JP2981270B2 - Marking film structure - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a marking film excellent in weather resistance, heat resistance, solvent resistance, stain resistance, and sharpness, and more particularly, to a hood roof of an automobile and the like. The present invention relates to a marking film structure that can be used on a surface that receives a large amount of light and is exposed to high temperatures.

[Conventional technology]

2. Description of the Related Art Conventionally, marking films have been widely used and are used as a substitute for paint in signboards, automobiles, vehicles, and the like. However, the conventional marking film is mainly composed of a vinyl chloride resin, and its weather resistance and heat resistance are insufficient, so that the weather resistance and heat resistance of the marking film are not sufficient. In particular, when used on a surface that is exposed to high temperatures for a long time, such as an automobile hood or roof, which has a large amount of received light, troubles such as browning, cracking, and peeling occur in just a few years, and have not been put to practical use. Further, it has been pointed out that, in recent years, when the level of automobile coating has been improved and applied on automobile coating, the marking film has poor clarity and is inferior in appearance.

In addition, the conventional marking film did not have sufficient solvent resistance, and thus could not be used in a case where the solvent was directly exposed to a solvent.

Further, once the conventional marking film is stained, the stain is difficult to remove, and its appearance deteriorates over time, and it often does not return to its original state even if it is wiped.

So, in some cases, PV
It is considered to laminate a transparent film of F or PVdF, but in fact, heat resistance, weather resistance, and sharpness have not been sufficiently improved.

[Problems to be solved by the invention]

The object of the present invention is to solve the above-mentioned disadvantages of the prior art, and the heat resistance, weather resistance, solvent resistance, sharpness, and stain resistance of the conventional marking film are not sufficient. It is an object of the present invention to provide a marking film structure that can be used in places that cannot be practically used, for example, a car roof, a hood, and the like.

[Means for solving the problem]

The present invention has been made to solve the above-mentioned problems, and at least a colored layer made of a solvent-soluble fluororesin on the back surface, an uncolored fluorine layer laminated in the order of an adhesive layer and a peelable substrate layer. Has a resin-based layer and the surface clarity is PGD value
It is intended to provide a marking film structure characterized by being 0.3 or more.

In the present invention, as the fluororesin constituting the fluororesin layer, ethylene-tetrafluoroethylene-based copolymer, ethylene trifluoride copolymer, vinylidene fluoride copolymer,
Examples include vinyl fluoride polymers, fluorinated alkoxyethylene polymers, and tetrafluoroethylene / hexafluoropropylene copolymers, and particularly preferred are ethylene / tetrafluoroethylene-based copolymers. /
The molar ratio of ethylene is 40 / 60-60 / 40, and the general formula
The perfluoroalkylvinyl monomer represented by CH ₂ = CH · CnF _{2n + 1} (where n is an integer of 2 to 10) having a content of 0.1 to 10 mol% is a transparent, colored layer. It is particularly preferable from the viewpoints of adhesion to the film and film forming properties. Such an ethylene-tetrafluoroethylene copolymer can be produced, for example, by the method described in JP-B-59-50163, or a commercially available product can be used. As commercially available products, for example, Aflon COP (manufactured by Asahi Glass Co., Ltd.), NEOFLON ETFE (manufactured by Daikin Industries, Ltd.), and Texel (manufactured by DuPont) are preferable.

In addition, prior to laminating the coloring layer on the fluororesin layer, the surface of the fluororesin layer may be subjected to an activation treatment so that “wetting” according to JIS K6768 becomes 30 to 54, and further 35 to 54. It is preferable from the viewpoint of enhancing the properties. The method of the activation treatment is not particularly limited, and any method may be used, but a corona discharge treatment is preferably used in the process.

Although the thickness of the fluorine-based resin layer is not particularly limited, it is generally 10 μm to 200 μm, preferably 15 μm to 150 μm, and more preferably 20 μm to 100 μm. If it is too thin, it is difficult to handle and is not preferable from the viewpoint of physical durability as a marking film. On the other hand, if it is too thick, not only is it disadvantageous in terms of cost, but also haze is noticeable in appearance, which is not preferable.

