absorbing properties and a method incorporating ultraviolet absorber to the surface layers 3.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention has good printing suitability such as ink adhesion, blocking resistance, and transportability, as well as light resistance that prevents color fading due to ultraviolet rays of the applied printing. The present invention relates to a printing sheet with excellent properties and printed matter using the same.

<Prior art> In recent years, with the diversification of printing, a wide variety of media such as paper, synthetic paper, thermoplastic resin film, metal foil, metal-deposited sheet, etc. , printing sheets) is desired, and printing methods such as offset printing, gravure printing, flexo printing, screen printing, and letterpress printing are employed. Among these printing methods, there has been a strong demand for offset printing on various media because it is easy to make plates, is inexpensive, and has a beautiful finish. Against this background, printing sheets that have been proposed in the past have been produced by printing, for example, modified polyethyleneimine (JP-A-1-14
1736) or n-butyl methacrylate resin (Japanese Unexamined Patent Publication No. 1-163093). It had good printability. And since good prints can be obtained,
Its uses are also expanding, and printed matter is now being displayed and displayed outdoors.
It is often posted.

However, conventional printing sheets only have good printability, but they have the problem that the printed images fade due to ultraviolet rays, that is, the printing ink that forms the printed image fades. Therefore, there is a strong demand for printing sheets with excellent light resistance for printed matter.

<Problems to be Solved by the Invention> In view of the above-mentioned circumstances, the present invention provides a printing sheet that has good printability and excellent light resistance that can prevent the printed color from fading, and the same. This is to provide printed matter using .

Means for Solving the Problems> The present invention provides a printing sheet in which a surface layer mainly composed of n-butyl methacrylate resin is provided on one side of a transparent film, in which the transparent film and/or the surface layer is A printing sheet characterized by having ultraviolet absorbing properties, and further comprising a printed layer and an ultraviolet protection layer sequentially laminated on the surface layer of the printing sheet. It is.

In the present invention, in order to impart ultraviolet absorbency to the transparent film and/or the surface layer, there are two methods: (1) using a transparent film having ultraviolet absorbency as the transparent film, and (1) incorporating an ultraviolet absorber into the surface layer. Either one or both of these can be used in combination.

The above-mentioned transparent films with ultraviolet absorbing properties are: ■ Ultraviolet absorbers are contained in various light-transmitting resin films such as polyester, polyolefin, polyvinyl chloride, acrylic resin, styrene resin, polycarbonate, and triacetate. ■ A resin film in which an ultraviolet absorbing layer containing an ultraviolet absorber is provided on at least one side of the above-mentioned various optically transparent resin films; ■ A transparent resin film made of a resin in which the resin itself has ultraviolet absorbing properties. (1) A resin film in which an ultraviolet absorbing layer made of the resin itself having ultraviolet absorbing properties is laminated on at least one side of the various light-transmitting resin films described in Items 0 and 0 above. Can be mentioned. Note that the above-mentioned items 0 to 0 may be used alone or in an appropriate combination. As the ultraviolet absorber used here, any conventionally commonly used ultraviolet absorber can be mentioned, and specific examples include phenyl salicyle),
Salicylic acid compounds such as p-t-butylphenyl salicylate and p-octylphenyl salicylate, 2,4-
Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4
'-dimethoxybenzophenone, 2-hydroxy-4-
Benzophenone compounds such as methoxy-5-sulfobenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)benzotriazole, 2
(2'-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3't-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2 '-Hydroxy-3',5'-di-t-amylphenyl)benzotriazole, 2-12'-hydroxy-3'(3'',4'',5'',6'-tetrahydrophthalimidomethyl)-5'-methyl Benzotriazole compounds such as phenyl-1benzotriazole, cyanoacrylate compounds such as 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, camphor derivatives, para-aminobenzoic acid derivatives, cinnamic acid derivatives, urocanic acid derivatives, nitrogen-containing heterocyclic compounds, etc.In order to incorporate these ultraviolet absorbers into a light-transmitting resin film, melt extrusion method, In a film manufacturing process using a melt casting method or the like, a resin raw material and an ultraviolet absorber may be blended in a predetermined ratio to form a film.

