JP2002356073A - Method for making printed matter incombustible and printed matter made incombustible - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printed matter made incombustible without making an operation complicated, while holding down the cost of the printed matter. SOLUTION: The printed matter has a pattern layer 2 provided at least on one side of a base sheet 1. An overcoat layer 4 formed of an ionizing radiation cured type resin composition and having a thickness of 0.5-20 μm is provided on the whole surface of either side of the base sheet 1, and an adhesive layer 5 is provided on the opposite side to the side whereon the overcoat layer 4 is provided. Thereby the printed matter 6 made incombustible is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printed material provided with nonflammability or flame retardancy.

[0002]

2. Description of the Related Art Various printed materials are posted on railway vehicles, and they are required to conform to a material combustion test for railway vehicles generally specified in railway structure regulations.

[0003] This flammability standard is classified into five stages of nonflammability, extremely flame retardancy, flame retardancy, slow burning, and flammability in order from the one that is difficult to burn. In particular, printed matter adhered to a wall surface or a glass portion in a vehicle is required to be nonflammable, which is the highest standard among these five standards.

[0004] A printed material to be attached to a wall surface or a glass portion of an ordinary store or the like has a pattern to be displayed on one surface of a base sheet such as paper or film, and an adhesive layer is provided on the other surface. And adhered through this adhesive layer. However, such printed matter is flammable and almost burns away if left unburned.

[0005] For this reason, it is conceivable to use a non-combustible resin sheet as a base material sheet in order to adapt the printed matter to be adhered to a wall surface inside a railway vehicle or a glass portion inside or outside a railway vehicle. However, a resin sheet generally referred to as non-flammable does not always satisfy the non-flammability performance stipulated in the Railway Construction Regulations, and although it has a degree of flame retardancy, it cannot always be made non-flammable. In addition, since such a resin sheet is expensive, the cost of printed matter is increased.

It is also conceivable to laminate the above-mentioned resin sheet via a pressure-sensitive adhesive on a printed matter on which a pattern is printed. However, in this case as well, the cost of the printed matter increases, and a special laminator is required,
This leads to further cost increases and work complexity,
As described above, although a degree of flame retardancy can be obtained, it is not always possible to make it nonflammable.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present invention provides a method for controlling the cost of printed matter without complicating the operation.
An object of the present invention is to obtain a printed material having noncombustibility.

[0008]

In other words, the method for non-combustible printed matter according to the present invention comprises forming a pattern layer on at least one surface of a base sheet, and forming a pattern layer on a surface of the base sheet to be adhered to an adherend. Is characterized in that an ionizing radiation-curable resin composition is printed on the entire opposite surface and cured by irradiation with ionizing radiation to form an overcoat layer.

Further, the method for non-combustible printed matter of the present invention is characterized in that an adhesive layer is formed on a surface of a substrate sheet to be adhered to an adherend.

[0010] The non-combustible printed material of the present invention is a printed material in which a pattern layer is provided on at least one surface of a base sheet, and is provided on the entire surface of one of the surfaces of the base sheet. An overcoat layer formed of an ionizing radiation-curable resin composition is provided.

Further, the non-combustible printed material of the present invention is characterized in that an adhesive layer is provided on the surface of the base sheet opposite to the surface on which the overcoat layer is provided.

Further, the thickness of the overcoat layer of the printed matter subjected to the non-combustibility treatment is 0.5 μm to 20 μm.

[0013]

Embodiments of the present invention will be described below. First, the method for making the printed matter non-combustible and the printed matter subjected to the non-combustible treatment according to the present invention will be described with reference to FIGS. 1, 2, and 3. FIG.

FIG. 2 is a cross-sectional view of a printed material used in the present invention, in which a pattern layer 2 is provided on one surface of a base sheet 1.

