JP2003103706A - Printing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a printing film having ultraviolet absorbing capacity, good in the adhesiveness of a plastic film and printing ink, not generating a crack in the printing ink, capable of being corrected in wiping-off due to an organic solvent and hard to damage its surface. SOLUTION: The printing film is constituted by providing an ink adhesive layer having light fastness on at least the single surface of the plastic film and the ink adhesive layer is formed by curing treatment using an ultraviolet absorbable acrylic polyol resin, a photopolymerizable prepolymer and monomer having an active proton, an amino compound or an isocyanate compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing film for producing a printed matter that is exposed to outside light or illumination light such as a display screen for a destination of a bus. Not about printing film.

[0002]

2. Description of the Related Art Usually, a printed matter such as a bus destination display screen is directly printed on a plastic film such as a polyester film or a polycarbonate film by using a printing ink such as silk printing. However, such a display screen has a drawback that the printing ink is easily peeled off from the plastic film because the display screen is used for winding and unwinding a roll many times.

Further, there has been a problem that the plastic film is deteriorated and discolored when exposed to ultraviolet rays for a long period of time. Therefore, in order to protect the plastic film, it may be possible to provide a layer having light resistance on the plastic film. However, when a monomer type ultraviolet absorber is mixed with a binder resin to form a layer having these light resistances, the monomer may bleed over time. For this reason, the amount that can be added is limited, and it is not possible to obtain sufficient ultraviolet absorption performance. Further, when the ultraviolet absorber bleeds, there is a problem that the adhesiveness with the printing ink further deteriorates and the printing ink peels off.

In order to solve such a problem, it is conceivable to use a polymer type ultraviolet absorber, that is, an ultraviolet absorbing resin. However, although there is no bleeding problem, the adhesiveness to a plastic film is low and the display curtain When it is repeatedly wound around the roll or unwound, the printing ink is peeled off from the plastic film.

Further, since it has no solvent resistance, when printing is carried out using an organic solvent-containing printing ink such as silk printing, there arises a problem that the printing ink is cracked after drying. Furthermore, when it is desired to correct printed characters, etc., it is difficult to correct using an organic solvent such as methyl ethyl ketone, and it may be rubbed off with a solvent that does not attack the UV absorbing resin, but the scratch resistance is low. Therefore, there is also a problem that the surface is scratched.

[0006]

SUMMARY OF THE INVENTION Therefore, the present invention is a printing film having an ultraviolet absorbing property, which has good adhesiveness between a plastic film and a printing ink, and does not cause cracks in the printing ink, and an organic solvent. An object of the present invention is to provide a printing film which can be wiped and corrected by the method and whose surface is not easily scratched.

[0007]

Therefore, the inventors of the present invention have found that the ink adhesive layer has the above-mentioned ultraviolet absorption performance and imparts ink adhesiveness, solvent resistance and scratch resistance, and at the same time, a plastic film. As a result of intensive research into whether or not it is possible to improve the adhesiveness to, the present invention has been completed.

That is, the printing film of the present invention is a printing film in which a light-resistant ink adhesive layer is provided on at least one surface of a plastic film, wherein the ink adhesive layer is (A): UV absorption having active protons. Resin, (B): a photopolymerizable prepolymer and / or monomer having an active proton, (C): a composition containing (A) and (B) and a curable composition It is characterized by being.

Further, the printing film of the present invention is characterized in that the ultraviolet absorbing resin having active protons is an ultraviolet absorbing acrylic polyol resin.

Further, in the printing film of the present invention, the ultraviolet absorbing acrylic polyol resin contains 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole as a monomer having an ultraviolet absorbing group. It is characterized by including.

Further, the printing film of the present invention is characterized in that the crosslinking agent is an amino compound and / or an isocyanate compound.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the printing film of the present invention will be described in detail below.

The printing film of the present invention is a printing film in which at least one surface of a plastic film is provided with an ink adhesive layer having light resistance, and the ink adhesive layer comprises (A): UV absorption having active protons. A resin, (B): a photopolymerizable prepolymer and / or monomer having an active proton, (C): a composition obtained by curing a composition containing a crosslinkable crosslinkable crosslinking agent (A) and (B) is there.