The fluororesin layer may contain an ultraviolet absorber for the purpose of improving weather resistance.

The colored layer is formed by applying or drying a resin solution containing a colorant on the fluororesin layer. The coloring layer may be formed on the entire surface of the fluororesin layer, or may be formed only on a part thereof, depending on the purpose. Further, two or more layers may be stacked. As the resin forming the colored layer, an acrylic resin, a urethane resin, a silicone resin, a solvent-soluble fluorine-based resin, and the like are preferable. Among them, a solvent-soluble fluorine-based resin is preferable from the viewpoint of weather resistance and heat resistance. . Examples of the solvent-soluble fluorine-based resin include vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene and / or monochlorotrifluoroethylene-hydroxyalkyl vinyl ether-alkyl vinyl ether copolymer resin, and the like. .

As the coloring agent to be blended in the coloring layer, particularly those having excellent weather resistance and heat resistance are preferable general organic pigments,
In addition to inorganic pigments, metal flakes such as aluminum known as metallic pigments and titanium dioxide-coated mica known as pearl pigments may be mentioned. These metallic pigments or pearl pigments preferably have a particle size of 2 to 200 μm, more preferably 4 to 150 μm, especially 5 to 100 μm.
Those having a particle size of μ are preferred.

In the case of a pearl pigment, the titanium oxide of the coating layer is preferably of a rutile type from the viewpoint of weather resistance. Further, a coloring agent such as silver oxide may be colored, may exhibit an interference color, and may have a silver tone or a silk tone.

General organic pigments and inorganic pigments that can be preferably used are specifically described in Color Index 3rd Edition (1971) and Supp
lements (1975) Publisher; The Society of Dyers and Col
You can choose from ourists.

The following colorant names are the Color Index Ge-neric N specified in the same book.
According to ame. For example, Y-1 means CIPi-gment Yellow1. O is Orange, R is Red, V is Violet, B is Blu
e and G represent Green, Br represents Brown, Bk represents Black, and W represents White, respectively.

First, as the yellow pigment, an azo-based condensed polycyclic pigment or a metal complex salt-based pigment is particularly preferable, and among the azo-based pigments, insoluble monoazo pigments (Y-97, Y-116, Y-120, Y-151, Y-151) are preferable.
-154), disazo pigments (Y-81, Y-83, Y-155),
Condensed azo (Y-93, Y-94, Y-95, Y-128) is preferred, and in the condensed polycyclic system, anthraquinone pigments (Y-24, Y
-108, Y-147, Y-123, Y-99), isoindolinone pigments (Y-109, Y-110, Y-173), isoindoline pigments (Y-139), quinophthalone pigments (Y-138) Is preferable, and a copper azomethine pigment (Y-117,
Y-129), a nickel nitroso pigment (Y-153) and a nickel azo pigment (G-10) are preferred. Further, in the inorganic system, iron oxide yellow (Y-42), titanium-antimony-nickel oxide (Y-53) and the like are preferable.

Azo pigments and condensed polycyclic pigments are particularly preferred as orange pigments, and insoluble monoazo pigments (O-36, O-5, O-38, O-60, O-62) and diazo pigments are preferred as azo pigments. Pigments (O-34) and condensed azo pigments (O-31) are preferable. As condensed polycyclic pigments, perylene pigments (O-4)
3), anthraquinone pigments (O-40, O-51), isoindolinone pigments (O-42), and quinacridone pigments (O-48, O-49).

As the red pigment, azo pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferable. As the azo pigment, insoluble monoazo pigments (R-2, R-6, R-7, R-9, R-
10, R-12, R-14, R-112, R-146, R-147, R
-170, R-171, R-175, R-185, R-187, R-18
8, R-208), azo lake pigments (R-52: 2, R-11
5, R-151, R-243), condensed azo pigments (R-144, R-144)
-166, R-214, R-220, R-221, R-242) and disazo pigments (R-38, R-37). As the condensed polycyclic pigment, anthraquinone pigments (R-168) , R-17
7, R-216), thioindigo pigment (R-88), perinone pigment (R-194), perylene pigment (R-123, R-
149, R-178, R-179, R-190, R-224), quinacridone pigments (V-19, R-122, R-202, R-207,
R-209, R-206), and as a new pigment, a diketopyrrolopyrrole-based pigment (manufactured by Ciba Geigy)
Irgazin DPP Red BO). Inorganic pigments include red iron oxide (red iron R-101), zinc / iron oxide (R-225) and the like.

