JPWO2013024781A1 - Film and adhesive film using the same - Google Patents

Abstract

Provided are a film and an adhesive film that can exhibit decontamination over a long period of time. The film 1 contains a base resin containing at least one of a vinyl chloride resin and an acrylic resin, an alkylene glycol compound (A) having a glycidyl group, and an alkylene glycol compound (B) having a benzotriazole group.

Description

  The present invention relates to a film that can be used for a marking film, a protective film, and the like, and an adhesive film using the same.

  Marking films are widely used indoors and outdoors as outdoor signboards and automobile decoration / display substrates because they have better design uniformity, mass productivity, and ease of implementation than painting. When the marking film is used outdoors, dirt such as dust, dust, exhaust gas, etc. may adhere to the exterior due to rain and wind. Therefore, there is a demand for a marking film having a function (hereinafter referred to as contamination removal property) that can be easily removed by washing even if dirt is attached.

  In order to improve the decontamination property, it is known that it is effective to make the surface of the film hydrophilic. However, if the film itself is hydrophilic, there may be a problem in the water resistance and durability of the film. Therefore, it is preferable that only the surface of the film is hydrophilic.

  JP-A-2001-87721 (Patent Document 1) describes a protective film in which a specific hydrophilicity-imparting agent is blended in a resin film. Since this hydrophilicity imparting agent is a relatively low molecular weight compound, it bleeds out to the surface, where it chemically decomposes to generate hydrophilic chemical species, thereby rendering the surface of the film hydrophilic. Thereby, the surface of the film exhibits decontamination.

JP 2001-87721 A

However, since this hydrophilicity imparting agent bleeds out on the surface of the film, the binding strength with the resin is weak, and there is a possibility that the hydrophilicity imparting agent may flow out when exposed to rainwater or the like for a long time. Therefore, this protective film has a drawback that it is difficult to maintain the decontamination property.
Then, an object of this invention is to provide the film which can exhibit a decontamination property over a long period of time, and an adhesive film using the same.

  In order to achieve the above object, the present invention is characterized by any of the following items (1) to (9).

(1) A film containing a base resin containing at least one of a vinyl chloride resin and an acrylic resin, an alkylene glycol compound (A) having a glycidyl group, and an alkylene glycol compound (B) having a benzotriazole group.

(2) The film according to (1), wherein both the alkylene glycol compound (A) and the alkylene glycol compound (B) contain polyethylene glycol.

(3) The film according to (2), wherein the alkylene glycol compound (A) is polyethylene glycol diglycidyl ether.

(4) The alkylene glycol compound (B) is a reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol. The film as described in (3) above, wherein

(5) Said (1)-(4) whose total content of the said alkylene glycol compound (A) and the said alkylene glycol compound (B) is 1-10 mass parts with respect to 100 mass parts of said mother resins. ).

  (6) The total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is 2 to 10 parts by mass with respect to 100 parts by mass of the base resin. the film.

  (7) The film according to (5) or (6), wherein a mass ratio of the alkylene glycol compound (A) to the alkylene glycol compound (B) is 1/5 to 5/1.

  (8) The film according to (7), wherein a mass ratio of the alkylene glycol compound (A) to the alkylene glycol compound (B) is 1/2 to 2/1.

  (9) A pressure-sensitive adhesive film comprising the film according to any one of (1) to (8) and a pressure-sensitive adhesive layer disposed on one surface of the film.

  ADVANTAGE OF THE INVENTION According to this invention, the film which can exhibit decontamination property over a long period of time, and an adhesive film using the same can be provided.

It is a figure which shows the mode of the cross section of the film which concerns on embodiment of this invention. It is a figure which shows the mode of the cross section of the adhesive film which concerns on embodiment of this invention.

  Hereinafter, the film and the pressure-sensitive adhesive film of the present invention will be described in detail by taking preferred embodiments as examples.

<Embodiment of Film>
As shown in FIG. 1, the film 1 of this embodiment has one surface 11 and the other surface 12. Although the thickness of the film 1 is not specifically limited, For example, you may be 20 micrometers-200 micrometers, More preferably, you may be 30-150 micrometers. In addition, it is preferable that the film 1 has moderate flexibility.
The film 1 includes at least a base resin containing at least one of a vinyl chloride resin and an acrylic resin, an alkylene glycol compound (A) having a glycidyl group, and an alkylene glycol compound (B) having a benzotriazole group. Is done. The film 1 may further contain other components such as a pigment, a colorant, an ultraviolet absorber, a heat stabilizer, a plasticizer, and a modifier as necessary.