Here, (A): an ultraviolet absorbing resin having an active proton (hereinafter, also referred to as "A component"), (B):
A photopolymerizable prepolymer and / or monomer having an active proton (hereinafter, also referred to as “B component”), (C):
(A) and (B) are cross-linkable and curable cross-linking agent (hereinafter,
A composition containing “C component”) will have two curing mechanisms. That is, the composition of the present invention is
A component and B component, between A components, and between B components,
The C component has a mechanism of crosslinking and curing, and the B components have a mechanism of photo-curing by irradiation of ionizing radiation (ultraviolet ray or electron beam). Note that the order of curing of these two curing mechanisms is not limited, and after the A component and the B component are bridged and cured by the C component, the B component after the bridged curing by the C component is cured. It can also be photo-cured by irradiation with ionizing radiation.
After the components are photopolymerized to the ionizing radiation-curable polymer having active protons by irradiation with ionizing radiation, the active protons of the ionizing radiation-curable polymer and the A component can be crosslinked and cured by the C component. Also, when heating and irradiation of ionizing radiation are performed simultaneously,
It is possible that these two reaction mechanisms proceed simultaneously.

Therefore, by providing an ink adhesive layer obtained by curing a composition having such two curing mechanisms on at least one side of a plastic film, adhesion to the plastic film, solvent resistance, scratch resistance, etc. It is possible to form an excellent ink adhesive layer.

As the plastic film, a transparent or opaque film such as polyester, polycarbonate, polyethylene, polypropylene, triacetyl cellulose, polyvinyl chloride, acryl, polystyrene, polyamide, polyimide, vinylidene chloride is used.
A vinyl chloride copolymer or the like can be used.

When a printed image or the like is viewed through a plastic film, the plastic film needs to be substantially transparent. The term “substantially transparent” means that the characters and the like printed through a plastic film are transparent enough to be seen through. Therefore, the plastic film may be colored. Further, when the printed image or the like is directly viewed, the plastic film may be opaque. Further, the plastic film may be subjected to antistatic treatment, easy adhesion treatment and the like.

The thickness of the plastic film is not particularly limited, but in consideration of supply to a printing machine, transportation, etc., for example, 1
Those having a thickness of 0 μm to 250 μm are used. In the case of being used by repeatedly winding and unwinding like a destination display curtain of a bus, the thickness of about 30 μm to 125 μm is suitable.

Next, in the printing film of the present invention, the ink adhesive layer comprises (A): an ultraviolet absorbing resin (component A) having active protons, (B): a photopolymerizable prepolymer having active protons, and And / or a monomer (component B), (C): a composition containing a cross-linking agent (component C) that can be cured by bridging (A) and (B). This makes it possible to obtain a printing film which has an ultraviolet absorbing property and is excellent in adhesion to a plastic film, ink adhesion, solvent resistance, scratch resistance and the like.

Examples of the component A include acrylic resins having active protons, polyester resins, polyether resins, polyurethane resins, etc. Among them, it is preferable to use an ultraviolet absorbing acrylic polyol resin. Particularly, as such an ultraviolet absorbing acrylic polyol resin, 2- (2'-
Hydroxy-5'-methacryloxyethylphenyl)-
A copolymer containing 2H-benzotriazole, an ethylenically unsaturated double bond monomer having an active proton, and an ethylenically unsaturated double bond monomer having no active proton is preferable.

2- which is a constituent component of such a copolymer
(2'-Hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole is a benzotriazole skeleton represented by the following formula (1) in which a methacryloyl group is introduced and is a component for absorbing ultraviolet rays. is there.

[0022]

[Chemical 1]

An ultraviolet-absorbing acrylic polyol resin containing the above-mentioned 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole (hereinafter sometimes referred to simply as "benzotriazole") as a monomer component is It has an absorption property for light of 290 nm to 400 nm, and since an ultraviolet absorbing group is introduced into the acrylic polyol resin, bleeding does not occur,
It does not reduce the adhesion to printing ink.

