JPH09254327A - Marking film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film excellent in tearing strength, weatherability and curved surface following properties by a method wherein a base material layer is obtained by turning a composition made of ethylene α-olefin copolymer having the specified properties, which are obtained through polymerization in the presence of metallocene catalyst, and organic phosphate metal salt, which has the specified component and is represented with the specified formulae, into a film. SOLUTION: The base material layer of this film is produced by turning a composition made of ethylene/α-olefin copolymer, which is obtained through polymerization in the presence of metallocene catalyst so as to have the density of 0.86-0.92g/cm<3> and the ratio of weight-average molecular weight to number- average molecular weight of 1.5-5, 5-30 pts.wt. of titanium oxide to 100 pts.wt. of the copolymer, 0.1-5 pts.wt. of ultraviolet absorber, 0.1-3 pts.wt. of organic phosphate metal salt represented with the formula I and/or the formula II, in which M is a metal element selected from the group consisting of Zn, calcium, barium, magnesium and strontium, R1 -R5 represent respectively 1-22C alkyl group, aryl group, aralkyl group, alkyl aryl group and hydrocarbon group containing ether linkage, into a film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a marking film used for advertisement stickers, decorative stickers and display stickers, and more particularly, it has excellent tear strength, weather resistance and curved surface followability and is simple. The marking film that can be processed by various incinerators.

[0002]

2. Description of the Related Art Marking films are generally used on one side after a vinyl chloride resin film is used as a base material and a pigment is kneaded into the base material for coloring depending on the purpose or after the base material is printed. The pressure-sensitive and / or heat-sensitive adhesive is applied to form a pressure-sensitive adhesive layer, and a release material such as release paper is attached for the purpose of protecting the pressure-sensitive adhesive layer. The release material is peeled off and attached to a predetermined place. The marking film is often used outdoors, and it is an advertising sticker used for signboards, advertising towers, shutters, show windows, etc .; ornamental stripe stickers used for vehicles such as automobiles and motorcycles, and ships such as motor boats. Used for traffic signs, road signs, display stickers used for guide boards, etc. Therefore, the marking film is required to have tear strength and weather resistance, and to have appropriate flexibility for sticking to a cubic curved surface.

A marking film having a vinyl chloride resin film as a base material is usually added with a plasticizer in order to impart appropriate flexibility. The flexibility and weather resistance of the plasticizer due to bleeding out. However, there is a problem of deterioration in adhesive strength retention, printing ink adhesion, ultraviolet absorbent retention, etc., and various improvements have been made to solve these problems. For example, JP-A-60-195146 proposes a semi-rigid vinyl chloride resin molding composition in which a vinyl chloride resin is mixed with a liquid polyester plasticizer and an ethylene / vinyl ester resin. Japanese Unexamined Patent Publication (Kokai) No. 63-24619 proposes a semi-rigid vinyl chloride resin molding composition in which a liquid polyester plasticizer and a low molecular weight acrylic resin are used as a vinyl chloride resin.

However, these effects have not reached a satisfactory level, and various improvements are still being studied. Moreover, since hydrogen chloride is generated when incinerating and discarding a marking film having a vinyl chloride resin film as a base material, it cannot be treated by a simple incineration facility, and further, the durability of the incineration facility is deteriorated. there were. Therefore, recently, there has been an increasing demand for marking films that can be processed with simple incineration equipment, but polyolefin-based resin films have appropriate flexibility without the addition of additives such as plasticizers, and can be disposed of by incineration. Easy, but
It has not been used as a base material for a marking film because it has insufficient weather resistance, or even if it has sufficient surface resistance, it is inferior in curved surface followability.

[0005]

PROBLEM TO BE SOLVED BY THE INVENTION It is an object of the present invention to provide a marking film which is excellent in tear strength, weather resistance and curved surface followability and which can be processed by a simple incineration facility.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve the above-mentioned problems relating to marking films, and as a result, a specific ethylene-α-olefin copolymer obtained by polymerization using a metallocene catalyst was obtained. Use as a base material layer a film formed by molding a polyolefin resin composition containing a polymer as a main component, a specific organic phosphate metal salt, a hindered amine compound, titanium oxide and an ultraviolet absorber. It was found that a marking film excellent in tear strength and weather resistance, and also excellent in curved surface followability can be obtained, and thus the present invention was completed.

