JP2000117187A - Weatherable printed matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the stain of a printed matter which is placed outdoors for a long period to be exposed to wind and rain or displayed for a very long period caused by the adhesion and accumulation of dust in the air on its surface, the discoloration of pigment, and the discoloration of the printed matter associated with it and to obtain a weatherable printed matter having good durability for keeping a beautiful printed matter. SOLUTION: At least a printing layer 6, an activity cut-off layer 31 for cutting off photoactivity which comprises an inorganic substance or a metal oxide vapor deposition layer, and a protective layer 10 composed of a stainproof layer 2 having photoactivity are laminated in turn to make a weatherable printed matter 20. In this way, even when dust and stains by oil components adhere to a printing surface, the oil components can be decomposed, washed out, or wiped off so that the stains of the surface by dust can be prevented. The discoloration or fading of a printed matter by light can be prevented by the synergistic effect of it and an ultraviolet cut-off layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is directed to direct (outside air) sunlight and for a long period of time, as represented by election posters, storefront posters, decorative materials for building materials, art reproductions, and the like. This is a printed matter in which contamination and discoloration of a printed matter of a duplicate image used for the above are prevented.

[0002]

2. Description of the Related Art Conventionally, printed matter posted outdoors or on a show window has stains such as dust on its surface,
Due to the action of sunlight or chemical change, the original state as a printed matter cannot be maintained due to fading (color density is reduced) or discoloration (color hue is changed), and there has been a problem that the posting effect is impaired. Also, color prints composed of a mixture of three primary colors differ in the fastness of the pigment (colorant) used and the resistance to chemical substances.
It is common to see strong hues of good fastness, resulting in significant discoloration. For example, when a human's complexion is formed from a mixture of three primary colors of yellow, red, and indigo and, if necessary, a black color, it becomes a flesh color, and the yellow which is easily discolored disappears, and the flesh color changes to red / black. Next, the discoloration in which the skin color turns blue due to red fading is a phenomenon seen in posters and the like displayed for a long period of time.

[0003] Printed materials have been prepared by replacing easily fading colorants with pigments having better weather resistance. However, the hue of the substituted pigment is inferior to the color mixing of the three primary colors, so that beautiful colors cannot be reproduced. There is a problem that a printed matter having a color tone that can be obtained cannot be obtained. In addition, varnishes containing an ultraviolet inhibitor are also applied to the entire surface of the printed matter, but the degree of fading of the primary colors used varies, and discoloration cannot be avoided. There is a problem that foreign matter such as dust adheres to the surface and contaminates it. Further, an antistatic agent or the like for preventing foreign matter from adhering to a varnish containing an ultraviolet inhibitor has also been added, but not only does not provide a sufficient effect, but also in some cases, impairs the moisture resistance of the printed matter. there were. Further, in order to prevent contamination of printed matter, a surface treatment of providing a protective layer on the surface with a coating material using a photodegradation-active catalyst is also performed. However, the action of the photocatalyst decomposes not only the pigments and binders of the ink of the printed matter but also the print medium, and thus there has been a problem that discoloration occurs in a long-term use or the printed layer falls off.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a printed material requiring weather resistance, which is exposed to the wind and rain, is installed outdoors for a long period of time, or has a surface which is displayed or displayed for a very long time. It is an issue to provide weather-resistant prints with excellent durability that prevent dust from adhering and accumulating dust in the atmosphere, accumulating dust, discoloring and discoloring pigments, and accompanying discoloration of prints, and maintaining beautiful prints. Is what you do.

