JPH04141414A - Marking film structure - Google Patents

Abstract

PURPOSE:To obtain the marking film structure which may be used for e.g. the roof and the bonnet of an automobile by a method in which the film has the fluoroplastic layer with at least colored layer, an adhesive layer and the base layer of peeling property, and the clearness of its surface is caused to be at least specified value by PGD value. CONSTITUTION:This marking film structure has the fluoroplastic layer with at least a Colored layer, an adhesive layer and the base layer of peeling property, and the clearness of its surface is caused to be at least 0.3 by PGD value, and then it has the clearness equal to the high grade coated object of the outer plate of an automobile. As the fluoroplastic, the copolymer of ethylene.tetrafluoroethylene is preferably especially, but in said materials, the resin in which the contained mol ratio of tetrafluoroethylene/ethylene is 40/60 - 60/40 and the content of the perfluoroalkyl vinyl monomer shown by the general formula of CH2=CH.CnF2n+1 (n is the integer of 2-10) is 0.1-10mol%, is especially preferably from the points of transparency, the adhesion with a colored layer and film-making property etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a marking film with excellent weather resistance, heat resistance, solvent resistance, stain resistance, and image clarity.
This invention relates to a marking film structure that can be used on surfaces that receive a large amount of light and are exposed to high temperatures, such as the bonnet roof of an automobile.

[Conventional technology]

Marking films have been widely used for signboards,
It is used as an alternative to paint on automobiles, vehicles, etc. However, conventional marking films are mainly made of vinyl chloride resin, and their weather resistance and heat resistance are insufficient.
Heat resistance was also not sufficient. In particular, when used on surfaces that receive a large amount of light and are exposed to high temperatures for long periods of time, such as car bonnets and roofs, problems such as browning, cracking, and peeling occur within just a few years, and the reality is that they have not been put to practical use. Furthermore, in recent years, it has been pointed out that when a marking film is applied to a level 4 (7) level of automobile painting, the sharpness of the marking film is poor and the appearance is poor.

In addition, conventional marking films did not have sufficient solvent resistance, so they could not be used in cases where they would be directly exposed to solvents.

Furthermore, once dirt adhered to conventional marking films, the dirt could not be removed, and the appearance deteriorated over time and often did not return to its original state even after wiping.

Therefore, some people are using PV to replace the conventional marking film.
It has been considered to laminate a transparent film of F2 or PVdF, but in reality, sufficient improvements have not been made particularly in terms of heat resistance, weather resistance, and image clarity.

[Problem to be solved by the invention]

The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and the conventional masking film does not have sufficient heat resistance, weather resistance, solvent resistance, sharpness, and stain resistance. The object of the present invention is to provide a marking film structure that can be used in places where it could not be used practically due to lack of markings, such as the roof and bonnet of a car.

[Means for solving problems]

The present invention was made to solve the above-mentioned problems, and includes at least a fluororesin layer having a colored layer, an adhesive layer,
and a releasable base material layer, and a marking film structure characterized in that the surface has a PGD value of 0.3 or more.

In the present invention, examples of the fluororesin constituting the fluororesin layer include ethylene-tetrafluoroethylene copolymer, trifluoroethylene copolymer, vinylidene fluoride copolymer, vinyl fluoride polymer, and alkoxy fluoride. ethylene polymer,
Tetrafluoroethylene/hexafluoropropylene copolymers are mentioned, and ethylene/tetrafluoroethylene copolymers are particularly preferred, but among these, tetrafluoroethylene/ethylene molar ratios are 40/60 to 60/ 40, and the content of perfluoroalkyl vinyl monomer represented by the general formula CI (□-〇H-Cn F2n+1 (where n in the formula is an integer of 2 to 10) is 01 to 10 mol%. It is particularly preferable in terms of transparency, adhesion with colored layers, film formability, etc. Such ethylene-tetrafluoroethylene copolymers can be produced, for example, by the method described in Japanese Patent Publication No. 59-50163. It is also possible to use commercially available products. Examples of commercially available products include
Aflon COP (manufactured by Asahi Glass (4Q)), Neoflon ETI?E (manufactured by Daikin Industries, Ltd.), and Texel (manufactured by DuPont) are preferred.