In addition, in order to provide a UV absorbing layer containing these UV absorbers on a light-transmitting resin film, a suitable polymeric binder with film-forming properties, such as ethyl cellulose,
Cellulose derivatives such as cellulose acetate, hydroxypropylcellulose, and carboxymethylcellulose sodium salt; vinyl polymers such as vinyl chloride and vinyl acetate;
Ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, (meth)acrylic polymer, polyester polymer, polyurethane polymer, alkyd polymer,
Along with polymers such as butyral polymers, epoxy polymers, silicone polymers, fluorine polymers, casein, starch, etc., solvents such as benzene, toluene, xylene, tetrahydrofuran, chloroform, acetone, dimethylformamide, methylene chloride, etc. Then, the ultraviolet absorber may be dissolved or dispersed, applied, and dried. The proportion of the ultraviolet absorber in the resin film or in the ultraviolet absorbing layer is usually 1 to 70% by weight, preferably 20 to 50% by weight.

In addition, examples of the resin film which itself has ultraviolet absorbing properties include polymers and copolymers of the compounds listed as the ultraviolet absorbers, polypyromellitic acid imide,
Polyimide resins such as polybiphenyl imide, polyketone imide, polyamide imide, and polyparabanic acid; polymers such as polyether ether ketone, polyether sulfone, polyether imide, polysulfone, polyphenylene sulfide, polyarylate, and polyethylene naphthalate. Can be mentioned. Films made using these polymers by melt extrusion, melt casting, etc. can be applied to the present invention.

In addition, in the present invention, a coating solution obtained by dissolving or dispersing these polymers in the above-mentioned solvents is applied to the various light-transmitting resin films mentioned above and dried, or a resin having ultraviolet absorbing properties is formed into a film by the above-mentioned method. The film can be bonded to various light-transmitting resin films to form a laminated structure, thereby producing a transparent film having ultraviolet absorbing properties constituting the present invention.

In addition, in the transparent film having ultraviolet absorption as described above, a light stabilizer can be contained in the resin film or the ultraviolet absorption layer in order to keep the ultraviolet absorption property stable for a long period of time. Examples of light stabilizers include nickel bis(octylphenyl) sulfide, (2,2'-thiobis(4-t-octylphenyl)))-n-butylamine nickel, nickel complex-3,5-di-t
-butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyl-dithiocarbamate, benzoate type quenchers, amine light stabilizers, and the like.

In addition, in the transparent film having ultraviolet absorbing properties used in the present invention, pigments, plasticizers, etc. may be added to the transparent film and/or the ultraviolet absorbing layer as necessary, or they may be mixed with the resin having ultraviolet absorbing properties. A blend of various soluble resins can be used. In addition, "transparent" as used in the present invention means having a light transmittance of 50% or more according to JISK-6714. Further, the transparent film having ultraviolet absorbing properties may be colored to the extent that the desired light transmittance is not impaired.

On the other hand, when the surface layer contains an ultraviolet absorber, the above-mentioned ultraviolet absorber is added to the coating liquid used to form the surface layer mainly composed of n-butyl methacrylate resin, which will be described later. Just form it. In this case, the content of the ultraviolet absorber in the surface layer is 5 to 50% by weight, preferably 1
It is 0 to 20% by weight.

The surface layer in the present invention contains n-butyl methacrylate resin as a main component.

Here, the n-butyl methacrylate resin refers to a homopolymer of n-butyl methacrylate, a copolymer of n-butyl methacrylate and at least one other vinyl monomer, and the surface layer It is preferable that such an n-butyl methacrylate resin is contained in an amount of 30% by weight or more. In addition, in the present invention, the surface layer may or may not contain an ultraviolet absorber, but in any case, other resins may be added as necessary, for example, for the purpose of improving conveyance and printing properties. It is possible to blend or use various additives.
As the resin to be blended as necessary, resins having good compatibility with n-butyl methacrylate resins such as other acrylic and methacrylic resins can be used as appropriate. Further, as additives, for example, polyethylene oxide, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, alumina, zinc oxide, lithopone, satin white, etc. can be used. can.

The surface layer can be formed by dissolving or dispersing n-butyl methacrylate resin and optionally added resins or additives in a solvent, applying the resulting paint onto a transparent film, and drying it. .

Alternatively, a mixture of the n-butyl methacrylate resin and optionally added resins or additives may be laminated onto a transparent film by melt extrusion. The thickness of the surface layer is usually 1 to 20 μm, preferably 2 to 10 μm. In addition, the surface layer in the present invention is
It can be applied to various printing methods such as offset printing, gravure printing, flexographic printing, and screen printing.
It is particularly suitable for printing methods using oxidative polymerization type inks.