Since the glycidyl group contained in the alkylene glycol compound (A) and the benzotriazole group contained in the alkylene glycol compound (B) are lipophilic groups, they are compatible with the lipophilic vinyl chloride and acrylic resin constituting the mother resin. It is easy to be taken into the film 1.
On the other hand, since the alkylene glycol group contained in the alkylene glycol compound (A) and the alkylene glycol compound (B) is a hydrophilic group, it is difficult to be compatible with the lipophilic vinyl chloride or acrylic resin constituting the mother resin, and the surface of the film. 11 and 12 are easily localized.
Thus, since the alkylene glycol compound (A) and the alkylene glycol compound (B) have both a lipophilic group and a hydrophilic group, the base resin constituting the film 1 is composed of the glycidyl group and the benzotriazole group of the lipophilic group. In addition, the surface of the film 1 is imparted with hydrophilicity, that is, contamination removal property by the alkylene glycol group of the hydrophilic group localized on the surfaces 11 and 12 of the film 1.

  And in the film 1, by using both the alkylene glycol compound (A) and the alkylene glycol compound (B), the respective alkylene glycol groups localized on the surface of the film 1 are mutually compatible and entangled with each other. As a result, it is more firmly fixed to the mother resin.

  That is, the film 1 of this embodiment contains both the alkylene glycol compound (A) having a glycidyl group and the alkylene glycol compound (B) having a benzotriazole group, whereby the alkylene glycol compound (A) and the alkylene glycol compound ( B) is separated from the base resin and bleeds out, and the decontamination property can be exhibited over a long period of time.

Hereinafter, each component which comprises the film 1 is explained in full detail.

− Base resin −
As described above, the base resin used for the film 1 includes at least one of a vinyl chloride resin and an acrylic resin.
The mother resin is composed of, for example, a polymer compound having a weight average molecular weight of 30,000 or more. In addition, what is necessary is just to measure a weight average molecular weight with measuring instruments, such as a well-known gel permeation chromatography (GPC).

The vinyl chloride resin contained in the base resin is a resin polymerized with vinyl chloride as an essential component, and even if it is a homopolymer of a resin containing vinyl chloride, it can be copolymerized with a resin containing vinyl chloride And a copolymer thereof.
The acrylic resin contained in the mother resin is a resin polymerized with (meth) acrylic acid ester as an essential component, and even if it is a homopolymer of a resin containing (meth) acrylic acid ester, (meth) acrylic It may be a copolymer of a resin containing an acid ester and a copolymerizable monomer.

  The mother resin may further contain a resin such as a polyester resin, a polyurethane resin, a polyolefin resin, a cellulose resin, or a silicone resin as necessary.

-Alkylene glycol compound (A)-
The alkylene glycol compound (A) used for the film 1 is an alkylene glycol compound having a glycidyl group as described above.

Specific examples of the alkylene glycol compound (A) include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol di Examples include glycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, and polyglycerol polyglycidyl ether. .
Among these, polyethylene glycol diglycidyl ether is particularly preferable because it improves the decontamination of the film. By using polyethylene glycol diglycidyl ether, the methylene chain length can be shortened compared to propylene glycol, tetramethylene glycol and the like. Thus, hydrophilicity can be improved by shortening the methylene chain length.

-Alkylene glycol compound (B)-
The alkylene glycol compound used for the film 1 is an alkylene glycol compound having a benzotriazole group as described above.