Furthermore, prior to laminating the colored layer on the fluororesin layer, the surface of the fluororesin layer was activated to have a "wetting" level of 30 to 54 with J]'S 6768, and further 35 to 54. It is preferable to leave it on to improve adhesion. The activation treatment method is not particularly specified and may be any method, but corona discharge treatment is preferred from the viewpoint of the process.

The thickness of the fluororesin layer is not particularly limited, but is generally 10μ to 200μ, preferably 15μ to 150μ.
μ, more preferably 20 μ to 100 μ.

If it is too thin, it will be difficult to handle, and it is also unfavorable from the viewpoint of physical durability as a marking film. Moreover, if it is too thick, not only is it disadvantageous in terms of cost, but also the haze in appearance becomes noticeable, which is undesirable.

An ultraviolet absorber may be added to the fluororesin layer for the purpose of improving weather resistance.

The colored layer is formed by coating or printing a resin solution containing a coloring agent on the fluororesin layer and then drying it. The colored layer may be formed on the entire surface of the fluororesin layer depending on the purpose, or may be formed only on a part of the fluororesin layer. Furthermore, two or more layers may be stacked. Preferable examples of the resin forming the colored layer include acrylic resins, urethane resins, silicone resins, solvent-soluble fluororesins, etc. Among them, solvent-soluble fluororesins are preferred from the viewpoint of weather resistance and heat resistance. . Examples of the solvent-soluble fluororesin include vinylidene fluoride-tetrafluoroethylene-hexafluorobrobylene copolymer resin, tetrafluoroethylene and/or monochlorotrifluoroethylene-hydroxyalkyl vinyl ether alkyl vinyl ether copolymer resin, etc. .

The coloring agent to be added to the colored layer is preferably one with excellent weather resistance and heat resistance, in addition to general organic pigments and inorganic pigments, as well as metal flakes such as aluminum, known as metallic pigments, or var pigments. Examples include known titanium dioxide-coated mica. These metallic pigments or bar pigments preferably have a particle size of 2 to 200μ, more preferably 4 to 150μ, especially 5 to 150μ.
A particle size of 100 microns is preferred.

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

Common organic pigments and inorganic pigments that can be preferably used include Co1our Index 3rd Edi.
tion (1971) and supplements
s (1975) Publisher The Society of D
You can choose from Yersand Colourists.

The following colorant names are based on the Co1our Index specified in the same book.
By Ge-neric Name. For example, Y-1
means C,TPi-gment Yellow. Also, O is Orange.

R is RedSV is Violet, B is Blue, G
is Green, Br is Brown, Bk is Black
, W represents White, respectively.

First, as yellow pigments, azo condensed polycyclic pigments and metal complex salt pigments are particularly preferable, and among azo pigments, insoluble monoazo pigments (Y-97, Y-116, Y-120, Y15
], Y-154), disazo pigment (YB2, Y-83)
, Y-155), fused azo (Y-93, Y-94, Y
-95, ¥-128) are preferable, and anthraquinone pigments (Y-24, Y-108, Y-1,47
, Y-123, Y-99), inintrinon pigment (
¥109, Y (10, Y-173), isoindoline pigment (Y-1,39), quinophthalone pigment (Y-13)
8) is preferred, and copper azomethine pigment (Y
117, Y-129), nickel nitroso pigment (Y-1
53), nickel azo pigment (G-10) is preferred. Furthermore, among inorganic compounds, iron oxide yellow (Y-42), titanium-antimony-nickel oxide (Y-53), etc. are preferable.

