JPH04145483A - Marking film structure - Google Patents

Abstract

PURPOSE:To obtain the marking film structure having sufficient heat resistance, weatherability, solvent resistance, and contamination resistance by having a fluororesin layer contg. coloring agents, an adhesive layer and a releasable base material layer. CONSTITUTION:The surface of the fluororesin layer of an ethylene/tetrafluoroethylene copolymer is previously subjected to an activation treatment (for example, corona discharge treatment). The thickness of the resin layer is 10 to 200mu. A UV absorbent is previously compounded with the resin layer in order to improve the weatherability. The coloring layer is formed by coating printing the surface of the resin layer with a resin soln. contg. the coloring agents, then drying the soln. A solvent soluble type fluororesin is more preferable in terms of the weatherability and heat resistance as the resin to form the coloring layer. The coloring agents are preferably org. pigments, inorg. pigments, metallic pigments and pearl pigments having the excellent weatherability and heat resistance. The adhesive layer is directly formed on the colored resin layer or is applied on the releasable base material layer and dried; thereafter, this layer is stuck. The releasable base material layer of an easier release type is stuck onto the adhesive layer for the purpose of protecting the adhesive layer before use.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a marking film that has excellent weather resistance, heat resistance, solvent resistance, and stain resistance. The present invention relates to a marking film structure that can be used on surfaces exposed to high temperatures.

[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 the bonnet or roof of a car, problems such as browning, cracking, and peeling occur within just a few years, and the reality is that it has not been put to practical use.

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, in some cases, PVF is used on top of conventional marking film.
Alternatively, it has been considered to laminate a transparent film of 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. Conventional marking films do not have sufficient heat resistance, weather resistance, solvent resistance, or stain resistance, making them impractical for practical use. It is an object of the present invention to provide a marking film structure that can be used in places where the marking film cannot be used, such as the roof and bonnet of a car.

[Means for solving problems]

The present invention has been made to solve the above-mentioned problems, and provides a marking film structure characterized by having at least a fluororesin layer containing a colorant, an adhesive layer, and a releasable base material layer. It provides:

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 general formula CH2=CH'CnFza+x (however, n in the formula
is an integer of 2 to 10) in which the content of the perfluoroalkyl vinyl monomer is 0.1 to 10 mol%, which is particularly preferable from the viewpoint of transparency, adhesion with the colored layer, film formability, etc. . Such an ethylene-tetrafluoroethylene copolymer can be produced, for example, by the method described in Japanese Patent Publication No. 59-50163, and commercially available products can be used. Commercially available products include Aflon COP (manufactured by Asahi Glass) and Neoflon ETFE.
(manufactured by Daikin Industries, Ltd.) and Texel (manufactured by DuPont) are preferred.

In addition, before laminating the colored layer on the fluororesin layer, the surface of the fluororesin layer is
It is preferable to perform the activation treatment so that the wettability becomes 30 to 54, more preferably 35 to 54, in order to improve adhesion. The method of activation processing is not particularly stipulated;
Any treatment may be used, 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, it is not only disadvantageous in terms of cost, but also has a noticeable haze in appearance, 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-hexafluoropropylene copolymer resin, tetrafluoroethylene and/or monochlorotrifluoroethylene-hydroxyalkyl vinyl ether-alkyl vinyl ether copolymer resin, etc. .

The above-mentioned coloring agent is preferably one with excellent weather resistance and heat resistance, and in addition to general organic pigments and inorganic pigments, metal flakes such as aluminum, known as metallic pigments, and titanium dioxide-coated mica, known as Burl pigments, etc. Can be mentioned. The particle size of these metallic pigments or Burr pigments is preferably from 2 to 200 microns, more preferably from 4 to 150 microns, especially from 5 to 100 microns.

- Also, in the case of Burr pigments, 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.
t-ion (1971) and Supplement
ts (1975) Publisher: The 5ociety
of Dyers and Colorists.

The following colorant names are based on the Co1our Index specified in the same book.
By Generic Name. For example, Y-1 is C, I.

It means PifP3nt Yellow. O again
is Orange.

R is Red, V is Violet, B is Blue, G
is Green, SBr is Brown, Bk is Black
k and W represent whi-te, respectively.