As violet pigments, azo pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferable. Monoazo pigments (V-50) are used as azo pigments, and perylene pigments (V-29) are used as condensed polycyclic pigments. ), Anthraquinone pigments (V-31, V-
33), thioindigo pigments (V-38, V-36), quinacridone pigments (V-19), dioxazine pigments (V-2)
3, V-37), cobalt phosphate (V-14: 1) as an inorganic pigment, ferrolite violet pigment (V-1
8), cobalt lithium vanadium phosphate pigment (V-47) and the like.

As the blue pigment, a phthalocyanine pigment, a condensed polycyclic pigment, and an inorganic pigment are particularly preferred. As the fusocyanine pigment, an α-type copper phthalocyanine pigment (B-15: 1,
B-15: 2), β-type copper phthalocyanine pigment (B-15: 3,
B-15: 4), ε-type phthalocyanine pigment (B-15: 6),
As metal-free phthalocyanine pigments (B-16) and condensed polycyclic pigments, indanthrone pigments (B-60, B-21, B
-22, B-64), as an inorganic pigment, navy blue (B-27),
Ultramarine blue (B-29), cobalt-aluminum oxide pigment (B-28), cobalt-chromium-aluminum oxide pigment (B-36), and the like.

As the green pigment, a phthalocyanine pigment, a condensed polycyclic pigment, and an inorganic pigment are particularly preferable. As the phthalocyanine pigment, a medium chlorinated copper phthalocyanine pigment (G-3
7), highly chlorinated copper phthalocyanine pigments (G-7), highly chlorobrominated copper phthalocyanine pigments (G-36), and condensed polycyclic pigments such as biolanthrone green (G-47);
Examples of the inorganic pigment include a chromium oxide pigment (G-17) and a cobalt-titanium-nickel-zinc oxide pigment (G-1).
9) and cobalt-titanium pigments (G-50).

As brown pigments, azo pigments, condensed polycyclic pigments and inorganic pigments are particularly preferred. As azo pigments, monoazo pigments (Br-25, Br-32) and metal complex salt azo pigments (Br-
5, Br-2), condensed azo pigments (Br-23), anthraquinone pigments (Br-28) and perylene pigments (Br-26) as condensed polycyclic pigments, and iron oxide pigments as inorganic pigments Pigment (Br-6), iron-chromium oxide pigment (Br-29), zinc-iron oxide pigment (Br-31) and the like.

As black pigments, there are pigments that can be preferably used for organic pigments and inorganic pigments, respectively. As organic pigments, aniline black (Bk-1) and perylene black (Bk-
31), carbon black (Bk-
7), bone black (Bk-9), iron black (Bk-11), and cobalt oxide pigment (Bk-13).

As the white pigment or the extender (transparent) pigment, an inorganic pigment is particularly preferable. For example, zinc white (W-4), zinc sulfide (W-7), titanium dioxide (W-6), calcium carbonate (W-) 18), clay (W-19), barium sulfate (W-21), alumina white (W-24), silica (W-19)
-27), muscovite (W-20), talc (W-26) and the like.

In addition, an ultraviolet absorber or a light stabilizer can be used in the colorant layer for the purpose of improving weather resistance, and a leveling agent, an antifoaming agent or the like is added for the purpose of adjusting coating properties and printability. Agents can be used. As the ultraviolet absorber, benzotriazole-based, benzophenone-based, and cyanoacrylate-based ones are preferred, and benzotriazole-based ones are more preferred from the viewpoint of long-lasting effects. Hindered amine-based light stabilizers are effective and preferred.