As orange pigments, azo pigments and condensed polycyclic pigments are particularly preferred.As ab pigments, insoluble monoazo pigments (0
-36, O-5, 0-38, 0-6010-62), disazo pigment (0-34), condensed azo pigment (0-3
1) is preferred, and examples of the condensed polycyclic pigments include perylene pigments (0-43), Anne I/laquinone pigments (0-40,
Preferred examples include indolinone pigments (0-51), indolinone pigments (○-42), and quinacridone pigments (048,0-4,9).

As red pigments, azo pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferred; as ab pigments, insoluble monoazo pigments (R-2, R-6, R-7, R-9, R- 1
0, R-12, R-14, R-11,2, R-146,
R-xu, R-170, R, -171, R-175, R
-185, R-187, R-188, R-208),
Azo lake pigment (R-52:2, R-115, R, -
151, R-243), condensed azo pigment (R-144,
R, -166, R-21,4, R-220, R-221
, R-242), disazo pigments (R38, R-37)
), and examples of condensed polycyclic pigments include anthraquinone pigments (R-168, R-177, R-216), thioindigo pigments (R-88), perinone pigments (R
-194), perylene pigments (R123, R-149)
, R-178, R-179, R-190, R, -224
), quinacridone pigments (V-19, R-122, R,
-202, R-207, R-209, R-206) are preferred, and a newer pigment is a diketopyrrolobyrole pigment (Irgazine DPP RED〇-DOBO manufactured by Ciba Geigy). Inorganic pigments include red iron oxide (red iron oxide R-101), zinc iron oxide (R-2
25) etc.

Particularly preferable purple pigments are azo pigments, condensed polycyclic pigments, and inorganic pigments. Examples of the azo pigments include monoazo pigments (V-50), and perylene pigments (V-29) as the condensed polycyclic pigments. ), anthraquinone pigment (V-3
1, V-33), thioindigo pigment (V-38, V
-36), quinacridone pigment (V-19), dioxazine pigment (V-23, V-37), inorganic pigments include cobalt phosphate pigment (V-14.1), ferrolite violet pigment (V- 18), cobalt lithium vanadium phosphate pigment (V-47), and the like.

Phthalocyanine pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferred as blue pigments.
, B-15:2), β-type copper phthalocyanine pigment (B-15:2)
-15:3, B-15/4), ε-type phthalocyanine pigment (B-15/6), metal-free phthalocyanine pigment (B
-16), condensed polycyclic pigments include indanthrone pigments (B-60, B-21, B-22, B-64), and inorganic pigments include navy blue (B-27) and ultramarine blue (B-29). )
, cobalt-aluminum oxide pigment (B-28),
Cobalt-chromium-aluminum oxide pigment (B-
36) etc.

As the green pigment, phthalocyanine pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferable, and as the phthalocyanine pigments, medium chlorinated copper phthalocyanine pigments (G-37
), highly chlorinated copper phthalocyanine pigment (G-7), highly chlorinated copper phthalocyanine pigment (G-36), and violanthrone green (G-4) as the condensed polycyclic pigment.
7) As the inorganic pigment, chromium oxide pigment (G-1
7), cobalt-titanium-nickel-zinc oxide pigment (G-19), cobalt-titanium pigment (G-50)
) etc.

Particularly preferable brown pigments are azo pigments, condensed polycyclic pigments, and inorganic pigments. Examples of azo pigments include monoazo pigments (Br-25, Br-32) and metal complex azo pigments (Br-5). , Br-2), condensed azo pigment (Br-2)
3) As the condensed polycyclic pigment, anthraquinone pigment (
Br-28), perylene pigment (Br-26), inorganic pigments include iron oxide pigment (Br-6), iron-chromium oxide pigment (Br-29), zinc-iron oxide pigment ( B
r31), etc.

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

Inorganic pigments are particularly preferred as white pigments or extender (transparent) pigments, such as zinc white (W-4), zinc sulfide (W-7), titanium dioxide (W-6), and calcium carbonate (W-4). 18), clay (W-19), barium sulfate (W-21), alumina white (W-2)
4), silica (W-27), muscovite (W-20)
, talc (W-26), and the like.