That is, the gist of the present invention is a marking film obtained by laminating a base material layer / adhesive layer / release material layer in this order, which is obtained by polymerizing the base material layer using a metallocene catalyst. An ethylene-α-olefin copolymer having the following properties (a) and (b): 100
5 to 30 parts by weight of titanium oxide per part by weight, 0.1 to 5
1 part by weight of an ultraviolet absorber, 0.1 to 3 parts by weight of a hindered amine compound, and 0.1 to 3 parts by weight of an organic phosphoric acid ester metal salt represented by the following general formula [1] and / or [2]. A marking film, which is a film obtained by forming a film of the composition, wherein (a) the density is 0.86 to 0.92 g / cm ³ (b) the weight average molecular weight (Mw) and the number average molecular weight. (Mn)
And the ratio (hereinafter referred to as “Mw / Mn”) is 1.5 to 5

[0008]

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[0009]

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(In the formula, M means a metal element selected from the group consisting of zinc, calcium, barium, magnesium or strontium. Further, R ₁ , R ₂ ,
R ₃ , R ₄ and R ₅ each represent an alkyl group having 1 to 22 carbon atoms, an aryl group, an aralkyl group, an alkylaryl group or a hydrocarbon group containing an ether bond. ) Another aspect of the present invention is that a printing layer is laminated on the opposite surface of the marking film and the base material layer where the pressure-sensitive adhesive layer is made of an acrylic resin-based pressure-sensitive adhesive from the surface where the pressure-sensitive adhesive layer is laminated. In the above marking film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the present invention, the metallocene catalyst (also referred to as single-site catalyst or Kaminsky catalyst) is described in JP-A-3-163.
No. 088, Japanese Patent Application Laid-Open No. 7-118431, Japanese Patent Application Laid-Open No. 7-148895, etc., a catalyst composed of a metallocene-based transition metal complex and an organic aluminum compound, which is used by being supported on an inorganic substance. It may be done.

The metallocene-based transition metal complex includes, for example, a transition metal selected from Group IVB (titanium, zirconium, hafnium), a cyclopentadienyl group, a substituted cyclopentadienyl group, a dicyclopentadienyl group, and a substituted dimetal. A cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is coordinated with 1 or 2 ligands, or among these Coordinating the two groups of the above are covalently bonded, and additionally having a ligand such as a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an acetylacetonato group. Is mentioned.

Further, as the organoaluminum compound,
Alkyl aluminum and chain or cyclic aluminoxane can be mentioned, and as alkyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, Diethyl aluminum hydride, ethyl aluminum sesquichloride, etc. can be exemplified, and the chain or cyclic aluminoxane can be produced by contacting the above alkylaluminum with water. Water is added, or water of crystallization of complex salts or water of adsorption of organic or inorganic compounds and It can be obtained by reacting aluminum. Examples of the carrier supporting the metallocene catalyst include silica gel, zeolite, diatomaceous earth and the like.

As the α-olefin copolymerized with ethylene, it is preferable to use an α-olefin having 3 to 12 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene. , 1-octene, 4
-Methyl-1-pentene and the like. These α-
The olefins may be used alone or in combination of two or more. The ratio of α-olefin to ethylene is 5 to 4
It is preferably 0% by weight. Examples of the method for producing an ethylene-α-olefin copolymer using the above metallocene catalyst include JP-A-56-18607, JP-A-58-225106, JP-A-6-336539 and JP-A-6-36539. The gas phase method, the slurry method, the solution method, the high pressure ionic polymerization method, etc. as disclosed in JP-A-7-258481 can be exemplified.

Polymerized using the above metallocene catalyst,
Ethylene-α-olefin copolymer (polyolefin type
(Copolymer) using Ziegler catalyst, solid catalyst, etc.
Compared to the polymerized polyolefin copolymer,
Excellent in tensile strength, tear strength and flexibility
In addition, it is difficult for the film to stretch when it is attached,
It has excellent surface tracking properties and is suitable for use as a marking film.
You. In particular, of the ethylene-α-olefin copolymers described above
Density is 0.86-0.92g / cm^Three, Preferably 0.
88-0.91g / cm^Three, And more preferably 0.89-
0.91 g / cm ^ThreeAnd also gel permeation
Mw determined by chromatography (GPC)
/ Mn is 1.5 to 5, preferably 2 to 4,
The rum is flexible and has good curved surface followability. Dense
0.86g / cm^ThreeBelow, the film will soften
Since there is no "waist", secondary processing becomes difficult, and fill
Poor handleability when pasting. Density 0.92g
/ Cm^ThreeIf it exceeds, the curved surface followability of the film is poor. Change
In addition, the ethylene-α-olefin copolymer melt-in
If the dex is 0.5 to 5, especially 0.8 to 3,
It is preferable because the moldability of rum is good.