More specifically, the alkylene glycol compound (B) is a reaction product of a compound having a benzotriazole group and an alkylene glycol.
Specific examples of the compound having a benzotriazole group include methyl 3- (3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl) propionate, methyl 3- (3- (2H-benzotriazole-2- Yl) -5-tert-butyl-4-hydroxyphenyl) propionate, methyl 3- (3- (2H-benzotriazol-2-yl) -5-dodecyl-4-hydroxyphenyl) propionate, methyl 3- (3- (2H-benzotriazol-2-yl) -5-pentyl-4-hydroxyphenyl) propionate, methyl 3- (3- (2H-benzotriazol-2-yl) -5- (1-methyl-1-phenylethyl) ) -4-hydroxyphenyl) propionate, methyl 3- (3- (5-chloro (2H) -benzo Riazol-2-yl) -4-hydroxyphenyl) propionate, methyl 3- (3- (5-chloro (2H) -benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate, methyl 3- (3- (5-Chloro (2H) -benzotriazol-2-yl) -5-dodecyl-4-hydroxyphenyl) propionate, methyl 3- (3- (5-chloro (2H) -benzotriazole-2 -Yl) -5-pentyl-4-hydroxyphenyl) propionate, methyl 3- (3- (5-chloro (2H) -benzotriazol-2-yl) -5- (1-methyl-1-phenylethyl)- 4-hydroxyphenyl) propionate and the like.
Examples of the alkylene glycol compound (B) include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyisobutylene glycol, pentyl glycol, isopentyl glycol, neopentyl glycol and the like.
Among these, as the alkylene glycol compound (B), in particular, the reaction of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol A thing is preferable in order to improve the decontamination property of the film 1. Such a reaction product is liquid at room temperature, so it is easily mixed with other materials, and can be dissolved in a solvent faster than a powdery material. Moreover, such a reaction product is generally easily available and suitable for mass production.

  Moreover, it is preferable that both an alkylene glycol compound (A) and an alkylene glycol compound (B) contain polyethyleneglycol. By comprising in this way, compatibility with an alkylene glycol compound (A) and an alkylene glycol compound (B) improves more, the decontamination property of the film 1 improves, and the film 1 is contaminated over a long period of time. Removability can be demonstrated. These were clarified by experiments by the present inventors as will be described later. As an example in which both the alkylene glycol compound (A) and the alkylene glycol compound (B) contain polyethylene glycol, the alkylene glycol compound (A) is polyethylene glycol diglycidyl ether, and the alkylene glycol compound (B) is methyl 3- (3 A combination that is a reaction product of-(2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol can be given.

  The total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the base resin. If content is 1 mass part or more, since the surface of the film 1 exhibits hydrophilicity further, the outstanding decontamination property can be exhibited. Further, if the content is 10 parts by mass or less, it is considered that the compatibility between the alkylene glycol compounds (A) and (B) and the base resin can be maintained better, and the liquid dye in which a liquid substance oozes from the film 1 Protrusion can be reduced and the appearance of the film 1 can be kept good. These were clarified by experiments by the present inventors as will be described later. Moreover, it is thought that decontamination property continues further because content is 10 mass parts or less. Furthermore, the total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is more preferably in the range of 2 to 10 parts by mass with respect to 100 parts by mass of the base resin. When the total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is within such a range, the decontamination property of the film 1 can be further maintained. This has been clarified by experiments by the present inventors as will be described later.

  Moreover, in the film 1 whose total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the base resin, the alkylene glycol compound (A) and the alkylene glycol compound The mass ratio with (B) may be 1/5 to 5/1, and more preferably 1/2 to 2/1. When this mass ratio is in the range of 1/2 to 2/1, the decontamination property of the film 1 can be further maintained. This has been clarified by experiments by the present inventors as will be described later. Particularly in the film 1 in which the total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is 2 to 10 parts by mass with respect to 100 parts by mass of the base resin, the alkylene glycol compound (A) and the alkylene glycol compound ( The mass ratio with B) is preferably in the range of 1/2 to 2/1. Thus, the ultraviolet-absorbing ability of the film by a benzotriazole group is exhibited more by containing a predetermined amount of alkylene glycol compound (B).

  Moreover, an inorganic hydrophilic compound and a bleeding hydrophilic agent can be further added to the film 1 as necessary.

  Moreover, the film 1 may be colored with a colorant. The colorant is not particularly limited, but is preferably a colorant having weather resistance and durability that can be used for a long period of time. It is preferred to choose from colorants listed in Second Revision (1982) and SUPPLEMENT (1982).

  The film 1 can be formed by hot melt molding methods such as extrusion method and calender molding method, and film formation by solution casting method or sol casting method using a solution diluted to a viscosity that can be applied with a solvent or the like. It is. Among these, the film 1 is preferably formed by film formation by a solution cast method or a sol cast method, particularly considering the heat decomposability of the alkylene glycol compound (A) and the alkylene glycol compound (B).