As the base sheet 1, the base sheet 1
When the printed image is viewed through the hologram, it is necessary that the printed image be transparent to the extent that the printed image can be visually recognized. As a material, a plastic film such as polyester, polyvinyl chloride, polycarbonate, polypropylene, polyethylene, acrylic, and acetylcellulose is preferable as long as it is transparent. Examples of the opaque material include an opaque substrate such as paper, an opaque material containing a pigment or the like in the above-described plastic film, and a material in which a colored layer having a concealing property is provided on the above-described plastic film. .

The thickness of the base sheet 1 is not particularly limited.
Considering the workability of sticking, etc., 10μm or more, 250μ
m or less is generally considered.

Such a base sheet 1 is subjected to an easy adhesion treatment such as a plasma treatment, a corona discharge treatment, a far ultraviolet irradiation treatment, etc. in order to improve the adhesion with the design layer 2, the overcoat layer 4 and the adhesive layer 5. In order to improve the printability of the design layer 2, a printing ink easy-adhesion layer, an ink receiving layer, a toner receiving layer, and the like can be provided.

As a method of forming the design layer 2 on at least one surface of the base sheet 1, a print image can be formed by various printing methods. Printing methods include printing methods using printing inks such as offset printing, screen printing, and gravure printing, as well as printing methods using various printers such as inkjet printers, laser printers (PPC copiers), thermal transfer printers, and electrostatic printers. Is raised. The pattern layer 2 is formed on the base sheet 1 as a desired print image by such a printing method, and becomes a printed matter 3.

Next, a method for forming the overcoat layer 4 on the entire surface of the substrate sheet 1 opposite to the surface to be adhered to the adherend will be described. Here, the surface of the base material sheet 1 to be adhered to the adherend means the case where the printed matter is adhered to an adherend such as a wall surface inside a railway vehicle or a glass portion inside and outside the railway vehicle via an adhesive layer or the like. The surface to be stuck.

When the sticking surface of the base sheet 1 is the surface on which the design layer 2 is not provided, the ionizing radiation-curable resin composition is printed on the entire surface of the printed material 3 on which the design layer 2 is provided. And
The overcoat layer 4 is formed by curing by irradiation with ionizing radiation such as ultraviolet rays or electron beams (FIG. 1).

When the sticking surface of the base sheet 1 is the surface on which the design layer 2 is provided, the entire surface of the printed material 3 on which the design layer 2 is not provided is covered with the ionizing radiation-curable resin. The composition is printed and cured by irradiation with ionizing radiation such as ultraviolet rays or electron beams to form the overcoat layer 4 (FIG. 3).

The ionizing radiation-curable resin composition used in the overcoat layer 4 is cured by irradiation with ionizing radiation such as ultraviolet rays or electron beams to form the overcoat layer 4, and includes a photopolymerizable prepolymer and And / or an ionizing radiation-curable resin paint in which one or more kinds of photopolymerizable monomers are mixed.

Here, the photopolymerizable prepolymer and / or photopolymerizable monomer contained in the ionizing radiation-curable resin coating material undergoes radical polymerization and / or photopolymerization by irradiation of the functional group introduced into the skeleton with ionizing radiation. Those which undergo cationic polymerization, particularly those which are cured by radical polymerization, are preferred because they have a high curing rate and have a high degree of freedom in resin design.

As the prepolymer to be subjected to radical polymerization, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth)
Acrylic prepolymers such as acrylates and melamine (meth) acrylates are listed.
Monofunctional acrylic monomers such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, butoxypropyl acrylate, 1,6-hexanediol acrylate,
Bifunctional acrylic monomers such as neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate neopentyl glycol acrylate, and polyfunctional acrylics such as dipentaerythritol hexaacrylate, trimethylpropane triacrylate, and pentaerythritol triacrylate Monomers.

Examples of the prepolymer to be subjected to cationic polymerization include epoxy prepolymers such as bisphenol epoxy, novolak epoxy and alicyclic epoxy, vinyl ether prepolymers such as aliphatic vinyl ether, urethane vinyl ether and ester vinyl ether, and oxetane. Examples of the monomer include monomers having an epoxy group such as bisphenol A type epoxy, phenol novolak type epoxy and alicyclic epoxy, and monomers having a vinyl ether group such as triethylene glycol divinyl ether and hydroxy vinyl ether. can give.