Here, the polymerization ratio of the above-mentioned benzotriazole in the ultraviolet absorbing acrylic polyol resin is 80% by weight or less, preferably 60% by weight or less, more preferably 100% by weight of the ultraviolet absorbing acrylic polyol resin. Is 55% by weight or less, and the lower limit is 5
It should be more than weight%.

Next, as the ethylenically unsaturated double bond monomer having an active proton, a monomer having a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an acetoacetoxyethyl group is preferable. Examples of such a monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) as a monomer having a hydroxyl group.
Acrylate, N-methylol acrylamide, allyl alcohol, p-hydroxystyrene, etc., as a carboxyl group-containing monomer, β-carboxyethyl (meth) acrylate, (meth) acrylic acid, itaconic acid,
Aminomethyl (meth) acrylate, methylaminomethyl (meth) acrylate, methylaminoethyl (meth) acrylate, methylaminopropyl (meth) acrylate, acrylamide as amino group-containing monomers such as crotonic acid, maleic acid, and maleic anhydride. As an example of the monomer containing an acetoacetoxyethyl group, acetoacetoxyethyl (meth) acrylate and the like can be mentioned. By adding such a functional group-containing monomer, the ultraviolet absorbing resin has an active proton.

As the ethylenically unsaturated double bond monomer having no active proton, a (meth) acrylic acid ester having an alkyl group having 1 to 12 carbon atoms in the ester portion is preferable. By including such a (meth) acrylic acid ester, the adhesiveness of the printing ink can be enhanced and the physical properties of the coating film can be easily controlled. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. Can be given.

Further, adhesiveness with a plastic film,
Comonomers such as vinyl acetate, vinyl propionate, vinyl ether, styrene, and (meth) acrylonitrile that have ethylenically unsaturated double bonds are used as copolymerization components for synthesizing UV-absorbing resins to improve coating properties. May be added.

Since the ultraviolet absorbing resin having an active proton used as the component A of the present invention is a polymer resin in which an ultraviolet absorbing group is introduced into a resin having an active proton, the component B is added via the component C. It can be cured by cross-linking, does not bleed like a simple mixture of low molecular weight UV absorbers, and does not deteriorate the adhesiveness of ink. Therefore, this A component,
By curing a composition containing B and C components to form an ink adhesive layer, it has excellent UV absorption performance and has excellent adhesiveness to plastic films, ink adhesion, solvent resistance, scratch resistance, etc. An excellent ink adhesion layer can be formed.

Next, as the component B, it is necessary that the photopolymerizable prepolymer or the photopolymerizable monomer has an active proton. Such photopolymerizable prepolymers and photopolymerizable monomers are those that undergo radical polymerization or cationic polymerization when the functional groups introduced into the terminal and / or skeleton are irradiated with ionizing radiation, and are particularly cured by radical polymerization. What is done is preferable because the curing speed is fast and the degree of freedom in resin design is large.

Examples of the radical polymerization type photopolymerizable prepolymer having active protons include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate and polyol (meth). Acrylic prepolymers such as acrylate and melamine (meth) acrylate can be cited, and radical polymerization type photopolymerizable monomers having active protons include monofunctional acryl such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Monomer, 1,6-hexanediol acrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hydroxypentaate Relate, hydroxypivalic acid ester neopentyl glycol acrylate, polyfunctional acrylic monomers such as pentaerythritol triacrylate can be cited.

Examples of the cationic polymerization type photopolymerizable prepolymer or monomer having active protons include epoxy type prepolymers or monomers such as bisphenol A type epoxy, novolac type epoxy, alicyclic epoxy and phenol novolac type epoxy, and aliphatic groups. Examples thereof include vinyl ether-based prepolymers or monomers such as vinyl ether, urethane-based vinyl ethers and ester-based vinyl ethers, and oxetane-based prepolymers or monomers.

Further, the composition of the present invention may contain a photopolymerizable prepolymer having no active protons or a photopolymerizable monomer in addition to the photopolymerizable prepolymer having an active protons or a photopolymerizable monomer. It is possible

When ultraviolet rays are used in curing the composition of the present invention by irradiation with ionizing radiation,
In order to promote photopolymerization, it is preferable to include a photopolymerization initiator or an ultraviolet sensitizer in the composition of the present invention.