The printing sheet of the present invention is composed of the above-mentioned layers, and has a layer structure and a combination thereof as shown in FIGS. 1 to 5. In FIG. 1, a surface layer 3 is provided on a resin film 2 containing an ultraviolet absorber. Figure 2 shows a light-transmissive resin film 4.
An ultraviolet absorbing layer M5 containing an ultraviolet absorber is provided on one surface of the substrate, and a surface layer 3 is provided on the other surface.

In FIG. 3, a surface layer 3 is provided on one side of a light-transmitting resin film 6 made of a resin having ultraviolet absorbing properties. In FIG. 4, an ultraviolet absorbing layer 7 made of a resin having ultraviolet absorbing properties and a surface layer 3 are sequentially laminated on one side of a light-transmitting resin film 4. Further, in FIG. 5, a surface layer 8 containing an ultraviolet absorber is provided on one side of a light-transmissive resin film 40. Note that the layer structure 1 shown in various embodiments in FIGS. 1 to 4 corresponds to the transparent film having ultraviolet absorbing properties in the present invention.

The printed material of the present invention is obtained by printing a printing sheet having the above-mentioned structure to form a printing layer, and then providing an ultraviolet protection layer on the printed surface to cover the surface. FIG. 6 shows an example of the printed matter of the present invention, in which a printed layer 9 is printed on the surface layer 3 of the printing sheet shown in FIG.
is formed, and an ultraviolet protection layer 10 containing an ultraviolet absorber is further provided on the printed layer. Note that the printed layer does not necessarily have to be formed on the entire surface layer as shown in FIG. 6, and may be partially printed.

Here, the printing layer is provided by various printing methods such as offset printing, gravure printing, flexo printing, screen printing, letterpress printing, etc., but as mentioned above, it is particularly suitable for printing methods using oxidative polymerization type inks. Further, as the ultraviolet protection layer, an ultraviolet absorption layer containing the above-mentioned ultraviolet NIA absorber or an ultraviolet absorption layer made of a resin having ultraviolet absorbing properties can be used as is.

(Function) In general, printed matter printed on transparent film is examined by observing the printed image through the transparent film from the side opposite to the printed surface, so the fading properties of the printed matter can be determined by observing the printed image through the transparent film from the side opposite to the printed sheet. It is easily affected by light irradiation from the side opposite to the printed surface.

Therefore, in the present invention as well, the printed image printed on the surface layer is observed from the back side through the transparent film, so the back side of the transparent film is inevitably exposed to external light.

However, according to the printing sheet of the present invention, ultraviolet rays irradiated from the side opposite to the printed image through the transparent film,
The ultraviolet absorbency imparted to the transparent film and/or the surface layer absorbs ultraviolet rays before they reach the printed image, thereby preventing the printed image from fading. Furthermore, in the printed matter of the present invention, the printed surface is coated with a UV-absorbing protective layer after printing, so even when displaying or displaying both the front and back sides, it is possible to prevent UV irradiation from both sides. This can prevent printing from fading.

<Example> Next, the present invention will be explained in detail using examples.

Note that all parts indicating the formulations represent parts by weight.

Example 1 As a transparent film having ultraviolet absorbing properties, 40 parts of a hensitriazole-based ultraviolet absorber (TINIIBIN 326, manufactured by Ciba Geigy, Japan) was added to 60 parts of polyethylene terephthalate resin, and after heating and melting and mixing uniformly, A printing sheet of the present invention was prepared by using a resin film formed to a thickness of 100 μm by T-die extrusion, and applying a surface layer coating having the composition shown below on one side and drying it to form a surface layer of 10 μm in thickness. Created.

Example 2 As a transparent film having ultraviolet absorbing properties, a coating for an ultraviolet absorbing layer having the following composition was coated on both sides of polyethylene terephthalate (manufactured by Fuji Photo Film Co., Ltd., Fuji PT Film 100G), dried, and exposed to ultraviolet light to a thickness of 5 μm. A printing sheet of the present invention was prepared by providing a surface layer on one side of the sheet provided with an absorbent layer in the same manner as in Example 1.

Example 3 A polyimide resin film (manufactured by Mitsui Toatsu Co., Ltd., Kapton film, thickness 38 μm) was used as a transparent film having ultraviolet absorbing properties, and a surface layer was provided on one side in the same manner as in Example 1. A printing sheet of the invention was produced.