In addition, ultraviolet absorbers and light stabilizers can be used in the colorant layer to improve weather resistance, and leveling agents, antifoaming agents, etc. can be added to adjust coating properties and printability. Agents can be used. As the ultraviolet absorber, benzotriazole-based, benzophenone-based, and cyanoacrylate-based ones are preferred, and among these, benzotriazole-based ones are preferred from the viewpoint of long-lasting effects. As the light stabilizer, hindered amine type ones are effective and preferred.

Although the adhesive layer in the present invention is not particularly limited, organic polymer pressure-sensitive adhesives are preferably used in view of the form of use. Specifically, for example, acrylic resin, fluorine resin, natural or There are synthetic rubber resins, urethane resins, silicone resins, etc., and among them, acrylic resins, silicone resins, and fluorine resins are preferable.

Examples of acrylic resins include ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
Inbutyl acrylate, n-hexyl acrylate,
Acrylic acid ester resins such as 2-ethylhexyl acrylate, n-octyl acrylate, 2-methylbutyl acrylate, 2-hydroxyethyl acrylate, cyanoacrylate, and ethyl methacrylate, methyl methacrylate, n-propyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, 2-methylbutyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc. This is a methacrylic acid ester resin. Further, there are copolymers made of the above-mentioned acrylic acid compounds, and copolymers made of the above-mentioned acrylic compounds 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 preferred, and ethyl acrylate and butyl acrylate are particularly preferred.

The thickness of the adhesive layer is not particularly limited, but is generally 5μ to 500μ, preferably lO to 300μ,
More preferably, it is 20μ to 100μ.

Furthermore, various additives and colorants can be added to the adhesive layer to improve weather resistance, heat resistance, adhesive strength, and adhesive strength.

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

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

Such removable base material layers include paper, polyester, polypropylene, polyimide, which has been easily peeled off with a silicone resin coat and/or a fluorine resin coat, etc.
It is preferably a base material layer of polyethylene or the like, and more preferably a paper, polyester, or polypropylene base material coated with a silicone resin or/and a fluorocarbon resin. In particular, in the case of paper, it is preferable to use polyethylene coating or clay coating on both sides or one side, and it is particularly preferable to use supercalendering to improve smoothness.

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

The thickness of the above-mentioned releasable base material layer is not particularly limited, but is 10 to 1000μ, preferably 20 to 500μ,
More preferably, the thickness is 30 to 300μ, and if it is too thin or too thick, workability 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 constituent requirements of claim 1, but a particularly preferred manufacturing method will be described below. The layer can be formed according to the properties of the fluororesin used, such as casting method,
An appropriate method may be selected from among the calendar method, extrusion method, etc. The colored layer is obtained by coating or printing a resin solution containing a coloring agent and other necessary additives on the fluororesin layer, and then drying it. In order to improve the adhesion between the colored 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.

-1 of the fluororesin layer to further improve adhesion and weather resistance.
A colored layer may be formed after printing.

The same resin as the resin used for the colored layer can be used for the brimer layer, and for example, a resin composition containing a coloring agent for forming the colored layer without only the coloring agent can be used.

There are no particular limitations on the coating or printing method of the resin solution for forming the brimer layer or the colored resin layer, but examples include spray coating, curtain coating, roll coating, screen printing, rotary screen printing, and gladia. Preferred examples include printing methods. The thickness of the brimer layer or colored resin layer is not particularly limited, but is generally 05 to 100μ, preferably 1 to 50μ.
It is.

A support layer having a removable adhesive layer on the back side of the fluororesin layer for the purpose of improving workability and maintaining surface clarity when forming a brimer layer or a colorant (colored layer) on the fluororesin layer. can make a profit. As the material of the support layer, paper, polyester, polypropylene, polyethylene, etc. can be used, and the thickness is preferably 50 to 500 .mu.m from the viewpoint of workability.