As the radical polymerization type photopolymerization initiator, acetophenone, benzophenone, Michler's ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) is used.
2- (4-morpholinyl) -1-propane, α-acyloxime ester, thioxanthones and the like can be mentioned. Examples of the cationic polymerization type photopolymerization initiator include diazonium salts, diaryl iodonium salts and triarylsulfonium salts. , Triarylpyrylium salt, benzylpyridinium thiocyanate, dialkylphenacylsulfonium salt, dialkylhydroxyphenylphosphonium salt and the like. As such a photopolymerization initiator, a photopolymerization initiator having an absorption wavelength range peak at a position different from the absorption wavelength range peak of the ultraviolet absorbing resin as the component A by at least 20 nm or more is preferable.

Examples of the UV sensitizer include n-butylamine, triethylamine, tri-n-butylphosphine and the like.

Next, the C component will be described. The C component is not particularly limited as long as it is a cross-linking agent capable of acting on the crosslinking curing by reacting with the active protons contained in the A component and the B component. However, when the present inventor made various studies on these crosslinking agents,
From the viewpoint of improving the adhesiveness between the ink adhesive layer and the plastic film, it has been found that it is preferable to use an amino compound or an isocyanate compound as the crosslinking agent. The reason for this is not clear, but the amino compound and the isocyanate compound react with the active protons contained in the A component and the B component to contribute to crosslinking and improve solvent resistance and scratch resistance. It is considered that since the compound and the isocyanate compound also contribute to the bonding with the plastic film, the adhesiveness with the plastic film is improved.

The amino compound referred to here is melamine,
Examples thereof include melamine compounds such as methylolated melamine, etherified methylol melamine and its derivatives, and urea compounds such as urea, methylol urea and its derivatives.

The term "isocyanate compound" as used herein generally means a polyisocyanate prepolymer used in a room temperature curing system. Polyisocyanate prepolymers include toluene diisocyanate-based, methylene diisocyanate-based, xylene diisocyanate-based, isophorone diisocyanate-based, hexamethylene diisocyanate-based, etc. depending on the raw material isocyanate. System and hexamethylene diisocyanate system are preferably used.

Next, the content of each of A component, B component and C component in the ink adhesive layer composition of the present invention is 20% by weight of A component based on 100% by weight of the solid content of the composition. To 95% by weight, B component 5% to 50% by weight, and C component 0.5% to 30% by weight in the range of printability, solvent resistance, surface hardness and adhesiveness with a plastic film. It is suitable in that respect.

Particularly, it is preferable that the C component is 0.5 to 40 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the total of the A component and the B component. Further, the total content of the A component and the C component in the composition is preferably in the range of 50 to 95% by weight with respect to 100% by weight of the composition.

Further, the above-mentioned composition of the present invention contains other resins, other cross-linking agents, matting agents, plasticizers, antioxidants, colorants, lubricants, etc. within a range not impairing the function of the present invention. , Various additives such as antistatic agents, flame retardants, antibacterial agents, antifungal agents and the like can be included.

Particularly when a printed image or the like is directly viewed, it is preferable to add a white pigment such as titanium oxide to the ink adhesive layer. This is because the color of the printed image can be seen by making the ink adhesive layer white. By including such a white pigment, blocking of the coating is further suppressed.

The printing film of the present invention is prepared as a coating composition by adding other components, a diluting solvent, etc. to the mixture of the above-mentioned component A, component B and component C, if necessary.
The composition can be applied to one side or both sides of a plastic film by a conventionally known coating method, and can be formed as an ink adhesive layer by curing by heating and curing by irradiation with ionizing radiation. The method of irradiating with ionizing radiation is 100 nm to 400 nm, preferably 2 nm, emitted from 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.
Irradiate ultraviolet rays in the wavelength region of 00 nm to 400 nm,
Alternatively, it can be performed by irradiating with an electron beam in a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.

The thickness of the ink adhesive layer as described above is not particularly limited, but when it is provided by the coating method, it is 2 μm to 40 μm, preferably 4 μm to 20 μm.