Although the adhesive layer in the present invention is not particularly limited, an organic polymer-based pressure-sensitive adhesive is preferably used in view of the form of use, and specifically, for example, an acrylic resin, a fluororesin, natural or Among them are synthetic rubber-based resin, urethane-based resin, silicon-based resin and the like, and among them, acrylic resin, silicone-based resin and fluorine-based resin are preferable. Examples of the acrylic resin include ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate,
Acrylate resins such as -methylbutyl acrylate, 2-hydroxyethyl acrylate, cyanoacrylate and the like, and ethyl methacrylate, methyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-
It is a methacrylate resin such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, 2-methylbutyl methacrylate, 2-hydroxyethyl methacrylate, or hydroxypropyl methacrylate. Further, there are copolymers composed of the above-mentioned acrylic compound and copolymers composed of the above-mentioned acrylic compound and vinyl esters such as vinyl acetate and vinyl propionate, and styrene. As the acrylic compound forming these copolymers, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2hydroxyethyl acrylate and acrylic acid are preferable, and ethyl acrylate and butyl acrylate are particularly preferable.

Although the thickness of the adhesive layer is not particularly limited, it is generally 5 μm to 500 μm, preferably 10 μm to 300 μm, and more preferably 20 μm to 100 μm.

Further, various additives and colorants for improving weather resistance, heat resistance, adhesive strength, and imperica can be added to the adhesive layer.

As these additives and colorants, for example, ultraviolet absorbers, light stabilizers, antioxidants, tackifiers, organic pigments,
Examples include inorganic pigments and metal flakes.

The above-mentioned releasable base material layer is peeled off and discarded from the above-mentioned adhesive layer when the product of the present invention is adhered to an adherend and used. Therefore, before use of the product of the present invention, any material can be used as long as it is stably adhered to the adhesive layer and can be easily peeled off by hand at the time of use. It is preferable in improving the image quality.

Such a peelable base material layer is preferably a base material layer of paper, polyester, polypropylene, polyimide, polyethylene, or the like, which is easily peeled by a silicone-based resin coat or / and a fluorine-based resin coat. It is preferably paper or polyester coated with a resin coat and / or a fluororesin, or a polypropylene base material. In particular, in the case of paper, those coated with polyethylene or clay on both sides or one side, and those subjected to super calendering are particularly preferable in terms of improving smoothness.

The peeling force of the peelable substrate layer from the adhesive layer is not particularly limited, but is generally 180 at a speed of 300 mm per minute at room temperature.
0.5 to 100 g / cm when peeling is performed, preferably 1 to 50 g / cm
cm. If it is too light, it tends to peel off before use, and if it is too heavy, workability tends to be poor at the time of use.

The thickness of the releasable base material layer is not particularly limited, but is generally 10 to 1000 μm, preferably 20 to 500 μm, and more preferably 30 to 300 μm. Tends to decrease.

It goes without saying that the marking film structure of the present invention may be manufactured by any method that satisfies the constitutional requirements of Claims 1. However, a particularly preferable manufacturing method will be described below. The layer may be formed according to the properties of the fluororesin used, and an appropriate one may be selected from a casting method, a calendar method, an extrusion method, and the like. The colored layer is obtained by applying or printing a resin solution containing a coloring agent and other necessary additives on the fluororesin layer, followed by drying. In order to improve the adhesion between the coloring layer and the fluororesin layer, it is preferable to activate the surface of the fluororesin layer in advance by a method such as corona treatment.

Further, a colored layer may be formed after coating or printing a primer layer on the fluororesin layer for improving adhesion and weather resistance.

As the primer layer, those equivalent to the resin used for the colored layer can be used. For example, a layer obtained by removing only the colorant from the colorant-containing resin composition for forming the colored layer can be used.

The coating or printing method of the resin solution for forming the primer layer or the colored resin layer is not particularly limited, for example, a spray coating method, a curtain coating method, a roll coating method, a screen printing method, a rotary screen printing method,
A gravure printing method is preferably used.
The thickness of the primer layer or the colored resin layer is not particularly limited, but is generally 0.5 to 100 µm, preferably 1 to 50 µm.

Primer layer or colorant (colored layer) on fluororesin layer
A support layer having a removable adhesive layer on the back surface of the fluororesin layer can be provided for the purpose of improving workability and maintaining surface clarity when forming the film. As the material of the support layer, paper, polyester, polypropylene, polyethylene and the like can be used, and the thickness is preferably 50 to 500 μm from the viewpoint of workability.