  Such a film 1 may be used only by the film 1, and may be used in the state laminated | stacked on the surface of the film similar to the film 1 or a film different from the film 1. FIG.

<Embodiment of adhesive film>
The pressure-sensitive adhesive film 2 of the present embodiment is formed by laminating a pressure-sensitive adhesive layer 21 on one surface 11 of the film 1 described above.

The pressure-sensitive adhesive layer 21 can be a pressure-sensitive adhesive layer used in a normal pressure-sensitive adhesive film, and is a layer composed of a pressure-sensitive pressure-sensitive adhesive, a heat-sensitive pressure-sensitive adhesive (including a hot melt pressure-sensitive adhesive), a solvent activated pressure-sensitive adhesive, and the like. is there. The pressure-sensitive adhesive is sometimes called an adhesive.
Specific examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 21 include acrylic, polyolefin, polyester, polyurethane, silicone, and epoxy pressure-sensitive adhesives. Among these, it is particularly preferable to use an acrylic pressure-sensitive adhesive in terms of workability, workability, and weather resistance of the pressure-sensitive adhesive film.
In addition, when adhering the adhesive film 2 to an adherend having distortion or unevenness on the surface or an adherend having a curved surface, it has a peel strength of 5 to 50 N / 25 mm (180 degree peel, 300 mm / min). It is preferable to use an adhesive.

  The pressure-sensitive adhesive layer 21 may be formed by applying a solution containing a pressure-sensitive adhesive on one surface 11 of the film 1. The thickness of the pressure-sensitive adhesive layer 21 is sufficient if sufficient adhesive strength is obtained and the pressure-sensitive adhesive film 2 is not too thick, and is usually in the range of 5 to 500 μm, preferably 10 to 300 μm, more preferably 30 to 80 μm. It is said.

  Moreover, in order to improve a weather resistance, an ultraviolet absorber and a heat stabilizer may be added to the adhesive layer 21. Moreover, in order to improve the adhesive force of the adhesive film 2, a crosslinking agent (hardening agent), a tackifier, a plasticizer, etc. may be added in an adhesive layer.

  Various types of fillers may be dispersed in the pressure-sensitive adhesive layer 21. Examples of the filler include light calcium carbonate, heavy calcium carbonate, aluminum dioxide, aluminum hydroxide, talc, titanium dioxide, barium sulfate, and silicon dioxide. As silicon dioxide, those produced by various production methods such as a grinding method, a grinding and melting method, a sedimentation method, and a gas phase method can be used favorably. By dispersing such a filler in the pressure-sensitive adhesive layer, the pressure-sensitive adhesive performance can be further enhanced. As titanium dioxide, a rutile crystal structure, an anatase crystal structure, and those subjected to various surface treatments can be used favorably. Moreover, the total light transmittance of an adhesive film can be adjusted by disperse | distributing a filler.

  According to the adhesive film of this embodiment, the film 1 contains both the alkylene glycol compound (A) having a glycidyl group and the alkylene glycol compound (B) having a benzotriazole group, whereby the alkylene glycol compound (A) and the alkylene Release of the glycol compound (B) from the mother resin is reduced. Therefore, the adhesive layer 21 is reduced from being detached together with the bleed-out compound. For this reason, it can reduce that the film 1 peels in the state in which the adhesive film 2 was stuck to the object.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

(Example 1)
The following raw materials were prepared by T.M. K. Using a homodisper, the mixture was stirred at 2000 rpm for 30 minutes to obtain a uniform organosol.
The obtained organosol was applied to a G2ZPET 75 μm film manufactured by Teijin Ltd. using an applicator with a micrometer manufactured by Tester Sangyo Co., Ltd., the solvent was volatilized at 80 ° C. for 2 minutes, cured at 200 ° C. for 1 minute, and PET film And a film having a thickness of 50 μm was produced.
-Raw material-
・ Mother resin: Paste vinyl chloride resin manufactured by Vitec Co., Ltd. P-540 = 100 parts by mass ・ Alkylene glycol compound (A): Epolite 400E “Kyoeisha Chemical Co., Ltd.” “Polyethylene glycol diglycidyl ether” = 2 parts by mass ・ Alkylene glycol compound (B): Tinuvin 213 manufactured by Ciba Specialty Chemicals Co., Ltd. “Methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol having a molecular weight of 300 2) parts by mass of plasticizer: polyester plasticizer Fine Sizer NS-5701 manufactured by Dainichi Seika Co., Ltd. 31 parts by mass: modifier: solution type acrylic resin Nissetsu MM075A-1 manufactured by Nippon Carbide Industries Co., Ltd. 30 parts by mass / thermal stability : Katsuta Kako Co., Ltd. octyltin mercaptide TM-188J = 1 parts by stabilizing auxiliaries: Adeka Corp. Stab 1500 = 0.5 part by mass Solvent: Solvesso 100 = 50 parts by weight