In addition, ionizing radiation-curable resin coatings include:
In addition to the above photopolymerizable prepolymer and photopolymerizable monomer, if necessary, additives such as a photopolymerization initiator, an ultraviolet sensitizer, a pigment, a filler, and a leveling agent can be contained.

Particularly when ultraviolet rays are used for curing,
It is preferable to add a photopolymerization initiator. Examples of such a photopolymerization initiator include one that undergoes radical polymerization by cleavage, one that undergoes radical polymerization by abstracting hydrogen, or cationic polymerization that generates ions. These are selected as appropriate according to the prepolymer and monomer used.

Examples of the radical type photopolymerization initiator include benzoin ether type, ketal type, acetophenone type and thioxanthone type. Examples of the cationic photopolymerization initiator include diazonium salts, diaryliodonium salts, triarylsulfonium salts, triarylbilium salts, benzylpyridinium thiocyanates, dialkylphenacylsulfonium salts, dialkylhydroxyphenylphosphonium salts, and the like. These radical type photopolymerization initiators and cationic type photopolymerization initiators can be used alone or in combination of two or more.

Further, as a resin constituting the overcoat layer 4, a thermosetting urethane resin comprising a polyol and an isocyanate prepolymer, in addition to the ionizing radiation-curable resin composition, as long as the performance of the overcoat layer 4 is not impaired. And a thermosetting resin such as a phenol resin, an epoxy resin, or an unsaturated polyester resin, or a thermoplastic resin such as a polycarbonate, a thermoplastic acrylic resin, or an ethylene-vinyl acetate copolymer resin.

As such an ionizing radiation-curable resin composition, a UV-curable hard coat coating solution generally used for the purpose of preventing damage or the like can be used.

When the printed image is viewed through the overcoat layer 4, the overcoat layer 4 needs to be transparent to the extent that the printed image can be visually recognized. .

Although the thickness of the overcoat layer 4 cannot be determined unconditionally depending on the type of the ionizing radiation-curable resin composition, the type of the base sheet 1, the type of the ink used for the design layer 2, the thickness of the design layer 2, and the like. The lower limit is about 0.5 μm or more, preferably about 1 μm, and the upper limit is about 20 μm or less, preferably about 15 μm or less. When the thickness is 0.5 μm or more, incombustibility can be imparted to the printed matter, and when the thickness is 20 μm or less, the irradiation time of ionizing radiation can be reduced to increase the productivity and improve the workability of attaching the printed matter. .

The method for forming the overcoat layer 4 is as follows. The ionizing radiation-curable resin composition is used as a coating liquid by using an additive or a diluting solvent as required, and is printed by the printing method of the design layer 2 described above. In addition, printing may be performed by a coating method such as a bar coater, a blade coater, a spin coater, a roll coater, and a gravure coater. It is considered preferable to use a printing method similar to the printing method of the design layer 2 because the operation is not complicated and the equipment used for printing can be diverted.

The ionizing radiation used for curing the ionizing radiation-curable resin composition printed in this manner is an ultrahigh-pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp, or the like.
Examples include ultraviolet rays in a wavelength range of about 0 nm to 400 nm, and electron beams in a wavelength range of 100 nm or less emitted from a scanning or curtain type electron beam accelerator. The design layer 2
It is preferable to use an ultraviolet dryer or the like that is generally used in the drying step of the printing ink because it can be easily performed.

The non-combustible printed material 6 obtained by such a method has an adhesive layer 5 formed on the surface opposite to the surface on which the overcoat layer 4 is provided. Affixed to walls and glass surfaces.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 5 includes generally used acrylic pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and the like.
Urethane-based adhesives, rubber-based adhesives, and the like are used. Further, an adhesive having performance such as antistatic property may be used. When the printed image is viewed through the adhesive layer 5, the adhesive layer 5 needs to be transparent to the extent that the printed image can be visually recognized.