The adhesive layer may be formed directly on one of the colored resin layers, but it can also be obtained by coating it on the releasable base material layer in advance, drying it, and then bonding it with the coloring agent layer. It will be done. Furthermore, in order to protect the adhesive layer previously formed on the release base layer 2 until it is used, it is possible to bond a more easily releasable base material layer on top of the adhesive layer. can.

Although the marking structure of the present invention is not particularly limited as long as it satisfies claim 1, it is generally laminated with at least a fluororesin layer, a colored layer, an adhesive layer, and a releasable base material layer in order from the surface. This is a particularly preferred embodiment in terms of improving image clarity.

The marking film structure thus obtained has excellent weather resistance, heat resistance, solvent resistance, stain resistance as well as surface sharpness and has a PGD value of O2 or higher. Sharpness is a factor that controls the beauty of the external appearance of paint and marking films.In recent years, there has been a growing interest in high-quality painted products with relatively large areas such as automobile exterior panels, and as a result, Marking films that are applied to high-quality painted products or applied as a substitute for high-quality painted products are also required to have high image clarity. Regarding the definition and content of sharpness, please refer to "Survey Report on Sharpness Evaluation Methods (First Report)" edited by the Sharpness Subcommittee of the Japan Paint Inspection Association's Paint Testing Method Study Group (Western) (Showa (December 1959) for details. The sharpness increases as the surface becomes glossy and mirror-like, and decreases as the surface becomes matte. Devices that quantitatively evaluate image sharpness include PGD meter and image sharpness meter N.
There are PIG, flow comparator Dorigon, etc.
It is generally said that evaluation using a PGD meter has the highest correlation with visual evaluation by experts. A PGD meter illuminates test patterns of different sizes step by step, and images them on the sample surface for visual judgment.The higher the surface sharpness of the sample, the more detailed the test pattern can be read, and the larger the PGD value. Conventional marking film structures generally had a PGD value of 0.2 or less, but the marking film structure of the present invention has a PGD value of 0.3 or more, and has image clarity comparable to that of high-grade painted products such as automobile exterior panels. have.

EXAMPLES The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example-1 Ethylene-tetrafluoroethylene copolymer resin Aflon C
Dice temperature of 0P55AX (manufactured by Asahi Glass ■) at 300℃
A transparent film with a thickness of 40μ was obtained by forming a film using the T-die extrusion method of A PET processing paper having a thickness of 125 μm and having a removable adhesive layer was laminated and used as printing material 1.

Ink-1 was printed all over the corona-treated surface of printing original fabric-1 using a 180-mesh screen, and after drying at 80°C for 60 minutes, a colored layer with a thickness of 10 μm was obtained. Light Peeling of Adhesive Liner 1 The I) ET film was peeled off, pressure bonded to the colored layer, and the I) ET process paper on the surface was peeled off to obtain a marking film structure (1).

Paste it on the float glass (=j and then use the PGD meter (1)G
When I measured the image sharpness with D-TV (manufactured by Tokyo Kohden), it was 0.
．． It was 8.

Example-2 Three ink 2 applied to printing material 1 using reverse roll coater
A marking film structure (2) was obtained in the same manner as in Example 1, except that it was coated to a dry thickness of 15 μm and dried at 140° C. for 6 minutes.

Example 3 A composition obtained by removing all pigments from Ink-1 was used as a brimer on printing material-1, and solid printing was carried out using a 180-mesh screen, and then Ink-1 was similarly printed on it, and 80% of the pigment was removed from Ink-1. After drying at °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 that printing material 2 was used.

Example-5 A marking film structure (
5) was obtained.

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

Comparative Example-1 (Commercially available) White PVC marking film with a thickness of 50μ and having an adhesive layer with a thickness of 30μ ((Scotchcal 3650 manufactured by Sumitomo 3M)) High Niscal 5010
After printing Ink-1 on a 180-mesh screen (or omitted) and drying at 80°C for 60 minutes, the composition obtained by removing only the pigment from Ink-1 was used as a clear coat agent, and the same printing and drying was performed. A marking film structure (7) was obtained.