First, as yellow pigments, azo condensed polycyclic pigments and metal complex salt pigments are particularly preferred, and among azo pigments, insoluble monoazo pigments (Y-97, Y-116, Y-120, Y-
151, Y-154), disazo pigment (Y-81, Y
-83, Y-155), fused azo (Y-93, Y-9
4, Y-95, Y-128) are preferred, and in the case of condensed polycyclic systems, anthraquinone pigments (Y-24, Y-108, Y-
147, Y-123, Y-99), isoindolinone pigment (y-109, Y-110, Y-IT3), isoindoline pigment (Y-139), quinophthalone pigment (
Y-138) is preferred, and among metal complex salts, copper azomethine pigments (Y-117, Y-129) and nickel nitroso pigments (Y-153) are preferred.

Nickel azo pigment (G-10) is preferred. Among inorganic compounds, iron oxide yellow (Y-42) and titanium-antimony-nickel oxide (Y-53) are preferred.

As the orange pigment, azo pigments and condensed polycyclic pigments are particularly preferred.As the azo pigments, insoluble monoazo pigments (0
-36,0-5,0-38,0-60,0-62),
Disazo pigment (0-34), condensed azo pigment (0-34)
31) are preferred, and examples of the condensed polycyclic pigments include perylene pigments (0-43) and anthraquinone pigments (0-40).
,0-51), isoindolinone pigment (0-42)
, quinacridone pigments (0-48, 0-49) are preferred.

Particularly preferred red pigments are azo pigments, condensed polycyclic pigments, and inorganic pigments, and examples of azo pigments include insoluble monoazo pigments (R-2, R-6, R-7, R-9, R- 1
0, R-12, R-14, R-112, R-146, R
-147, R-170, R-171, R-175, R-
185, R-187, R-188, R-208), azo lake pigments (R-52:2, R-115, R-15
1, R-243), condensed azo pigment (R-144, R-
166, R-214, R-220, R-221SR-2
42), disazo pigments (R-38, R-37), and examples of condensed polycyclic pigments include anthraquinone pigments (R-168, R-177, R-216), and thioindigo pigments (R-88). ), perinone pigment (R-19
4) Perylene pigments (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) are preferred, and newer pigments include diketopyrrolobyroll pigments (Irgazine DPP Red BO manufactured by Ciba Geigy).
). Inorganic pigments include red iron oxide (red iron oxide R-101) and zinc/iron oxide (R-225).
etc.

Particularly preferable violet pigments are azo pigments, condensed polycyclic pigments, and inorganic pigments; examples of azo pigments include monoazo pigments (V-SO), and examples of condensed polycyclic pigments include perylene pigments (V-29). ), anthraquinone pigment (V-3
L V-33), thioindigo pigments (V-38, V
-36), quinacridone pigment (V-19), dioxazine pigment (V-23, V-37), inorganic pigments include cobalt phosphate pigment (V-14:l), 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-15:3, B-15:4), ε-type phthalocyanine pigment (B-L5:6), metal-free phthalocyanine pigment (B-16), indanthrone pigment (B-16) as a condensed polycyclic pigment -60, B-21, B-22, B-6
4) 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), and the like.

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), and the like.

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

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

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,
Isobutyl 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 5 μ to 500 μ, preferably 10 to 300 μ,
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 invading strength.

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

As the ultraviolet absorber, benzotriazole-based, benzophenone-based, and cyanoacrylate-based ones are preferable, and among them, benzotriazole-based ones are preferable because of their long-lasting effects.As the light stabilizers, hindered amine-based ones are preferable because they are effective.

Further, it is more preferable to use a UV absorber and a light stabilizer together.

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 and/or a fluororesin. 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/am when peeling is performed at 180 degrees at a speed of 300 mm per minute at room temperature.
Preferably it is 1 to 50 g/crn. 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 releasable base layer is not particularly limited, but is generally 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 adhesive layer may be formed directly on the colored resin layer, but
Generally, it is obtained by coating a releasable base material layer in advance, drying it, and then bonding it with a colorant layer. Furthermore, in order to protect the adhesive layer previously formed on the release base material layer until it is used, a more easily releasable base material layer can be bonded onto the adhesive layer. .

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 A transparent film with a thickness of 40 μm was produced from ethylene-tetrafluoroethylene copolymer resin Aphron C0P55AX (manufactured by Asahi Glass ■) containing 0.5% wt of Bengara by T-die extrusion method at a die temperature of 300°C. J I S on one side of 0 obtained
- was subjected to corona treatment so that the "wetness" by 6768 was 50, and then a 125μ thick PET processing paper with a 5μ thick removable adhesive layer was laminated on the non-corona surface to form printing material -1. did.

The easily peelable PET film of the adhesive liner 1 was peeled off, the colored layer was pressed and the PET processed paper on the surface was peeled off, and a marking film structure (1) was obtained.