The thickness of the pressure-sensitive adhesive layer 5 is not particularly limited, but in consideration of the adhesion to an adherend and the releasability, the lower limit is 2 μm or more, preferably 5 μm or more, and the upper limit is 60 μm or less, preferably Is about 40 μm or less.

The pressure-sensitive adhesive layer 5 is generally formed by dissolving or dispersing the above-mentioned pressure-sensitive adhesive in a solvent as required to form a coating liquid, and applying and drying this coating liquid by a known coating method. Is done.

As described above, according to the method for treating non-combustibility of printed matter of the present invention, the pattern layer 2 is formed on at least one surface of the base sheet 1 and the pattern layer 2 of the base sheet 1 is provided. After printing the ionizing radiation-curable resin composition on the entire surface of the surface on which the pattern layer 2 is not provided or the surface on which the symbol layer 2 is not provided, the ionizing radiation-curable resin composition is cured by irradiation with ionizing radiation. By forming the overcoat layer 4 and forming the adhesive layer 5 on the surface opposite to the surface on which the overcoat layer 4 is formed, an expensive noncombustible resin sheet can be used or the noncombustible resin sheet can be adhered. The printed matter can be easily made nonflammable without laminating through an agent.

According to the non-combustible printed material of the present invention, the pattern layer 2 is formed on at least one surface of the base sheet 1.
Is provided, and the entire surface of the base sheet 1 on which the design layer 2 is provided or the surface on which the design layer 2 is not provided is coated with the ionizing radiation-curable resin composition. The formed overcoat layer 4 is provided, and the adhesive layer 5 is provided on the surface opposite to the surface on which the overcoat layer 4 is provided.
Is provided, without using an expensive non-combustible resin sheet as described above, or without laminating the non-combustible resin sheet via an adhesive, a printed material that has been subjected to a simple non-combustible treatment. What you can get.

In the above description, FIGS. 1, 2 and 3
As shown in the figure, a pattern layer 2 is provided on one surface of a base material sheet 1, and the surface of the base material sheet 1 on which the design layer 2 is provided,
Or, on the entire surface on the side where the design layer 2 is not provided,
The method of forming the overcoat layer 4 and then forming the adhesive layer 5 on the surface opposite to the surface on which the overcoat layer 4 is formed and the printed matter which has been made non-combustible by this method have been described. The pattern layer 2 may be provided on both surfaces of the base sheet 1 as described above, and by providing on both surfaces, when affixed to the glass portion inside and outside the railway vehicle, from both inside and outside of the railway vehicle You can see the print image. The pattern layer 2, the overcoat layer 4, and the adhesive layer 5 may be formed in any order. For example, in the case of FIG. 1, the adhesive layer 5 is formed before printing the pattern layer 2 or the overcoat layer 4. In the case of FIG. 3, the overcoat layer 4 may be formed before the pattern layer 2 is printed, or the overcoat layer 4 may be formed after the pattern layer 2 and the adhesive layer 5 are formed. good. In the case of FIG. 1, the overcoat layer 4 is formed on the entire surface of the base sheet 1 so as to cover the design layer 2, but the printing ink used in the design layer 2 is stipulated by the railway structure regulations. For example, when the non-combustibility performance is satisfied, as shown in FIG.
Can be formed on the entire surface of the base sheet 1 without covering the base sheet 1.

[0042]

Embodiments of the present invention will be described below. In addition,
“%” And “parts” are based on weight unless otherwise specified.

[Example 1] A white polyester film having a thickness of 100 µm was used as a base sheet, and an ultraviolet-curing ink for screen printing (Recure M4700:
A predetermined pattern layer was printed by screen printing using Jujo Chemical Co., Ltd., and the pattern layer was dried and cured by an ultraviolet dryer to obtain a printed material. The entire surface of the printed material on which the pattern layer was provided, was subjected to solid printing by screen printing using a clear-type UV-curable ink (Recure VX4700: Jujo Chemical Co.), and then used for drying the pattern layer. 6μm thick cured by UV dryer
Was formed. An adhesive layer having a thickness of 25 μm is provided on the surface opposite to the surface on which this overcoat layer is formed,
The sample of Example 1 was used.