Example 4 A printing sheet of the present invention was produced in exactly the same manner as in Example 2, except that a paint having the following composition was used as the paint for the ultraviolet absorbing layer.

Example 5 A polyethylene terephthalate film (manufactured by Fuji Photo Film Co., Ltd., Fuji PT Film 100G) was used as a light-transmissive resin film, and a surface layer paint containing an ultraviolet absorber having the following composition was coated on one side and dried. A printing sheet of the present invention was prepared by providing a surface layer with a thickness of 10 μm.

A printing sheet of the present invention was produced in exactly the same manner as in Example 1, except that the following was used.

Example 7 A printing sheet of the present invention was produced in exactly the same manner as in Example 2, except that a paint having the following composition was used as the paint for the ultraviolet absorbing layer.

Example 8 A printing sheet of the present invention was produced in exactly the same manner as in Example 2, except that a paint having the following composition was used as the paint for the ultraviolet absorbing layer.

Example 6 The surface layer paint of Example 5 was used as the surface layer paint. Example 9 The printing material of the present invention was prepared in the same manner as in Example 2, except that a paint with the following composition was used as the ultraviolet absorbing layer paint. A sheet was produced.

Example 11 A printing sheet of the present invention was produced in exactly the same manner as in Example 2, except that a paint having the following composition was used as the paint for the ultraviolet absorbing layer.

Example 10 A printing sheet of the present invention was produced in exactly the same manner as in Example 2, except that a paint having the following composition was used as the paint for the ultraviolet absorbing layer.

Comparative Example Polyethylene terephthalate film with a thickness of 100 μm (manufactured by Fuji Photo Film Co., Ltd., Fuji PT Film 100G)
A comparative printing sheet was prepared by providing a surface layer on one side of the sheet in the same manner as in Example 1.

An offset printing machine (HEIDELBERG MO
) with offset printing ink (manufactured by Toyo Ink Manufacturing Co., Ltd., T
After printing using SP300 yellow), light fastness was evaluated. Light resistance was measured using a fade meter (Suga Test Instruments, PAL-
＾U), apply ultraviolet rays to the surface opposite to the printed surface for 10 minutes.
When evaluated after irradiation for 0 hours, the printed sheets of Examples 1 to 11 showed almost no fading of print and maintained clear printing, but the printed sheets of Comparative Examples clearly showed fading of color. , it was almost colorless.

In addition, off-cent printing was applied to the printing sheets prepared in Examples 1 to 5 in the same manner as above, and further, Example 7
A printed matter of the present invention was prepared by coating and drying the paint for the ultraviolet absorbing layer used in the above to provide an ultraviolet protective layer. The light resistance of these prints was examined using a fade meter by irradiating both sides of the prints with ultraviolet rays for 100 hours.As a result, there was almost no fading in any of the prints, and both sides maintained clear printing. was.

Therefore, it was confirmed that the printing sheet of the present invention and printed matter using the same had excellent light resistance.

<Effects of the Invention> Since the printing sheet of the present invention has the above-described configuration, it has the effect of imparting not only good printability but also excellent light resistance to printed matter. Further, the printed matter of the present invention can prevent fading of the print on both sides even when both sides are displayed or posted, and has excellent light resistance. Therefore, it can be used satisfactorily even under harsh conditions such as exposure to direct sunlight that would normally cause discoloration of prints, and is applicable to a wide range of applications.

[Brief explanation of drawings]

1 to 5 are cross-sectional views showing the layer structure of the printing sheet of the present invention. Moreover, FIG. 6 is a sectional view showing the layer structure of the printed matter of the present invention. ■・・・Resin film with ultraviolet absorber, 2...
Resin film containing ultraviolet absorber, 3... Surface layer, 4... Light-transparent resin film, 5... Ultraviolet absorbing layer containing ultraviolet absorber, 6... Resin having ultraviolet absorbing property. A light-transmitting resin film consisting of 7... an ultraviolet absorbing layer consisting of a resin having ultraviolet absorbing properties, 8...
Surface layer containing ultraviolet absorber, 9...Printing layer, 0.
・UV protection layer.

Claims (1)

[Scope of Claims] 1) A printing sheet in which a surface layer mainly composed of n-butyl methacrylate resin is provided on one side of a transparent film, wherein the transparent film and/or the surface layer has ultraviolet absorbing properties. A printing sheet characterized by: 2) A printed matter, characterized in that a printing layer and an ultraviolet protection layer are sequentially laminated on the surface layer of the printing sheet according to claim 1.