As the base material layer of the marking film of the present invention, the above-mentioned ethylene-α-olefin copolymer can be used as it is, but as long as its performance is not changed, high density polyethylene Density polyethylene, high-pressure polyethylene and their copolymers, crystalline polyolefin such as polypropylene, natural rubber,
Various synthetic rubbers, thermoplastic elastomers, various fillers such as calcium carbonate, silica, metal fibers and carbon fibers,
You may mix | blend antioxidants, a flame retardant, etc. as needed. The thickness of the base material layer is 20 to 150 μm, preferably 40.
-80 μm is suitable. If the thickness is less than 20 μm, the “waist” is weak and the secondary processing becomes difficult, and the handleability at the time of application is poor, which is not preferable. When it exceeds 150 μm, the ability to follow a cubic curved surface is deteriorated and the economical efficiency is deteriorated, which is not preferable.

The titanium oxide used in the present invention is preferably a rutile type, and one having an average particle size of 0.01 to 1 μm has good dispersibility and is suitable in terms of physical properties of the film. The rutile type titanium oxide itself has good weather resistance and enhances the durability of the base material as compared with the anatase type. The compounding amount of titanium oxide is 5 to 30 with respect to 100 parts by weight of the ethylene-α-olefin copolymer.
Parts by weight, preferably 10 to 20 parts by weight. When the blending amount is less than 5 parts by weight, the hiding property is poor and the light reflection amount is reduced, so that deterioration of the pressure-sensitive adhesive or the base material layer is likely to occur, which is not preferable. If it exceeds 30 parts by weight, the effect of improving the weather resistance corresponding to the blending amount cannot be expected, and on the contrary, the physical strength of the base material layer itself tends to decrease, which is not preferable. Generally, in the marking film, it is important to ensure uniform dispersion of the compounding agent in order to improve the weather resistance. It is preferable to mix it in the form of another compounding agent or an ethylene-α-olefin copolymer.

As the ultraviolet absorber, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber or a salicylic acid ester type ultraviolet absorber which has been conventionally used for polyolefin resins can be used. The amount of the ultraviolet absorber blended is 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the ethylene-α-olefin copolymer. The blending amount is 0.
If it is less than 1 part by weight, good weather resistance cannot be obtained, and if it exceeds 5 parts by weight, not only the effect of improving weather resistance commensurate with the compounding amount is not obtained, but conversely the shift to the adhesive layer. It is not so preferable because deterioration may be promoted by the above.

As the hindered amine-based compound, those conventionally blended with polyolefin resins may be used, and specific examples include the following. (1) 2,2,6,6-tetramethylpiperidyl-4-
Benzoate (2) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (3) Tris (2,2,6,6-tetramethyl-4-piperidyl) phosphite (4) Trade name " Kimasorb 944LD "

[0020]

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(5) 1,3,8-triaza-7,7,
9,9-Tetramethyl-3-n-octylspiro [4,4
5] Decane-2,4-dione (6) Trade name "Tinubin 144"

[0022]

[Chemical 6]

(7) 1,2,3,4-tetra (4-carbonyloxy-2,2,6,6-tetramethylpiperidyl) -butane (8) 1,3,8-triaza-7,7, 9,9-Tetramethyl-2,4-dioxo-spiro [4,5] decane (9) tri (4-acetoxy-2,2,6,6-tetramethylpiperidyl) amine (10) 4-acetoxy-2 , 2,6,6-teratomethylpiperidine (11) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine (12) 4-benzyloxy-2,2,6,6-tetramethylpiperidine (13) ) 4-Phenylcarbamoyloxy-2,2
6,6-Tetramethylpiperidine (14) 4-p-toluenesulfonyloxy-2,2
6,6-Tetramethylpiperidine (15) Bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate

The content of the hindered amine compound is 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the ethylene-α-olefin copolymer. If it is less than 0.1 part by weight, sufficient weather resistance cannot be obtained, and if it exceeds 3 parts by weight, the effect of improving weather resistance commensurate with the compounding amount cannot be obtained, and conversely deterioration due to migration to an adhesive layer or the like. It is not preferable because it may promote

Further, the alkyl group having 1 to 22 carbon atoms, the aryl group, the aralkyl group and the alkylaryl group which constitute the organophosphate metal salt represented by the general formula [1] or [2] used in the present invention. Alternatively, examples of the hydrocarbon group containing an ether bond include the following. As the alkyl group, a methyl group, an ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-amyl group, neopentyl group, isoamyl group, hexyl group,
Heptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, decyl group, lauryl group, tridecyl group, 1-octadecyl group,
Examples thereof include cyclopentyl group, cyclohexyl group, cyclooctyl group, 4-methylcyclohexyl group and the like.

Examples of the aryl group include phenyl group and naphthyl group, and examples of the aralkyl group include benzyl group and p.
Examples thereof include a phenethyl group and an α-phenylpropyl group. Examples of the alkylaryl group include tolyl group, xylyl group, ethylphenyl group, butylphenyl group, ter
Examples thereof include t-butylphenyl group, octylphenyl group, nonylphenyl group, and 2,4-di-tert-butylphenyl group.

Examples of the hydrocarbon group containing an ether bond include furfuryl group, tetrahydrofurfuryl group, 5-methylfurfuryl group, α-methylfurfuryl group, methyl cellosolve residue (ether obtained by removing the hydroxyl group from the above cellosolve. A hydrocarbon group containing a bond, the same shall apply hereinafter), ethyl cellosolve residue, isopropyl cellosolve residue, butyl cellosolve residue, isobutyl cellosolve residue, hexyl cellosolve residue, cyclohexyl cellosolve residue, phenyl cellosolve residue, methylcarbitol. A residue (referring to a hydrocarbon group containing an ether bond obtained by removing a hydroxyl group from the carbitol, the same applies hereinafter), an ethylcarbitol residue,
Isopropyl carbitol residue, butyl carbitol residue, isobutyl carbitol residue, triethylene glycol monomethyl ether residue (referred to as a hydrocarbon group containing an ether bond except the above hydroxyl group, the same applies hereinafter), triethylene glycol Monoethyl ether residue, triethylene glycol monobutyl ether residue,
2,3-dimethoxy-n-propyl group, 2,2'-diethoxyisopropyl group, 3-ethoxy-2-propoxy-n-propyl group and the like can be mentioned.

The organophosphate metal salt having various substituents as described above can be blended alone or in combination of two or more. The amount of the organic phosphate metal salt blended is such that the ethylene-α-olefin copolymer 1
0.1 to 3 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight.
It is 2 to 2 parts by weight. When the amount is less than 0.1 parts by weight, sufficient weather resistance cannot be obtained, and when the amount exceeds 3 parts by weight, the effect of improving the weather resistance corresponding to the compounding amount cannot be obtained, and conversely deterioration due to transfer to the adhesive layer or the like. It is not preferable because it may promote

The base layer of the marking film of the present invention is
After blending the above-mentioned titanium oxide, an ultraviolet absorber, a hindered amine compound, and an organic phosphoric acid ester metal salt with an ethylene-α-olefin copolymer, the obtained composition is treated with, for example, T-die. Although it can be obtained by forming a film by a vacuum method or an inflation method, it is preferable to use the T-die method from the viewpoint of dimensional stability. The formed substrate layer generally has a surface tension of about 30 dyne / cm.
Therefore, it is desirable to improve the adhesion of the printing ink or the pressure-sensitive adhesive by surface modification such as corona treatment before use.

The printing layer in the present invention may be formed by a solid continuous printing method such as a knife coater or spray coating, or a screen printing method, which is conventionally used, if necessary. Examples of the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer in the present invention include acrylic resin-based and rubber-based pressure-sensitive adhesives. Examples of the main agent include poly (meth) acrylic acid ester, chlorinated rubber, natural rubber, synthetic rubber and the like. From the viewpoint of weather resistance when used outdoors, it is preferable to use an acrylic resin-based adhesive, in order to obtain stronger holding power especially when exposed to high temperatures, isocyanate-based, epoxy-based, melamine-based, metal alkoxide A two-component curing type acrylic resin-based pressure-sensitive adhesive using a cross-linking agent such as a system or metal chelate system is desirable.