In the printing film of the present invention, a display screen or the like can be produced by printing on the surface on which the ink adhesive layer is formed with a printing ink such as silk printing.

In the above description, the case where the ink adhesive layer is provided on the entire surface of the plastic film has been described, but it is sufficient that the ink adhesive layer is provided at least on the portion to be printed, and such an ink adhesive layer is partially formed. Those provided with an ink adhesion layer are also included in the printing film of the present invention.

[0047]

The present invention will be described in more detail based on the following examples. In this example, "part" and "%"
Is by weight unless otherwise indicated.

1. 90 parts of toluene, 13.5 parts of butyl acrylate monomer, 60 parts of methyl methacrylate monomer in a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet tube for synthesizing an ultraviolet absorbing resin having active protons.
Part, 2-hydroxyethyl methacrylate monomer 6
Parts, methacrylic acid monomer 0.5 parts, 2- (2'hydroxy-5'-methacryloxyethylphenyl) -2H
20 parts of benzotriazole monomer and 0.2 parts of α, α′-azobis (isobutyronitrile) are mixed and added,
Heated to 75 ° C. with stirring under nitrogen. The reaction solution was continuously stirred for 7 hours and 30 minutes while maintaining the temperature at 75 ° C. to complete the reaction to synthesize an ultraviolet absorbing acrylic polyol resin. Toluene was added to this to prepare a solid content of 25% to obtain an ultraviolet absorbing acrylic polyol resin solution.

2. In a reaction vessel equipped with a synthetic stirrer of a UV absorbing resin having no active proton of Comparative Example 2, a condenser, a thermometer and a nitrogen introducing tube, 90 parts of toluene, 13 parts of butyl acrylate monomer, 67 parts of methyl methacrylate monomer,
20 parts of 2- (2'hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole monomer,
0.2 part of α, α′-azobis (isobutyronitrile) was mixed and added, and the mixture was heated to 75 ° C. with stirring under nitrogen. The reaction solution was stirred for 7 hours and 30 minutes while maintaining the temperature at 75 ° C. to complete the reaction to synthesize an ultraviolet absorbing acrylic resin. Toluene is added to this to obtain a solid content of 25%.
To prepare an ultraviolet absorbing acrylic resin solution.

3. Production of Printing Film [Example 1] A coating composition for an ink adhesive layer having the following composition was applied to both surfaces of a 100 μm-thick polyester film (Lumirror T-60: Toray), dried and cured, and further a high pressure mercury lamp. Was irradiated with ultraviolet rays to be cured to form an ink adhesive layer having a film thickness of about 8 μm, and the printing film of the present invention was produced.

The coating composition for an ink adhesive layer has an ultraviolet absorbing resin having an active proton as the A component (the ultraviolet absorbing acrylic polyol resin synthesized in 1. above), and an active proton as the B component. Photopolymerizable prepolymer (epoxy acrylate <Kayarad R-13
0: Nippon Kayaku Co., Ltd.>), a photopolymerizable monomer having an active proton (dipentaerythritol monohydroxypentaacrylate), a C component, a melamine compound (Nicalac MW-30M: Sanwa Chemical Co., Ltd.), and other components.
A photopolymerizable monomer having no active proton (dipentaerythritol hexaacrylate) and a radical polymerization type photopolymerization initiator (hydroxycyclohexyl phenyl ketone) were used.

[0052] <Paint composition for ink adhesive layer> ・ UV absorbing acrylic polyol resin solution 56 parts 2.4 parts of photopolymerizable prepolymer having active protons ・ Photopolymerizable monomer having active proton 0.8 part -Photopolymerizable monomer having no active proton 0.8 part Radical polymerization type photopolymerization initiator 0.3 part ・ Melamine compound 2 parts ・ Toluene 38 parts

Example 2 Instead of the melamine compound which is the C component in the ink adhesive layer coating composition of Example 1, as the C component, a xylene diisocyanate isocyanate compound (solid content 60%: <Takenate D110N: Mitsui) was used. Example 1 except that 3.3 parts of Takeda Chemical Co., Ltd.> was added.
A printing film of the present invention was produced in the same manner as in.