Example 2 A clear polyester film having a thickness of 25 μm was used as a base sheet, and an ultraviolet-curing ink for screen printing (Recure M470) was applied to one surface of the base sheet.
(0: Jujo Chemical Co., Ltd.), a predetermined pattern layer was printed by screen printing, and the pattern layer was dried and cured by an ultraviolet dryer to obtain a printed material. After diluting an ultraviolet-curing resin coating for hard coating (Diabeam UR6530: Mitsubishi Rayon Co., Ltd.) with a mixed solvent of methyl ethyl ketone and toluene, and performing solid printing by screen printing, Then, the overcoat layer was formed by curing with the ultraviolet dryer used for drying the design layer so that the thickness became 8 μm. An adhesive layer having a thickness of 25 μm was provided on the surface opposite to the surface on which the overcoat layer was formed, to thereby obtain a sample of Example 2.

Example 3 An ultraviolet-curable resin coating for hard coating (Diabeam UR6530: Mitsubishi Rayon Co.) was applied to the opposite side of the surface of the printed matter produced in the same manner as in Example 2 on which the design layer was provided, with methyl ethyl ketone. -Diluted with a toluene mixed solvent, coated with a bar coater, and cured by the ultraviolet dryer used for drying the
A μm overcoat layer was formed. On the surface opposite to the surface on which the overcoat layer is formed, that is, on the surface on which the design layer is provided,
An adhesive layer having a thickness of 25 μm was provided to obtain a sample of Example 3.

Example 4 A 75 μm thick foamed polyester film was used as a base sheet, and a predetermined pattern layer was screen-printed on one side of the screen with an ultraviolet-curing ink for screen printing (Lake cure M4700: Jujo Chemical Co., Ltd.). Was printed and the pattern layer was dried and cured by an ultraviolet dryer to obtain a printed material. After diluting an ultraviolet-curing resin coating for hard coating (Diabeam UR6530: Mitsubishi Rayon Co., Ltd.) with a mixed solvent of methyl ethyl ketone and toluene, and performing solid printing by screen printing, Then, the overcoat layer was formed by curing with the ultraviolet dryer used for drying the design layer so that the thickness became 8 μm. An adhesive layer having a thickness of 25 μm was provided on the surface opposite to the surface on which the overcoat layer was formed, to thereby obtain a sample of Example 4.

Comparative Example 1 A sample of Comparative Example 1 was prepared in the same manner as in Example 1 except that the printed matter of Example 1 was not provided with an overcoat layer.

Comparative Example 2 The printed matter of Example 1 was not provided with an overcoat layer, and a brominated flame retardant (CR-380: Daihachi Chemical Industry Co., Ltd.) was used as an adhesive on the opposite side of the design layer of the printed matter. A sample of Comparative Example 2 was provided with a 25 μm-thick adhesive layer having 5% added to the solid content.

[Comparative Example 3] The printed matter of Example 1 was not provided with an overcoat layer, and a phosphorus-based flame retardant (CR-733S: Daihachi Chemical Industry Co., Ltd.) was used as an adhesive on the opposite side of the design layer of the printed matter. A sample of Comparative Example 3 was provided with a 25 μm-thick adhesive layer added by 10% to the solid content.

Comparative Example 4 The same procedure as in Example 1 was carried out except that the white polyester film of Example 1 was changed to a flame-retardant polyester film (Dialamie: Mitsubishi Plastics, Inc.) and no overcoat layer was provided. 4 samples.

Comparative Example 5 A sample of Comparative Example 5 was prepared in the same manner as in Example 1 except that the printed matter of Example 1 was not provided with an overcoat layer and a commercially available polyethylene laminating film was laminated instead of the overcoat layer. And

Comparative Example 6 A sample of Comparative Example 6 was made in the same manner as in Example 3 except that the printed matter of Example 3 was not provided with an overcoat layer.