Example 2 100 parts by weight of ethylene-tetrafluoroethylene copolymer resin Aphron C0P88AX (manufactured by Asahi Glass) containing 0.5% wt of Bengara was mixed with benzotriazole ultraviolet absorber dimer mark LA-31 ( Manufactured by Adeka Argus) 0
．． A pellet containing 2 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.

Otherwise, the marking film structure (
2) was obtained.

Preparation of Adhesive Liner 1 Solvent-type acrylic adhesive: 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 Calcium Shiraishi), and a light stabilizer (Tinuvin 622LD manufactured by Ciba Geigy) (manufactured by Coronate EH Japan Polyurethane), 10 parts by weight of the solvent tertiary-butanol, 20 parts by weight of toluene, and 0.1 part by weight of the crosslinking agent (Coronate EH manufactured by Nippon Polyurethane) were thoroughly mixed and stirred, and a heavy release type with a thickness of 75 μm was prepared. PET-based releasable base material Lapeel 8M-
2 (manufactured by Toyo Metallizing ■) to a dry thickness of 40 μm, and after drying at 100°C for 10 minutes, 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.

Example 3 The molar ratio of tetrafluoroethylene/ethylene is 53/47
The flow start temperature is 280°C, and the thermal decomposition start temperature is 350°C.
℃, and the volumetric flow rate at 300℃ is 90i+m2/
Second ethylene-tetrafluoroethylene copolymer (ETFE)
Color pellets were obtained by kneading 100 parts of the resulting mixture and 10 parts of Bengara as an adhesive using a twin-screw extruder in the same direction. The crosstalk conditions at this time are a temperature of 300℃ and a rotation speed of 10O100rp/D.
=30.

A non-porous colored film with a thickness of 50 microns is prepared by molding the color pellets by hot melt extrusion. A marking film structure (
3) was obtained.

Example 4 A marking film structure was obtained in the same manner as in Example 3 except that 5 parts of phthalocyanine blue was added instead of 10 parts of the petals.

Examples 5 to 36 Marking film structures 5 to 36 of the present invention were obtained in the same manner as in Example 3, except that the colorant and the amount added were changed as shown in Table 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 thread (0KG-11ONCY, manufactured by Tamako 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 pressing O Items with only one discoloration observed compared to the original piece △ Items with significant discoloration to brown or black X ■ Weather-resistant marking film structure is coated with melamine alkyd white coated board Attach it to the Sunshine Weather Meter (W-0-M) (WEL-SUN-HC manufactured by Suga Test Instruments) (manufactured by Nippon Test Panel ■) (conditions: 120 minute cycle (including 18 minutes of rain) with a black panel temperature of 63± 50 at 3℃)
After 00 hours of exposure, the sample was taken out and the appearance was visually judged.

Compared to pressing, there is almost no discoloration or decrease in gloss ○ Slight discoloration or decrease in gloss △ Significant discoloration or decrease in gloss × ■ Methyl ethyl ketone on the surface of the solvent-resistant marking film structure The sample was placed in an airtight container kept at 30° C. with absorbent cotton soaked in it and taken out after one hour, and the surface was thoroughly wiped and changes in appearance were visually determined.

There is almost no abnormality such as a decrease in gloss compared to pressing ○ There is a considerable decrease in gloss compared to pressing 6 The surface layer has dissolved and the appearance has changed significantly × ■ Marking film with stain-resistant oil-based marker ink The surface of the 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.

No trace of marker ink remained ○ Only a few black areas remained △ Almost all black remained × Marking film structures obtained in Examples 1 to 36 were subjected to each of the above tests. The results are shown in Table-2.

Table 1 Table 2 [Effects of the Invention] The marking film structure of the present invention has weather resistance, heat resistance, solvent resistance, stain resistance, and image clarity at a high level that could not be achieved with conventional marking films. In addition, it can be used on high-grade painted panels such as automobile hoods without causing any discomfort in appearance, and can stably maintain its initial function for a long period of time even under severe conditions.

Claims (4)

[Claims] (1) A marking film structure characterized by having a fluororesin layer containing at least a colored layer, an adhesive layer, and a removable base material layer. (2) The marking film structure according to claim 1, wherein the fluororesin layer is a resin layer made of an ethylene-tetrafluoroethylene copolymer. (3) The marking film structure according to claim 1, wherein the releasable base layer is made of paper coated with a silicone resin or a fluorine resin, a polyester sheet, or a polypropylene sheet. (4) The marking film structure according to claim 1, wherein at least one of the fluororesin layer and the adhesive layer contains an ultraviolet absorber and/or a light stabilizer.