Comparative Example-2 Adhesive liner 1 was applied directly to the corona-treated surface of the ethylene-tetrafluoroethylene copolymer resin film used in Example-1.
After peeling off the light release PET film, the film was laminated together, and then the heavy release PET film (releasable base material layer) was peeled off and laminated with the marking film used in Comparative Example-1 to obtain a masking film structure (8). .

Comparative Example 3 (Commercially available) A 50μ thick silver metallic tone PVC marking film (Scotchcal 3658 manufactured by Sumitomo 3M■ High Niscal 70151 or omitted) having a 30μ thick adhesive layer was used as a marking film structure ( 9).

Comparative Example-4 In addition to the marking film of Comparative Example-3, a 50μ thick vinylidene fluoride/acrylic two-layer film (AT-50Y) was added to the marking film of Comparative Example-3.
A marking film structure (10) was obtained by press-bonding Kureha Chemical Industry Co., Ltd. (manufactured by Kiki) with a laminating hole at 180° C. with the vinylidene fluoride layer on the outside.

Preparation of printing original fabric-2 Ethylene-tetrafluoroethylene copolymer resin Aflon C
0P88AX (manufactured by Asahi Glass Co., Ltd.) Dimer mark LA of benzotriazole ultraviolet absorber per 100 parts by weight
-31 (manufactured by Adeka Argus) 02 parts by weight was formed into a film by T-die extrusion at a die temperature of 290°C to obtain a transparent film with a thickness of 50 μm.

"Wet" by JISK 6768 is 50 on one side.
A 75 μm thick PET processing paper having a 5 μm thick removable adhesive layer on the non-corona surface was bonded to the printed material to obtain a printing material 2.

Preparation of ink-1 Solvent-soluble fluororesin solution (manufactured by Lumiflon Asahi Glass) 1
00 parts by weight, 20 parts by weight of Lumiflon and pigment (Shinkasha Gold YT-823D manufactured by Ciba Geigy) mixed in a weight ratio of 3:1 and ground in a three-roll mill, -1440 Toyo Aluminum ■) 10
Parts by weight, 10 parts by weight of pearl pigment (Exterior Pride Goldmar Co., Ltd.), UV absorber (G-Sorb 7)
06 Shiraishi Calcium ■ and Tinuvin 234 Ciba Geigy) 0.8 parts by weight each, light stabilizer (Tinuvin 622LD
(manufactured by Ciba Geigy) 1 part by weight, antifoaming agent (SC・5570)
Thoroughly mix and stir 0.02 parts by weight of Toray Dow Corning Silicone (manufactured by Dow Corning Toray Silicone ■) and 20 parts by weight of diluent Cellosolve Acetate, then add 8 parts by weight of a hardening agent (Coronate EH manufactured by Nippon Polyurethane ■) and stir to create a gold metallic ink. -1 was obtained.

Preparation of Ink-2 20 parts by weight of a solvent-soluble fluororesin (Shina-9301 manufactured by Pennwalt) was dissolved in 80 parts by weight of a mixed solvent of equal amounts of cyclohexanone and isophorone, and aluminum paste (FM
-1130 Toyo Aluminum ■) 5 parts by weight, pearl pigment (Iriodin 103WS manufactured by Merck & Co.) 25 parts by weight,
1 part by weight of an ultraviolet absorber (Tinuvin 213 manufactured by Ciba Geigy) and 30 parts by weight of cyclohexanone were added and thoroughly stirred to obtain white pearlescent ink-2.

Preparation of Adhesive Liner 1 Add 100 parts by weight of a solvent-based acrylic adhesive to 100 parts by weight of PE 121 manufactured by Nippon Carbide Industries, 1.4 parts by weight of an ultraviolet absorber (G-Sorb 704 manufactured by Shiraishi Calcium), and a light stabilizer (Tinuvin 622LD manufactured by Ciba Geigy). 0.7 parts by weight (manufactured by Nippon Polyurethane Co., Ltd.), 10 parts by weight of the solvent tertiary-butanol and 20 parts by weight of toluene, and 0.1 part by weight of the crosslinking agent (manufactured by Coronate EH Nippon Polyurethane) were thoroughly mixed and stirred to form a 75μ thick heavy release type. PET-based releasable base material Rabil BM-
2 (manufactured by Toyo Metallizing ■) to a dry thickness of 40 μm, and after drying for 100° CIO, a light-peel type PET film with a thickness of 25 μm (Therapel BK manufactured by Toyo Metallizing ■) was attached to the adhesive liner. I got 1.