For the samples of the examples and comparative examples,
A material combustion test for railway vehicles specified in the Ordinance for Structural Railways was conducted.

The test was performed using a combustion test apparatus 1 as shown in FIG.
4, the sample 11 cut into a B5 size is held at an angle of 45 ° so that the surface provided with the adhesive layer faces upward, and the center of the bottom of the fuel container 12 is perpendicular to the center of the lower surface of the sample 11. The fuel container 12 was placed on a fuel container base 13 made of cork so as to be 25.4 mm below, and 0.5 cc of pure alcohol was put into the fuel container 12 and ignited, and the fuel container 12 was left until the fuel was burned out.

The flammability is determined according to the flammability criterion of the material combustion test for railway vehicles, and during combustion of the alcohol, the sample is ignited, ignited, smoked, and flamed, separately from during combustion. After observation, after combustion, residual flame, residual dust, carbonization and deformation were investigated. Table 1 shows the determination results during alcohol combustion, Table 2 shows the determination results after alcohol combustion, and Table 3 shows the determination results.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

According to the method for non-combustible printed matter of the present invention, a pattern layer is formed on at least one surface of a substrate sheet, and the pattern layer is formed on the opposite side of the surface of the substrate sheet to be adhered to an adherend. By printing an ionizing radiation-curable resin composition on the entire surface and curing it by irradiation with ionizing radiation to form an overcoat layer, the printed matter is easily made nonflammable without using an expensive nonflammable resin sheet. Is what you can do. Further, according to the non-combustible printed matter of the present invention, the printed matter is provided with a design layer on at least one surface of the substrate sheet, and the entire surface of either one side of the substrate sheet is ionized. By providing the overcoat layer formed of the radiation-curable resin composition, it is possible to easily obtain a nonflammable print without using an expensive nonflammable resin sheet as described above. It is.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one embodiment of a non-combustible printed material according to the present invention.

FIG. 2 is a sectional view showing an embodiment of a printed material used in the present invention.

FIG. 3 is a cross-sectional view showing another embodiment of the printed matter subjected to the non-combustible treatment of the present invention.

FIG. 4 is a sectional view showing another embodiment of a printed material used in the present invention.

FIG. 5 is a cross-sectional view showing another embodiment of the non-combustible printed material of the present invention.

FIG. 6 is a perspective view of a flammability test apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base sheet 2 ... Design layer 3 ... Printed matter 4 ... Overcoat layer 5 ... Adhesive layer 6 ... Non-combustible printed matter 11 ... Sample 12 ... Fuel container 13: Fuel container stand 14: Combustion test device

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H113 AA01 AA06 BA10 BB08 BC00 CA15 CA46 DA26 DA57 EA07 FA35 FA43 4F100 AK01B AK42 AT00A BA10B CB05C EJ08B EJ54 HB00 HB31 JB14B JJ07 JL10 JL13C

Claims (5)

[Claims] 1. A pattern layer is formed on at least one surface of a substrate sheet, and an ionizing radiation-curable resin composition is printed on the entire surface of the substrate sheet opposite to the surface to be adhered to an adherend. A non-combustible treatment method for printed matter, comprising forming an overcoat layer by curing by irradiation with ionizing radiation. 2. The method for treating non-combustibility of printed matter according to claim 1, wherein an adhesive layer is formed on a surface of the base sheet to be adhered to an adherend. 3. A printed material having a pattern layer provided on at least one surface of a substrate sheet, wherein an overcoat formed of an ionizing radiation-curable resin composition is formed on the entire surface of one of the surfaces of the substrate sheet. A non-combustible printed material comprising a coat layer. 4. The non-combustible printed matter according to claim 3, wherein an adhesive layer is provided on a surface of the base sheet opposite to a surface on which the overcoat layer is provided. 5. The method according to claim 1, wherein said overcoat layer has a thickness of 0.5 μm.
The non-combustible printed matter according to claim 3, wherein the printed matter has a size of m to 20 μm.