The adhesive layer may be formed directly on the colored resin layer, but is generally obtained by coating the releasable base material layer in advance, drying it, and then bonding it to the colorant layer. In addition, a lighter release type peelable substrate layer can be stuck on the adhesive layer for the purpose of protecting the adhesive layer formed on the release substrate layer before use. .

The marking structure of the present invention is not particularly limited as long as it satisfies Claim 1, but is generally laminated in order from the surface with at least a fluororesin layer, a coloring layer, an adhesive layer, and a peelable substrate layer. This is a particularly preferred embodiment from the viewpoint of improving sharpness.

The marking film structure thus obtained is excellent not only in weather resistance, heat resistance, solvent resistance and stain resistance but also in surface clarity and has a PGD value of 0.3 or more. The sharpness is a factor that governs the beauty of the finished appearance of coatings and marking films.In particular, recently, interest in high-quality painted products with relatively large areas such as automobile outer panels has increased,
Along with this, there is a demand for a marking film to be attached to these high-grade painted products, or to be applied as a substitute for the high-grade painted products, with high sharpness. The definition and content of sharpness are described in “Survey Report on Evaluation Methods for Sharpness (First Report)” edited by the Japan Paint Inspection Association, Paint Testing Method Study Group (Western) Sharpness Subcommittee (Showa) (December 59)
The sharpness is higher as the surface is glossier and closer to the mirror surface, and lower as the surface becomes matt. Instruments for quantitatively evaluating sharpness include a PGD meter, a sharpness measuring instrument NPIG, a flow comparator, and a dragon.
It is said that the evaluation by the total has the highest correlation with the visual evaluation by the expert. The PGD meter illuminates test patterns of different sizes in stages and visually judges them by transferring them to the surface of the sample. The higher the surface sharpness of the sample, the finer the test pattern can be read and the higher the PGD value. Conventional marking film structures generally have a PGD value of 0.2 or less,
The marking film structure of the product of the present invention is 0.3 or more, and has a sharpness comparable to that of a high-grade painted product such as an automobile outer panel.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

Example 1 Ethylene-tetrafluoroethylene copolymer resin Aflon
COP55AX (manufactured by Asahi Glass Co., Ltd.) was formed by a T-die extrusion method at a die temperature of 300 ° C. to obtain a transparent film having a thickness of 40 μm.
One side is corona treated so that the "wetting" according to JIS-K6768 becomes 50, and furthermore, the non-corona side is laminated with 125μ thick PET process paper having a 5μ thick removable adhesive layer. It was set to 1.

The ink-1 was solid-printed on the corona-treated surface of the printing material-1 using a 180-mesh screen, and dried at 80 ° C. for 60 minutes to obtain a colored layer having a thickness of 10 μm. Light release PET of adhesive liner 1
Peel off the film, press it according to the colored layer and press
The PET process paper was peeled off to obtain a marking film structure (1).

After sticking to the float glass, the sharpness was measured by a PGD meter (PGD-IV, manufactured by Tokyo Koden Co., Ltd.) and found to be 0.8.

Example 2 Ink 2 was applied to printing substrate 1 with a three-reverse roll coater to a dry thickness of 15 μm and dried at 140 ° C. for 6 minutes. Film structure (2) was obtained.

Example-3 A printing material-1 was solid-printed using a 180-mesh screen as a primer with a composition obtained by removing all the pigments from ink-1. Further, ink-1 was similarly solid-printed thereon. After drying at 60 ° C. for 60 minutes, a marking film structure (3) was obtained in the same manner as in Example-1.

Example 4 A marking film structure (4) was obtained in the same manner as in Example 1 except for using the printing raw material-2.

Example -5 PET film of printing raw material-1 A marking film structure (5) was obtained in the same manner as in Example 1 except that the paper was not attached.

Example -6 A marking film structure (6) was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive liner 2 was used.