Preparation of Adhesive Liner 2 Adhesive Liner 2 was prepared in the same manner as in the preparation of Adhesive Liner 1, except that the heavy release type PET-based releasable base material was replaced with a releasable base material of yarn (OKC・ll0N CY manufactured by Tamago Kako ■). I got it.

Evaluation method ■ The heat-resistant marking film structure was applied to a melamine alkyd white painted plate (manufactured by Nippon Test Panel ■) and placed in an oven at 100° C. After 1000 hours, the structure was taken out and the appearance was visually evaluated.

Items with almost no discoloration compared to the original pieces ○ Items with discoloration compared to the original pieces △ Items with significant discoloration and turned brown or black × ■ Weather-resistant marking film structure painted with white melamine alkyd Sunshine Weather Meter (W-O-M) (WEL-3UN-HC manufactured by Suga Test Instruments) was attached to a board (manufactured by Nippon Test Panel ■) (conditions = 120 minute cycle (including 18 minutes of rain) to measure the black panel temperature. 500 at 63±3℃)
After 0 hours of exposure, the sample was taken out and the appearance was visually judged.

Items with almost no discoloration or decrease in gloss compared to the original ○ Items with slight discoloration or decrease in gloss △ Items with significant discoloration or decrease in gloss × ■ Solvent-resistant marking film on the surface of the structure The sample was placed in a sealed container kept at 30°C with absorbent cotton impregnated with methyl ethyl ketone and taken out after one hour, and the surface was thoroughly wiped and changes in appearance were visually evaluated.

Items with almost no abnormalities such as reduced gloss compared to the original pieces ○ Items with significantly reduced gloss compared to the original pieces, but the surface layer has dissolved and the appearance has changed significantly × ■ Marked with stain-resistant oil-based marker ink The surface of the film structure was painted and exposed to W-0-M for 500 hours, and then taken out and the surface was wiped with a cotton cloth soaked with isopropyl alcohol to visually determine changes in appearance.

Items with no trace of marker ink left ○ Items with a slight black area △ Items that remain completely black × ■ A clear marking film structure is attached to a float glass plate and a PGD meter (PGD-IV The image clarity was measured using a camera (manufactured by Tokyo Koden).

0.2 or less Level 0.3 to 0.5, which is visually inferior to high-grade painted panels such as automobile exterior panels Level 0.6 or higher, which is inferior in sharpness to high-grade painted panels but not significantly inferior to high-quality painted panels Equivalent to high-grade painted panels Example of sharpness level,
The test results of each comparative example are shown in Table-1.

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

Claims (6)

[Claims] (1) It has at least a fluororesin layer with a colored layer, an adhesive layer, and a removable base material layer, and the surface clarity is PG.
A marking film structure having a D value of 0.3 or more. (2) In the fluororesin layer having a colored layer, the surface is the fluororesin layer and the inner side is the colored layer (
1) Marking film structure as described. (3) The marking film structure according to claim 1, wherein the fluororesin layer is a resin layer made of an ethylene-tetrafluoroethylene copolymer. (4) The marking film structure according to claim (1), wherein the resin constituting the colored layer is a solvent-soluble fluororesin. (5) Claim (1) characterized in that the releasable base material layer is made of paper, polyester sheet, or polypropylene sheet coated with silicone resin or fluorine resin.
Marking film structure as described. (6) The marking film structure according to claim (1), wherein at least one of the fluororesin layer, colored layer, and adhesive layer contains an ultraviolet absorber and/or a light stabilizer.