Examples of the cross-linking agent include the following. That is, as the isocyanate-based cross-linking agent, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, etc., as the epoxy-based cross-linking agent, ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, etc., as the melamine-based cross-linking agent. , N-butyl ether compound, isobutyl ether compound, methyl ether compound of methylol melamine, titanium, zirconium, etc.
Alkoxides of metals such as aluminum, for example, tetraisopropyl titanate, tetra-n-butyl titanate, aluminum-sec-butyrate, zirconium isopropylate and the like, as a metal chelate cross-linking agent,
Examples thereof include chelate compounds of metals such as titanium, zirconium, and aluminum, such as titanium acetylacetonate, diisopropoxytitanium bis (acetylacetonate), aluminum tris (ethylacetylacetonate), and zirconium tetraacetylacetonate.

The thickness of the pressure-sensitive adhesive layer varies depending on the intended use of the product marking film, but is preferably in the range of 15 to 60 μm. The marking film is generally prepared by applying a pressure-sensitive adhesive to a release material by a quantitative coating method such as a reverse roll coating method and heating and drying it, and then, when a printing layer is formed on the base material layer, It is manufactured by stacking on the side not having this. The release material that constitutes the marking film of the present invention is not particularly limited, and for example, silicone-coated release paper or the like can be used. The marking film obtained by the above method is cut into letters, figures, etc. in a desired size if necessary, peeled off the release material and attached to a desired adherend, and used for decoration, display, advertisement, etc. To be

[0033]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by the following examples without departing from the scope of the invention. The evaluation methods of the base material layer (film) and the marking film are as follows. <Evaluation of tear strength> The tear strength of the base material layer (film) made of a polyolefin resin or a vinyl chloride resin was measured according to JIS K 7128B method (Elemendorff tear test).

<Evaluation of weather resistance> A marking film of 5 cm × 11 cm was removed and attached to a steel plate of 5 cm × 11 cm after removing the release material, and a sunshine weatherometer manufactured by Suga Test Instruments Co., Ltd. (condition: black panel temperature 63 ° C., rainfall 12
Min / 60 minutes), the film was visually evaluated for peeling, discoloration, and generation of cracks (appearance change) after 2000 hours of exposure. ○ ……… Good appearance △ ……… Some changes in appearance × ………… Great change in appearance

<Evaluation of curved surface followability> 15 cm × 30 cm
The marking film of No. 1 was attached to the entire surface of the cubic curved surface shown in FIG. 1 after removing the release material, and the appearance immediately after the application and one day after the application was visually evaluated. ○ ……… Good appearance (no wrinkles, peeling, etc.) △ ……… Some wrinkles, peeling, etc. occurred × ……… A lot of wrinkles, peeling, etc. <Evaluation of incineration treatment> Burning the marking film in the combustion chamber And take out a part of the generated gas.
Qualitative analysis of hydrogen chloride, chlorine, carbon monoxide, and ammonia in the gas was performed using a gas detector tube manufactured by Gastec. ○ ……… Neither hydrogen chloride, chlorine, carbon monoxide nor ammonia was detected, and it can be treated with a simple incinerator. × ……… Hydrogen chloride was detected, and it could not be processed with a simple incinerator.

(Manufacture of Marking Film) (1) Marking Film Made of Polyolefin Resin The resin composition obtained by adding each compounding agent to the polyolefin resin in the composition shown in Table 1 and mixing with a Henschel mixer. The T-die method is used to form a film having a thickness of 60 μm, and the surface tension is 42 dyne / cm in-line.
Corona treatment was applied so that A printing layer having a thickness of 10 μm was formed on one surface of the obtained film as a substrate layer by a screen printing method using a heat-curable acrylic printing ink. Next, a pressure-sensitive adhesive layer having a thickness of 20 μm was formed by a reverse roll coating method using a two-component curing type acrylic pressure-sensitive adhesive on one surface of a release material made of silicone-coated release paper, and the obtained laminate was adhered. The laminate was laminated on the base material layer by the laminating method with the agent layer side facing inward to obtain a marking film in which the printing layer / base material layer / adhesive layer / release material layer were laminated in this order. The polyolefin-based resin used is as follows.