Comparative Example-1 Ink was applied to a 50 μm thick white PVC-based marking film having a 30 μm thick (commercially available) pressure-sensitive adhesive layer.
1 is solid printed using a 180 mesh screen and 80 ℃
After drying for 60 minutes in the same manner as above, the composition obtained by removing only the pigment from Ink-1 was used as a clear coating agent, and similarly printed and dried to obtain a marking film structure (7).

Comparative Example 2 Lightly peeling the adhesive liner 1 directly onto the corona-treated surface of the ethylene-tetrafluoroethylene copolymer resin film used in Example 1 and then laminating the adhesive liner 1 onto the corona-treated surface, followed by heavy peeling PET film (peelability) The base film was peeled off and bonded to the marking film used in Comparative Example 1 to obtain a marking film structure (8).

Comparative Example 3 A 50 μm thick silver metallic tone PVC-based marking film having a 30 μm thick (commercially available) pressure-sensitive adhesive layer was directly used as a marking film structure (9).

Comparative Example-4 A 50 μm thick vinylidene fluoride / acrylic two-layer film (AT-50Y manufactured by Kureha Chemical Industry Co., Ltd.) was further added to the marking film of Comparative Example-3 with the vinylidene fluoride layer on the outside.
It was press-bonded with a 180 ° C. laminating roll to obtain a marking film structure (10).

Preparation of printing stock-2 Ethylene-tetrafluoroethylene copolymer resin Aflon
100 parts by weight of COP88AX (manufactured by Asahi Glass Co., Ltd.) is blended with 0.2 parts by weight of a dimer mark LA-31 (manufactured by Adeka Argas Co., Ltd.) of a benzotriazole-based UV absorber. Extruded and formed into a thickness of 50μ
Was obtained.

Corona treatment is applied to one side so that the "wetting" according to JIS K 6768 becomes 50, and then a non-corona surface is laminated with a 75μ thick PET process paper with a 5μ thick removable adhesive layer. -2.

Preparation of Ink-1 100 parts by weight of a solvent-soluble fluororesin solution (Lumiflon manufactured by Asahi Glass Co., Ltd.) were mixed with Lumiflon and a pigment (Shinkasha Gold YT-823D manufactured by Ciba Geigy) at a weight ratio of 3: 1. 20 parts by weight of meat milled by this roll mill, 10 parts by weight of aluminum paste (manufactured by FM-1440 Toyo Aluminum Co., Ltd.), 10 parts by weight of pearl pigment (manufactured by Exterior Bright Goldmar Co., Ltd.), ultraviolet absorber (Seesorb 706 Shiroishi calcium Co., Ltd. and Tinuvin 234
0.8 parts by weight, light stabilizer (Tinuvin 622)
1 part by weight of LD Ciba Geigy), 0.02 parts by weight of an antifoaming agent (SC-5570, manufactured by Toray Dow Corning Silicone Co., Ltd.), and 20 parts by weight of diluent cellosolve acetate are thoroughly mixed and stirred, and then a curing agent (Coronate EH Nippon Polyurethane ( stock)
8 parts by weight) and stirred to obtain Gold Metallic Ink-1.

Preparation of Ink-2 20 parts by weight of a solvent-soluble fluororesin (manufactured by Kainer 9301 Penwort) were dissolved in 80 parts by weight of a mixed solvent of equivalent amounts of cyclohexanone and isophorone, and an aluminum paste (FM-1130) was prepared.
5 parts by weight of Toyo Aluminum Co., Ltd., 25 parts by weight of pearl pigment (manufactured by Iriodin 103WS Merck), 1 part by weight of an ultraviolet absorber (manufactured by Tinuvin 213 Ciba Geigy), and 30 parts by weight of cyclohexanone were added, and the mixture was sufficiently stirred to obtain white pearl. Ink-2 was obtained.