[0005]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, a weather-resistant printed material according to the present invention can be used in a printed material which is directly exposed to the outside air or displayed for a long period of time. A weather-resistant printed material comprising a layer-sequential laminate of a protective layer composed of an active blocking layer and a photoactive antifouling layer. And the second invention is
In the above-mentioned printed matter, furthermore, an ultraviolet shielding layer comprising an ultraviolet absorber and a resin binder, a layer-sequential lamination of an active shielding layer and an antifouling layer, or a protective layer formed on the printing layer side of the active shielding layer. It is a weather-resistant printed material consisting of a body. According to a third aspect of the present invention, the active barrier layer is a hybrid layer formed by coating using a sol-gel method or a vapor deposited layer of a metal oxide (including a silicon oxide in this specification), or And a weather-resistant printed material comprising two layers: the above-mentioned hybrid layer and a metal oxide deposited layer. According to a fourth aspect of the present invention, there is provided a laminate of a protective film having the above-mentioned protective layer provided on one side of a transparent film and a print layer of a printed material via an adhesive layer provided on the non-protective layer side as necessary. It is a weather-resistant printed material consisting of a body. The binder of the antifouling layer and / or the ultraviolet ray blocking layer is a weather-resistant print which is a blend or a reaction product of a bifunctional silicone-modified polymer and an acrylic resin, an alkyd resin, a polyester resin, or an epoxy resin. The above-mentioned ultraviolet absorber is a weather-resistant printed material comprising ultrafine particles of metal oxide of 0.1 μm or less and / or an organic ultraviolet absorber. One or more of the above-mentioned antifouling layer, active blocking layer and ultraviolet blocking layer are weather-resistant prints comprising a formed product on the primer layer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION A weather-resistant print intended for long-term posting or display or direct exposure to the outside air is:
As shown in FIG. 1, at least the [printing layer 6] provided on the printing medium 5, the [activity blocking layer 31] made of an inorganic substance that blocks photoactivity, and the [photoproof antifouling layer 2] having photoactivity. Is a weather-resistant print 20 comprising a layer-sequential laminate with a protective layer 10 composed of: And the printed matter 15
In addition, although not shown, an [ultraviolet ray blocking layer 1] comprising an ultraviolet ray absorbing agent and a resin binder is further provided between the active shielding layer 31 and the antifouling layer 2 or the active shielding layer 3 as shown in FIG.
This is a weather-resistant printed material 21 composed of a layer-sequential laminate with the protective layer 11 formed on the side of the first print layer 6. In addition, the above-mentioned activity blocking layer is a hybrid layer formed by coating using a sol-gel method or a metal oxide deposited layer, or FIG.
The weather-resistant printed matter 22 is composed of an active barrier layer 31 composed of a hybrid layer and a metal oxide deposited layer 32 shown in FIG.
Then, a protective film 17 provided with a protective layer 13 on one side of a transparent film 50 as shown in FIG. 11 and a printed layer 6 of a printed matter 15 on the other side via an adhesive layer 7 as necessary. The weather-resistant printed matter 27 is a laminate of the above. The binder of the antifouling layer and / or the ultraviolet blocking layer is a weather-resistant printed material that is a blend or reaction product of a bifunctional silicone-modified polymer and an acrylic resin, an alkyd resin, a polyester resin, or an epoxy resin. is there. Further, the ultraviolet absorber is 0.1% of metal oxide.
It is a weather-resistant printed material comprising ultra-fine particles of not more than μm and / or an organic ultraviolet absorber. Further, one or more of the antifouling layer, the active blocking layer and the ultraviolet blocking layer are weather-resistant printed matter comprising a formed product on the primer layer.

[0007] The photoactive substance forming the antifouling layer of the present invention comprises:
Dust that adheres to the surface of the antifouling layer is decomposed by the action of light to reduce the molecular weight, destroying the adhesiveness, and cleaning (washing out) / removing the surface with wind and rain to keep the surface clean. Substance. For example, TiO ₂ , ZnO, SrT
iO ₃ , CdS, CaP, InP, GaAs, BaTi
O ₃ , K ₂ TiO ₃ , K ₂ NbO ₃ , Fe ₂ O ₃ , Ta
₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , NiO, Cu
₂ O, SiC, SiO ₂ , MoS ₂ , InPb, RuO
₂ , CeO _{2 and the} like, and Pt, Rh, RuO ₂ ,
A composition in which metals such as Nb, Cu, Sn, Ni, and Fe and / or oxides thereof are mixed can be used.

[0008] The higher the content of the photocatalytic powder or the particles contained in the sol contained in the coating liquid for the antifouling layer, the higher the activity as a catalyst. However, not only does the adhesion between the antifouling layer and the ultraviolet blocking layer and the suitability for coating in the coating process (the coating liquid shows dilatancy when the amount of powder is large), but also the antifouling layer becomes brittle. In some cases, the adhesive strength to the active blocking layer or the ultraviolet blocking layer is reduced and the adhesive layer may fall off. Therefore, although it depends on the density and the particle shape of the photocatalyst fine powder, 0.1 to 30% by weight is preferable.