[0037]

(2) Vinyl Chloride Resin Marking Film Each compounding agent was added to the vinyl chloride resin in the composition shown in Table 2 and mixed and kneaded with a Hobart mixer to prepare an organosol. This sol is applied on a stainless steel plate, and 60
The film was dried at 100 ° C. for 10 minutes and then at 100 ° C. for 10 minutes to obtain a film having a thickness of 60 μm. A printing layer, a pressure-sensitive adhesive layer and a release agent layer were formed in the same manner as in (1) using the obtained film as a base layer to obtain a marking film. The base layer film and the marking film obtained in (1) and (2) above were evaluated for tear strength, weather resistance, curved surface followability and incineration treatment, and the results are shown in Table-
3 is shown.

[0039]

[Table 1]

LLDPE: Linear low-density polyethylene HDPE: High-density polyethylene CR-60: Ishihara Sangyo Co., Ltd. rutile titanium oxide Tinuvin 326: Ciba-Geigy benzotriazole-based UV absorber SANOL LS-700: Ciba-Geigy (The hindered amine compound (2)) MARK LA-57: manufactured by Adeka Argus Chemical Co., Ltd. (the hindered amine compound (7))

[0041]

[Table 2]

P440: Mitsubishi Chemical Co., Ltd. vinyl chloride resin for paste (average degree of polymerization 1500) DOP: Mitsubishi Chemical Co., Ltd. dioctyl phthalate PM-446: ADEKA ARGUS CO., LTD. Polyester plasticizer acrylic resin : Low molecular weight acrylic Mn = 7400 IM-181PJS: Katsuta Kako Co., Ltd. tin stabilizer AP-539: Adeka Argus Co., Ltd. Ba / Zn
System stabilizer CZ-19J: Katsuta Kako Co., Ltd. Ca / Zn system stabilizer Bu-St: Kawaken Fine Chemical Co., Ltd. ester lubricant TINUVIN 328: Ciba-Geigy benzotriazole UV absorber CR-90: Ishihara Sangyo Co., Ltd. rutile type titanium oxide MIBK: methyl isobutyl ketone

[0043]

[Table 3]

[0044]

EFFECTS OF THE INVENTION The marking film of the present invention has excellent tear strength and weather resistance of the base material layer and does not contain a substance having a migration property such as a plasticizer, so that it does not deteriorate with time. Further, it is excellent in curved surface followability and can be processed by a simple incinerator, which is extremely useful.

[Brief description of drawings]

FIG. 1 is a perspective view of a cubic curved surface used in <Evaluation of curved surface followability> in [Example].

Claims (3)

[Claims] 1. A marking film in which a base material layer / adhesive layer / release material layer are laminated in this order, wherein the base material layer is obtained by polymerizing using a metallocene catalyst (a) and (b) below. An ethylene-α-olefin copolymer having the following characteristics, 5 to 30 parts by weight of titanium oxide, 0.1 to 5 parts by weight of an ultraviolet absorber, and 0.1 to 5 parts by weight of 100 to 100 parts by weight of the copolymer.
It is a film formed by forming a film of a composition comprising 3 parts by weight of a hindered amine compound and 0.1 to 3 parts by weight of an organophosphate metal salt represented by the following general formula [1] and / or [2]. Marking film characterized by (A) Density is 0.86 to 0.92 g / cm ³ (b) Weight average molecular weight (Mw) and number average molecular weight (Mn)
The ratio (hereinafter referred to as “Mw / Mn”) is 1.5 to 5 Embedded image (In the formula, M means a metal element selected from the group consisting of zinc, calcium, barium, magnesium or strontium. Further, R ₁ , R ₂ , R ₃ , R ₄ and R ₅
Each represents an alkyl group having 1 to 22 carbon atoms, an aryl group, an aralkyl group, an alkylaryl group or a hydrocarbon group containing an ether bond. ) 2. The marking film according to claim 1, wherein the adhesive layer is made of an acrylic resin adhesive. 3. The marking film according to claim 1, wherein a printing layer is laminated on the surface of the base material layer opposite to the surface on which the pressure-sensitive adhesive layer is laminated.