[Comparative Example 1] In place of the ultraviolet absorbing acrylic polyol resin which is the component A of the coating composition for an ink adhesive layer of Example 2, 3 parts of an ultraviolet absorbing agent (Chemisorb 79: Chemipro) and acrylic were used. In the same manner as in Example 2 except that 22 parts of a polyol resin (solid content 50%: <Acridic A817: Dainippon Ink and Chemicals, Inc.>) was added,
A printing film of Comparative Example 1 was produced.

[Comparative Example 2] Instead of the ultraviolet absorbing acrylic polyol resin which is the component A of the coating composition for an ink adhesive layer of Example 2, an ultraviolet absorbing resin having no active proton (synthesized in 2. above) was used. Comparative Example 2 in the same manner as in Example 2 except that the ultraviolet absorbing acrylic resin
The printing film of was produced.

[Comparative Example 3] A photopolymerizable prepolymer having an active proton as a component B of the coating composition for an ink adhesive layer of Example 2, and a photopolymerizable monomer having no active proton as another component. A printing film of Comparative Example 3 was produced in the same manner as in Example 2 except that the radical polymerization type photopolymerization initiator was not added and the ultraviolet irradiation was not performed.

Comparative Example 4 A printing film of Comparative Example 4 was prepared in the same manner as in Example 2 except that the isocyanate compound which was the component C of the ink adhesive layer coating composition of Example 2 was not added. did.

4. Printing of Printing Film Using a solvent printing ink containing an organic solvent (vinyl ink HIP710 black: Seiko Advance Co., Ltd.) on the ink adhesive layer on one side of the printing films of Examples and Comparative Examples, a silk screen mesh was used. A mirror image character was printed at # 200.

5. Performance evaluation of printing film 4. With respect to the printed printing film prepared in, the light resistance, solvent resistance, scratch resistance, adhesiveness of the ink adhesive layer to the polyester film, and adhesiveness of the printing ink to the ink adhesive layer were evaluated as follows. It was

[Evaluation of light resistance] Printing was carried out using an accelerated tester (ultraviolet fade meter FAL-5: Suga Test Instruments Co., Ltd.) having an accelerated ability equivalent to one year's worth of ultraviolet irradiation of 200 hours of irradiation. 600 from the side not facing
After irradiating ultraviolet rays for a period of time, visually evaluate the discoloration / discoloration of the printed image, and those with severe discoloration / discoloration are marked with “X”, and those that have hardly discolored / discolored are marked with “○”.
Evaluated as. The evaluation results are shown in Table 1.

[Evaluation of Solvent Resistance] First, after printing characters and drying the printing ink, those having cracks in the printing ink were evaluated as "x", and those without cracks were evaluated as "○". did.

For the printed characters, a soft cloth impregnated with methyl ethyl ketone was used, and the contact area was 2
With a load of 1 kg in cm ² , the printed characters were completely wiped off, and the ink adhesive layer melted and lost was marked with “x”,
The case where part of the ink adhesion melted and disappeared was evaluated as "△", and the case where it did not melt at all was evaluated as "○". The evaluation results are shown in Table 1.

[Evaluation of scratch resistance] The ink adhesive layer was rubbed 20 times with a load of 1 kg at a contact area of 2 cm ² using a soft cloth impregnated with a solution of isopropyl alcohol and toluene mixed at a ratio of 1: 1. The presence or absence of scratches on the surface of the ink adhesive layer was visually evaluated, and those with scratches were marked with "x", and those without scratches were marked with "○". The evaluation results are shown in Table 1.

[Adhesiveness of Ink Adhesive Layer to Polyester Film] The adhesiveness of the ink adhesive layer to the polyester film is determined by the cross-cut tape method (JIS-K540).
It was evaluated according to 0). As a result of the peeling test by the cross-cut tape method, "X" indicates that the area of the cross-cut portion has peeled by 30% or more, and "X" indicates that the part of the cross-cut portion has peeled but the peeled area is less than 30%. Δ ”, and those in which the cross-cut portion did not peel at all were marked as“ ◯ ”. The evaluation results are shown in Table 1.