The binder used in the coating solution for the antifouling layer is selected from materials having excellent light resistance, such as acrylic silicone resin and epoxy silicone resin. To form a silicon layer, the general formula _{R 3 S i O (RS i} O) n S
_i O _3, alkylsiloxane compounds polyorganosiloxane represented by like _{(R 2 S i O) n} ,
And arylsiloxanes (R ₁ and R ₃ are the same or different alkyl groups having 1 to 6 carbon atoms). Further, from the structure thereof, they are classified into types such as chain, ring, and net. Preferred polyorganosiloxanes are mixtures of organotrialkoxysilanes such as methyltriethoxysilane, methyltrimethoxysilane, and ethyltriethoxysilane, and fluoroalkylalkoxysilanes, and diorganopolysiloxanes having hydroxyl groups at both terminals of the molecule. is there. The above-mentioned polyalkoxysilane mainly increases the hardness of the cured film and improves the scratch resistance and abrasion resistance.

The application of the antifouling layer varies depending on its viscosity and drying / curing conditions, but can be applied by a usual method depending on the material. For example, it can be appropriately selected from a gravure coat using a gravure plate, a roll coat using a rubber or steel roll, an air knife coat, a spray coat, a spin coat, a dip coat, and the like. The diameter of the catalyst particles in the antifouling layer is 40 nm or less. The total light transmittance of the antifouling layer using a metal oxide and / or hydroxide sol having a specific surface area after curing of 50 m ² / g or more is 70% or more. When a transparent base film having a wavelength of 550 nm and a total light transmittance of 70% or more is used, transmitted visible light can be used as illumination.

When the antifouling layer cannot firmly adhere to the ultraviolet blocking layer or the active blocking layer, it is preferable to provide a primer layer to form the antifouling layer. As the primer layer applied before applying the antifouling layer of the present invention, it is preferable to select an inorganic primer layer which is not decomposed by the photoactivity of the antifouling layer as a constituent material. For example, typical organic titanium compounds include alkyl titanates such as tetraisopropyl titanate, tetrabutyl titanate, and tetrastearyl titanate, and products produced by hydrolysis of titanium chelates. Preferred are tetraisopropyl titanate and tetrabutyl titanate, which have a very high hydrolysis rate and can be decomposed after the solution is applied.

FIGS. 1, 2, 3, 5 and 8 of the present invention.
The active barrier layer 31 made of an inorganic substance shown in FIGS.
A hybrid layer made of an organic and inorganic material formed by a sol-gel method and acting as a primer layer of the antifouling layer 2 is formed by coating. The hybrid layer not only functions as a primer layer for strengthening the adhesion of the antifouling layer, but also has an action of blocking the photoactivity of the antifouling layer.
Organotrialkoxysilanes such as methyltriethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, and fluoroalkylalkoxysilanes formed by coating from sols containing silicon, or diorganopolysiloxanes having hydroxyl groups at both terminals of the molecule An organic-inorganic hybrid layer formed by coating from an alcohol solution such as a mixture of these. In addition, there are hydrolysis products such as inorganic polysilazaran (perhydropolysilazaran).

The ultraviolet absorber of the ultraviolet blocking layer which can be used for the protective layer of the weather-resistant print of the present invention includes an inorganic compound and an organic compound. For example, for inorganic materials, titanium oxide,
There are zinc oxide, iron oxide, cerium oxide and the like. And
The particle size is preferably 0.1 μm or less in order to secure transparency, and in order to facilitate dispersion when preparing a coating solution, a material which has been surface-treated with aluminum oxide or silicon oxide or alcohol. Some are wet with a solvent such as Further, the organic type includes benzophenone type, benzotriazole type, oxalic anilide type, cyanoacrylate type and triazo type. Preferably, it is an inorganic one which is not decomposed by an ultraviolet ray or a photoactive antifouling layer. By using the above-mentioned inorganic ultrafine particles and an organic ultraviolet absorber in combination, the effect of blocking ultraviolet rays can be further exhibited.