Preparation of Adhesive Liner 1 100 parts by weight of a solvent-type acrylic pressure-sensitive adhesive (Nissetsu PE-121 manufactured by Nippon Carbide Industry Co., Ltd.), 1.4 parts by weight of an ultraviolet absorber (Seasorb 704, manufactured by Shiroishi Calcium Co., Ltd.), and a light stabilizer (Tinuvin) 622LD Ciba Geigy) 0.7 parts by weight, solvent tertiary butanol 10 parts by weight and toluene 20 parts by weight, crosslinking agent (Coronate EH Nippon Polyurethane Co., Ltd.)
0.1 parts by weight are sufficiently mixed and stirred, and coated on a 75-μm-thick heavy release type PET-based release base material (Therapy BM-2 manufactured by Toyo Metallizing Co., Ltd.) to a dry thickness of 40 μm. After drying at 100 ° C for 10 minutes, light release type 25μ PET
Film (Therapy BK Toyo Metallizing Co., Ltd.)
Manufactured) was obtained to obtain an adhesive liner 1.

Preparation of Adhesive Liner 2 Adhesion was performed in the same manner as in the preparation of Adhesive Liner 1 except that the heavy release type PET-based release substrate was replaced with a paper-based release substrate (OKC 110NCY manufactured by Oji Chemical Co., Ltd.). Liner 2 was obtained.

Evaluation method Heat resistance The marking film structure was attached to a melamine alkyd white coated plate (manufactured by Nippon Test Panel Co., Ltd.), placed in an oven at 100 ° C., taken out after 1000 hours, and visually evaluated for appearance.

Substantially no discoloration compared to the original piece ○ Discoloration was observed slightly compared to the original piece △ Discoloration was noticeably changed to brown or black × Weather resistance Marking film structure with melamine alkyd white coated plate (Made by Nippon Test Panel Co., Ltd.) Sunshine weather meter (WOM) (WEL-SUN-HC manufactured by Suga Test Machine Co., Ltd.) (Condition: 120 minutes cycle (including 18 minutes rainfall))
, The black panel temperature was set to 63 ± 3 ° C.), and after exposure for 5000 hours, the sample was taken out and visually evaluated.

Hardly discolored or reduced gloss compared to the original piece ○ Slightly discolored or reduced gloss △ Notable discoloration or reduced gloss × Solvent resistance Methyl ethyl ketone on the surface of the marking film structure Was placed in a closed container kept at 30 ° C. for 1 hour, taken out, and the surface was thoroughly wiped. Then, the appearance change was visually judged.

Those with little abnormality such as gloss reduction compared to the original pieces ○ Those with considerable gloss reduction compared to the original pieces △ Those whose surface layer dissolved and significantly changed in appearance × Stain resistance Marking film with oil-based magic ink The surface of the structure was wiped off, exposed to WOM for 500 hours, and taken out. The surface was wiped with a cotton cloth coated with isopropyl alcohol, and the appearance change was visually determined.

What did not remain after the magic ink at all ○ Slightly black portion remained △ Almost all remained black × Visibility Marking film structure was adhered to a float glass plate PGD meter (PGD-IV Tokyo photoelectric (Manufactured by Co., Ltd.).

0.2 or less A level that is inferior at first glance compared to high-grade painted panels such as automobile outer panels 0.3-0.5 A level that is inferior to high-grade painted panels but not so inferior 0.6 or more A level of sharpness equivalent to that of high-grade painted panels Table 1 shows the test results of each of the examples.

[Effects of the Invention] The marking film structure of the present invention combines weather resistance, heat resistance, solvent resistance, stain resistance, and sharpness at a high level that could not be achieved with conventional marking films, such as automobile bonnets. It can be used on a high-grade painted plate without any discomfort in appearance, and can maintain its initial function stably for a long time even under severe conditions.

Claims (4)

(57) [Claims] At least a colorless layer made of a solvent-soluble fluororesin, an adhesive layer, and a non-colored fluororesin layer laminated on a peelable substrate in this order on the back surface, and the sharpness of the surface is enhanced. Is PG
A marking film structure having a D value of 0.3 or more. 2. The resin layer according to claim 1, wherein said fluorine-based resin layer is a resin layer made of an ethylene-tetrafluoroethylene-based copolymer.
A marking film structure as described. 3. The marking film structure according to claim 1, wherein said releasable base material layer is made of paper, polyester sheet or polypropylene sheet coated with a silicone-based release agent or a fluorine-based release agent. Stuff. 4. The marking film structure according to claim 1, wherein at least one of said fluororesin layer, coloring layer and adhesive layer contains an ultraviolet absorber and / or a light stabilizer. .