[Adhesiveness of Printing Ink to Ink Adhesive Layer] Regarding the adhesiveness of the printing ink to the ink adhesive layer, "X" means that the printing ink was peeled off by the adhesive tape, and "○" means that the printing ink did not peel off. . The evaluation results are shown in Table 1.

[0066]

[Table 1]

As is clear from the results shown in Table 1, the printing films of Examples had light resistance, solvent resistance, scratch resistance, adhesion of the ink adhesive layer to the polyester film, and printing ink of the ink adhesive layer. Excellent evaluation was obtained in all of the adhesiveness.

Since the printing film of Comparative Example 1 uses an acrylic polyol resin and a monomer type ultraviolet absorber instead of the ultraviolet absorbing acrylic polyol resin, the ultraviolet absorber causes bleeding and printing on the ink adhesive layer. The ink adhesion was not sufficient.
Further, the surface of the ink adhesive layer was whitened by the bleeding of the ultraviolet absorber and could not be put to practical use.

Since the printing film of Comparative Example 2 uses an ultraviolet absorbing acrylic resin having no active protons instead of the ultraviolet absorbing acrylic polyol resin,
It had no solvent resistance and scratch resistance. For the adhesiveness of the ink adhesive layer to the polyester film, see B.
Since the component and the C component were cross-linked and cured, as a result of the cross-cut peeling test, some were not peeled off, but sufficient adhesiveness was not obtained.

The printing film of Comparative Example 3 contained the components A and C.
Since the components were cross-linked and cured, solvent resistance was obtained to the extent that the printing ink did not crack, but since component B was not added, solvent resistance evaluation with methyl ethyl ketone showed that the ink adhesion layer The part melted and disappeared, and a sufficient evaluation could not be obtained. The same applies to scratch resistance, and since the component B was not added, the surface was scratched and sufficient evaluation could not be obtained.

In the printing film of Comparative Example 4, since the component C was not added and only the component B was cured by ultraviolet rays, solvent resistance other than light resistance, scratch resistance, and ink adhesion layer for the polyester film. About adhesiveness,
Sufficient evaluation was not obtained. Moreover, the adhesiveness of the printing ink to the ink adhesive layer could not be evaluated because the printing ink was peeled off together with the ink adhesive layer by the adhesive tape.

[0072]

According to the printing film of the present invention, by providing an ink adhesive layer having good adhesiveness to printing ink and good adhesiveness to plastic film on at least one side of the plastic film, Even if the printed matter is used for winding and unwinding many times like a display screen, the printing ink may peel off from the plastic film, or the printing ink may fall off from the plastic film even after long-term use. There is no. Further, there is no problem that the printing ink is cracked when printing is performed using a printing ink containing an organic solvent such as silk printing. Further, since it is excellent in solvent resistance and scratch resistance, it is possible to easily correct printed characters and the like by using an organic solvent, and at that time, the surface is not damaged. Furthermore, because a polymer type UV absorbing resin is used, the UV absorbing agent does not bleed, and even when it is exposed to external light or illumination light for a long time, it does not fade or deteriorate, and a clear printing state is maintained. Be drunk

Claims (4)

[Claims] 1. A printing film comprising an ink adhesive layer having light resistance provided on at least one surface of a plastic film, wherein the ink adhesive layer is (A): an ultraviolet absorbing resin having active protons, (B): A photopolymerizable prepolymer and / or monomer having an active proton, (C): (A) and (B), which is a composition obtained by curing a composition containing a crosslinkable curable agent. Printing film. 2. The printing film according to claim 1, wherein the ultraviolet absorbing resin having active protons is an ultraviolet absorbing acrylic polyol resin. 3. The ultraviolet-absorbing acrylic polyol resin is used as 2- (2′-) as a monomer having an ultraviolet-absorbing group.
Hydroxy-5'-methacryloxyethylphenyl)-
The printing film according to claim 2, comprising 2H-benzotriazole. 4. The printing film according to any one of claims 1 to 3, wherein the crosslinking agent is an amino compound and / or an isocyanate compound.