The binder for forming the ultraviolet shielding layer can be selected from ordinary weather-resistant binders, those which cure at low temperatures of about 100 ° C. to about 100 ° C., and two-component reaction-type and ionizing radiation-curable resins. . Particularly preferably, it consists of bifunctional and trifunctional, and is composed of Si-OH, SiO
A modified silicone having Me, and a resin that reacts with the modified silicone;
For example, it is a resin varnish obtained by blending or heat-reacting an epoxy ester, a phenol resin, an acrylic resin, a linear polyester, an alkyd, or the like. The ratio of the modified silicone to the resin that is blended or heat-reacted at the solid content is 2%.
-8: 8-2 can be arbitrarily selected, and preferably, the higher the ratio of the modified silicone, the better the weather resistance. The ratio of the ultraviolet absorbent contained in the coating liquid is 5 to 30.
%. If it is 5% or less, the effect as an ultraviolet blocking layer is small, and if it is 30% or more, the binder tends to fall off due to decomposition.

Since the ultraviolet shielding layer of the present invention is provided between the active shielding layer 31 and the printing layer 6 as shown in FIG. 2, it is usually not decomposed by light to reduce its function. Absent. However, when the ultraviolet blocking layer 1 is provided between the printing layer 6, the active blocking layer 31, and the active blocking layer 32 formed by vapor deposition as shown in FIG. The activity of the photocatalyst, which is an antifouling layer, is strongly blocked by the two-layered activity blocking layer, and the binder of the ultraviolet blocking layer 1 is hardly decomposed. In such a case, cellulose acetate, polyvinyl butyral, a copolymer of acrylic acid and / or methacrylate, a vinyl chloride-based copolymer or a plasticized product thereof, a fluorine-based resin, an ionomer, which are ordinary weather-resistant binders, Polyamide, polyimide, polyester, saponified ethylene / vinyl acetate copolymer, etc., and two-part reactive resins such as polyether / isocyanate, epoxy resin / isocyanate, and, if necessary, stable epoxidized oil and phosphorous acid compound A binder made of an agent can also be used.

An SiO _x layer (in the present invention, as described above,
O _x is included in the metal oxide. ), The total thickness of the SiO _x active barrier layer is preferably in the range of 100 to 1500 °. If the thickness of the active barrier layer exceeds 2000 mm, not only transparency is lost but also flexibility is impaired.
However, depending on the type and use of the active barrier layer, the thickness of the active barrier layer is not limited to a maximum of 2000 °, and the effect of the active barrier layer can be increased by increasing the thickness to, for example, about 3000 °. For the purpose of strengthening the adhesion between the SiO _x active barrier layer and the antifouling layer that form the transparent active barrier layer, a corona discharge treatment, a plasma treatment or a primer layer described below may be applied to the surface of the active barrier layer as necessary. It is preferable to perform an easy adhesion treatment such as application.

The _x of SiO _x is preferably from 1.4 to 2.0. x is less than 1.2 or 2.1
Above, the adhesive strength between the activity blocking layer (deposition layer) and other layers such as an antifouling layer decreases. Therefore, _x of SiO _x is
Those having 1.3 to 2.0 can be preferably used. Also, A
As _x of 10 x, those of 1.0 to 1.5 can be preferably used. When x is 0.9 or less or 1.6 or more,
The adhesive strength between the active barrier layer and other layers such as an antifouling layer is reduced.
Therefore, _x of AlO _x is preferably 1.0 to 1.5.

The vapor deposition is performed by a physical vapor deposition method (hereinafter, referred to as PVD) or a chemical vapor deposition method (hereinafter, referred to as a CVD method).
However, the CVD method is preferable as a method that is superior in adhesion to other layers such as an antifouling layer and a base film as compared with the physical vapor deposition method. A mere metal oxide vapor-deposited layer serving as the active barrier layer 32 has excellent activity barrier properties, but often has insufficient adhesion to the surface to be vapor-deposited. Therefore, in such a case, a primer layer 43 used for a later-described vapor deposition layer may be provided on the surface on which the activation blocking layer is to be vapor-deposited.

The active blocking layer formed by the CVD method has transparency, and the constituent elements are carbon, hydrogen, or hydrogen contained in the organosilicon compound or a derivative thereof depending on the selection of the deposition material of the CVD method in addition to SiO _x. Compounds such as oxygen can be included in the active barrier layer.

The organosilicon compound used in the CVD method is
1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethyldisilane, hexamethyldisilane, methyltrimethylsilane, hexamethyldisiloxane, propylsilane, phenylsilane, vinyltrimethoxysilane, tetramethoxysilane, Examples thereof include tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, and octamethylcyclotetrasiloxane. Preferred are 1,1,3,3-tetramethyldisiloxane and hexamethyldisiloxane, which can uniformly form the direction in which the carbon content of the active barrier layer decreases in the depth direction.

When the PVD method is employed, as shown in FIG. 6 and the like, the active blocking layer 32 is formed on the surface on which the primer layer 43 having a primer function for enhancing the adhesion of the active blocking layer is provided on the surface to be deposited. Preferably, metal oxide is deposited. The primer layer 43 for the active blocking layer provided between the active blocking layer 31 and the printing layer 6 as shown in FIGS. 6, 7 and 9 is not necessarily an inorganic substance because it is not affected by photoactivity. No need. Depending on the type of the base film, vinyl chloride / vinyl acetate copolymers, linear polyesters, polyethers and those cured with polyisocyanate, polyurethanes, epoxy resin modified products, especially acids with maleic anhydride A cured product or a cured product of polyisocyanate can be used. Needless to say, even in the case of the CVD method, a certain effect can be expected if the primer layer is provided.

The material which can be used for the printing medium of the present invention is not particularly limited, but is suitable for printing aptitude (ink transferability and adhesion), an active blocking layer deposition step, and an ultraviolet blocking layer coating step. It is fine. For example, if the grammage is 50-5
The paper can be selected from thin paper-based paper such as art paper, cast-coated paper, and machine-coated paper of 00 g / m ² and thick paperboard. In addition to a laminated paper such as a laminated paper of metal foil and paper, an aluminum vapor-deposited paper, and the like, a metal plate such as a steel plate, a tin plate aluminum plate, a colored plastic sheet, a synthetic paper, and the like can be selected according to the application. .

The transparent film 50 used for the protective film 17 of the weather-resistant printed material 27 shown in FIG. 11 is a transparent plastic film and has no problem in printing, vapor deposition and coating processes, and has excellent transparency and durability. Material selected. Cellulose acetate, polyvinyl butyral, acrylic acid and / or methacrylic acid ester copolymer, vinyl chloride copolymer or plasticized product thereof, fluororesin, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer It is a stretched or unstretched film of a thermoplastic resin such as a polymer, an ethylene / acrylate copolymer, an ionomer, a polyamide, a polyimide, a polyester, a saponified ethylene / vinyl acetate copolymer, and polycarbonate. The thickness of the base film depends on the material and the production method, but is 10 to 200 μm, preferably 15 to 50 μm.
μm.

The formation of the printing layer can be performed by a printing method suitable for a printing medium. For example, a plate type such as planographic offset printing, intaglio type gravure printing, letterpress printing, or silk screen printing can be freely selected. The binder of the ink used easily dissolves in the solvent of the coating liquid such as a primer like gravure ink for paper, mainly rosin, when processing the UV blocking layer and the active blocking layer in the subsequent process. Materials or processes that are difficult to repel or adhere to after-treatment coating liquids, such as fully cured linseed oil-based offset inks, should be avoided. UV curable ink mainly composed of acrylic resin, polyether
Binders such as isocyanate type can be preferably used.

The colorant of the colored layer is preferably a pigment having excellent weather resistance and transparency. For example, insoluble azo pigments (disazo yellow, carmine FB), polyazo pigments (chromophthalo yellow, chromophthal red), copper phthalocyanine (phthalocyanine blue) which is a polycyclic pigment, quinacridone (quinacridone red, quinacridone magenta),
Anthraquinone (indasulon blue, pyrimidine yellow), isoindolinone (isoindolinone yellow),
It can be appropriately selected from perylene / perinone (perylene red) and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. In order to evaluate changes in antifouling property and transparency of each sample to be prepared, the thickness 2 used in Example 10 was used.
A protective film having the same protective layer as in each example was prepared on the surface of a biaxially stretched polyester film of 5 μm. (Example 1) Using a synthetic paper (printing material 5) having a base material of 130 μm thick polypropylene as the printing material 5 (printing material 5), a printing layer 6 having a picture layer shown in FIG. Printing was performed to produce a printed matter 15. In addition,
The printing ink is a red (pigment: carmine FB), indigo (pigment: phthalocyanine blue), yellow (pigment: disazo yellow), and a mixed color portion in which three colors are overprinted.
Printed at%, 70%, 50% and 30%. The red printed portions are denoted by A, and regions corresponding to the densities of 100%, 70%, 50%, and 30% are denoted by A-10, A-7, A-5, and A-3. The print area of indigo is B, the print area of yellow is C, and the mixed color area is D. The areas indicating the respective densities are indigo, B-10, B-7, B-5, B-5
-3 and yellow are C-10, C-7, C-5, and C-3, and the mixed color portion is D-10, D-7, D-5, and D-3.
Next, as shown in FIG. 1, an alcohol solution of alkoxysilane was applied at a rate of 1 g / m ² to form an active blocking layer 31 made of an inorganic substance constituting a sol-gel layer by roll coating.
Then, an antifouling layer having the following composition was provided with a gravure coat of 1 g / m ² , and the antifouling layer 2 was formed by coating to prepare a weather resistant print 20 having an antifouling layer 10. (Coating solution for antifouling layer) Anatase type titanium oxide Particle size 30 nm 20 parts by weight Silica sol Specific surface area 180 g / m ² 20 parts by weight Tetraethoxysilane 60 parts by weight Solvent 200 parts by weight

Example 2 2 g of a coating liquid for an ultraviolet shielding layer having the following composition was applied to the printing layer 6 of the printed matter 15 prepared in Example 1.
/ M ² gravure coat to form an ultraviolet blocking layer 1. Further, the same active blocking layer 31 and antifouling layer 2 as in Example 1
Was formed by coating to prepare a weather-resistant print 21 having a protective layer 11 composed of an ultraviolet blocking layer 1, an antifouling layer 2 and an active blocking layer 31 shown in FIG. (Coating liquid for ultraviolet blocking layer) Zinc oxide Particle size 0.01 μm 20 parts by weight Benzophenone type ultraviolet absorber 5 parts by weight Silicone for modification 60 parts by weight Acrylic resin 25 parts by weight Solvent 200 parts by weight

(Embodiment 3) A primer layer 41 made of polyether / isocyanate is provided on the printed layer 6 of the printed matter 15 prepared in Embodiment 1 and then the ultraviolet shielding layer 1 and the active shielding layer 31 are formed in the same manner as in Embodiment 2. The antifouling layer 2 was formed by coating to form a weather-resistant printed matter 21 having a protective layer 11 composed of the ultraviolet blocking layer 1 and the antifouling layer 2 and the active blocking layer 31 shown in FIG.

[0029] consisting of SiO _x by the CVD method on the print layer 6 of the printed matter 15 created in (Example 4) Example 1 Thickness 25
A 0 ° active blocking layer 32 was formed. Then, the same antifouling layer 2 as in Example 1 was provided by coating, and the active blocking layer 3 shown in FIG.
Thus, a weather-resistant printed matter 22 provided with the protective layer 12 composed of the antifouling layer 2 and the antifouling layer 2 was formed. The processing conditions of the active blocking layer are as follows. Reaction mixture gas (unit: slm) Hexamedisiloxane: oxygen gas: helium gas = 1:
10:10 ・ Degree of vacuum in vacuum chamber: 5 × 10 ^-6 mbar ・ Degree of vacuum in evaporation chamber: 6 × 10 ^-2 mbar ・ Power supply to cooling drum: 20 KW

(Embodiment 5) As shown in FIG. 5, a 250 ° -thick active blocking layer 32 made of SiO _x is formed on the printed layer 6 of the printed matter 15 prepared in Embodiment 1 by the CVD method in the same manner as in Embodiment 4. did. Then, an active barrier layer 31 and an antifouling layer 2 made of the same inorganic substance as in Example 1 were provided by coating, and a weatherproof layer provided with the protective layer 12 composed of the active barrier layers 32 and 31 and the protective layer 2 shown in FIG. A printed matter 22 was formed.

Example 6 A primer layer 43 made of polyether / isocyanate was provided by gravure coating on the printed layer 6 of the printed matter 15 prepared in Example 1. Then, as shown in FIG. 6, the active blocking layer 32 and the antifouling layer 2 were formed respectively in the same manner as in Example 4, and the protective layer 12 composed of the active blocking layer 32 and the antifouling layer 2 provided on the primer layer 43 was laminated. A weatherable print 22 was formed.

Example 7 As shown in FIG. 7, a primer layer 43 made of polyether / isocyanate was provided on the print layer 6 of the printed matter 15 prepared in Example 1 by gravure coating. Further, a vapor deposition layer (active blocking layer 32) having a thickness of 200 ° was formed by a PVD method using an electron beam heating method by using aluminum as a vapor deposition source. Further, isopropyl titanate was applied to the above-mentioned activity blocking layer 32, and an inorganic primer layer 42 which was not dried and hydrolyzed under humidification but could not be expected to have the activity blocking property but had a strong adhesion was provided. Further, the antifouling layer 2 was provided on the primer layer 42 by using the antifouling layer coating liquid used in Example 1 in the same manner as in Example 1, and the primer layer 43, the active blocking layer 32, and the primer shown in FIG. Layer 4
2 and a protective layer 12 composed of the antifouling layer 2 were laminated to form a weather-resistant printed matter 22.

(Embodiment 8) As shown in FIG. 8, the printed layer 15 of the printed matter 15 prepared in the embodiment 1 has an active blocking layer 32 as in the embodiment 3 and an ultraviolet blocking layer 1 as in the embodiment 2. , An active blocking layer 31 and an antifouling layer 2 were provided to form a protective layer 13 to form a weather-resistant printed material 23.

Example 9 As shown in FIG. 9, a primer layer 43 similar to that of Example 6 was provided on the print layer 6 of the printed matter 15 prepared in Example 1, and Active blocking layer 32, ultraviolet blocking layer 1, and active blocking layer 3
1 and an antifouling layer 2 were laminated to form a protective layer 13 to prepare a weather-resistant printed material 23.

(Embodiment 10) As shown in FIG. 10, a primer layer 43, an active blocking layer 32, and an active blocking layer 31 similar to those of the ninth embodiment are provided on the printed layer 6 of the printed matter 15 prepared in the first embodiment. Provided, furthermore, an ultraviolet shielding layer 1, an active shielding layer 31
The anti-fouling layer 2 was laminated to form a protective layer 13 to form a weather-resistant print 23.

(Example 11) As shown in FIG. 11, a biaxially stretched polyester film (transparent film 50) having a thickness of 25 μm was coated with the same ultraviolet shielding layer 1 as in Example 2, and the same activity blocking as in Example 4. Protective film 1 in which a protective layer 13 composed of a layer 32, an active blocking layer 31 and an antifouling layer 2 is laminated
7 was created. Then, the printed matter 15 created in the first embodiment
The printed layer 6 and the non-protective layer side of the protective film 17 were laminated via the urethane-based adhesive layer 7 to form a weather-resistant print 27.

(Comparative Example 1) Although not shown, a printed matter of a comparative example in which a protective layer was formed from an acrylic resin on the printed layer 6 of the printed matter prepared in Example 1 by applying 3 g / m ² was formed. .

Table 1 shows the results of evaluation and comparison of the weather-resistant prints of the above Examples and Comparative Examples by the following methods.・ Weather resistance test For the samples of the examples and the comparative examples, JIS B77
Using a sunshine carbon arc lamp-type weathering tester specified in No. 53, the change in color of the printed matter after irradiation for 500 hours was visually evaluated in comparison with that before irradiation.・ Anti-fouling test Methylene blue is adsorbed on the surface of the printed matter, 600nm
Was measured. Next, the sample was exposed to black light of 0.5 m / irradiation, and the degree of reflectivity after 30 minutes was evaluated as an index of resolution (contamination by foreign matter). And each evaluation is described as follows. Good for little change. Those that have changed slightly. Those markedly changed are indicated by x.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

[0044]

[Table 6]

[0045]

[Table 7]

[0046]

[Table 8]

[0047]

[Table 9]

[0048]

[Table 10]

[0049]

[Table 11]

[0050]

[Table 12] (Comparative example)

[0051]

As described above in detail, the weatherable printed material of the present invention comprises a primer layer or a metal oxide vapor-deposited layer in which the printed layer is coated with a sol-gel material having an activity-blocking property composed of an inorganic substance. It is a layered laminate of a protective layer composed of an active blocking layer and a photoactive antifouling layer. Therefore, even if dirt due to dust or oil adheres to the printing surface, the oil can be decomposed and washed off or wiped off, thereby preventing contamination by dust on the surface. And
The synergistic action with the ultraviolet blocking layer has an effect of preventing discoloration and fading of printed matter due to light.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a basic part of a weather-resistant printed material of the present invention.

FIG. 2 is a basic cross-sectional schematic view of a weather-resistant printed material provided with an ultraviolet blocking layer.

FIG. 3 is a schematic cross-sectional view showing another configuration of a weather-resistant printed material provided with an ultraviolet blocking layer.

FIG. 4 is a schematic cross-sectional view showing a configuration of a weather-resistant printed material provided with an active blocking layer.

FIG. 5 is a schematic cross-sectional view showing another configuration of a weather-resistant printed material provided with an active blocking layer.

FIG. 6 is a schematic cross-sectional view showing a configuration provided with an activity blocking layer and a primer layer.

FIG. 7 is a schematic cross-sectional view showing another configuration provided with an activity blocking layer and a primer layer.

FIG. 8 is a schematic cross-sectional view showing the structure of a weather-resistant printed material including an antifouling layer, an ultraviolet blocking layer, and an active blocking layer.

FIG. 9 is a schematic cross-sectional view showing another configuration of a weather-resistant printed material including an antifouling layer, an ultraviolet blocking layer, and an active blocking layer.

FIG. 10 is a schematic cross-sectional view showing another configuration of a weather-resistant printed material including an antifouling layer, an ultraviolet blocking layer, and an active blocking layer.

FIG. 11 is a schematic cross-sectional view showing another configuration of a weather-resistant printed material provided with a protective film.

FIG. 12 is a diagram showing a printing pattern for evaluating weather resistance.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 UV blocking layer 2 Antifouling layer 5 Printed object 6 Printing layer 10, 11, 12, 13 Protective layer 15 Printed matter 17 Protective film 20, 21, 22, 23, 27 Weatherproof printed matter 31, 32 Active cutoff layer 41, 42 , 43 Primer layer 50 Transparent film A Red printing part B Blue printing part C Yellow printing part D Color mixing part

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4D075 AC23 AC25 CA32 CA34 CA50 DA06 DB18 DB36 DB48 DC50 EA07 EA41 EB22 EB38 EB42 EC02 4F006 AA02 AA12 AA13 AA17 AA18 AA19 AA22 AA35 AA36 AA38 AA39 AB03 AB18 AB19 AB AB35 AB36 AB37 AB38 AB39 AB64 AB65 AB67 AB74 AB76 BA03 BA11 CA00 DA00 DA01 DA03 DA04 EA03

Claims (7)

[Claims] 1. A printed material which is directly exposed to the outside air or displayed for a long period of time, and a protective layer comprising at least a printed layer, an active blocking layer made of an inorganic substance that blocks photoactivity, and a photoactive antifouling layer. And a layer-sequential laminate of 2. The printed matter according to claim 1, further comprising an ultraviolet shielding layer comprising an ultraviolet absorbent and a resin binder, between the active shielding layer and the antifouling layer, or on the printing layer side of the active shielding layer. A weather-resistant printed matter, which is a layered laminate with a protective layer formed thereon. 3. The method according to claim 1, wherein the active blocking layer comprises a hybrid layer formed by a sol-gel method or a metal oxide vapor-deposited layer, or the hybrid layer and the metal oxide vapor-deposited layer. The weather-resistant printed matter according to claim 1 or 2, wherein 4. A laminate comprising a protective film having the above-mentioned protective layer provided on one side of a transparent film and a printed layer of a printed matter via an adhesive layer provided on the non-protective layer side as required. A weather-resistant printed matter, characterized in that: 5. The method according to claim 1, wherein the binder of the antifouling layer and / or the ultraviolet blocking layer is a blend or reaction product of a bifunctional silicone-modified polymer and an acrylic resin, an alkyd resin, a polyester resin, or an epoxy resin. The weather-resistant printed matter according to any one of claims 1 to 3, wherein: 6. The method according to claim 1, wherein said ultraviolet absorber is 0.1% of a metal oxide.
The weather-resistant printed matter according to any one of claims 2 to 4, which is an ultrafine particle having a particle size of not more than μm and / or an organic ultraviolet absorber. 7. The weather resistance according to claim 1, wherein one or more of the antifouling layer, the active blocking layer and the ultraviolet blocking layer are formed on a primer layer. Printed matter.