(Example 2)
The following raw materials were dissolved in an autoclave at 100 ° C. for 1 hour to obtain a resin solution.
The obtained resin solution was applied to a G2Z PET 75 μm film manufactured by Teijin Limited, dried at 60 ° C. for 1 minute, and subsequently dried at 130 ° C. for 2 minutes, and peeled from the PET film to prepare a film having a thickness of 50 μm.
-Raw material-
・ Mother resin: Paste vinyl chloride resin manufactured by Vitec Co., Ltd. P-540 = 100 parts by mass ・ Alkylene glycol compound (A): Epolite 400E “Kyoeisha Chemical Co., Ltd.” “Polyethylene glycol diglycidyl ether” = 2 parts by mass ・ Alkylene glycol compound (B): Tinuvin 213 manufactured by Ciba Specialty Chemicals Co., Ltd. “Methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol having a molecular weight of 300 2) parts by mass of plasticizer: polyester plasticizer Fine Sizer NS-5701 manufactured by Dainichi Seika Co., Ltd. 31 parts by mass: modifier: solution type acrylic resin Nissetsu MM075A-1 manufactured by Nippon Carbide Industries Co., Ltd. 30 parts by mass, heat stable Agent: Octyl tin mercaptide manufactured by Katsuta Chemical Co., Ltd. TM-188J = 1 part by mass. Stabilizing aid: Adeka Co., Ltd. Adeka Stub 1500 = 0.5 part by mass. Solvent: Tetrahydrofuran manufactured by Mitsubishi Chemical Co., Ltd. = 600 parts by mass.

Example 3
A mixture was obtained using the following raw materials using a Henschel mixer manufactured by Mitsui Miike Kako Co., Ltd. Next, the mixture was put into a 14-inch two roll heated to 165 ° C., preliminarily kneaded, and then the uniformly melted mixture was heated to 180/180/170/165 ° C. The film was put into a 4-inch calendar roll, and a film having a thickness of 50 μm was prepared by adjusting the gaps.
-Raw material-
・ Mother resin: Straight vinyl chloride resin manufactured by Vitec Co., Ltd. MT1100 = 100 parts by mass ・ Alkylene glycol compound (A): Epolite 400E “Kyoeisha Chemical Co., Ltd.” “Polyethylene glycol diglycidyl ether” = 2 parts by mass ・ Alkylene glycol compound (B ): Tinuvin 213 manufactured by Ciba Specialty Chemicals Co., Ltd. Condensation of “methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate with polyethylene glycol having a molecular weight of 300” Product] = 2 parts by mass. Plasticizer: Polyester plasticizer fine sizer NS-5701 manufactured by Dainichi Seika Co., Ltd. 31-5 parts by mass. Heat stabilizer: SC-1001 manufactured by Adeka Co., Ltd. = 0.8 parts by mass.
: SP-2002 = 1.6 parts by mass manufactured by Adeka Co., Ltd./Stabilizing aid: Adeka stub 1500 manufactured by Adeka Co., Ltd. = 0.5 parts by mass

Example 4
The following raw materials were dissolved in an autoclave at 100 ° C. for 1 hour to obtain a resin solution. The obtained resin solution was applied to a G2Z PET 75 μm film manufactured by Teijin Limited, dried at 60 ° C. for 1 minute, and subsequently dried at 130 ° C. for 2 minutes, and peeled from the PET film to prepare a film having a thickness of 50 μm.
-Raw material-
-Mother resin: Nippon Carbide Industries Co., Ltd. acrylic resin (MMA / BA = 63/37) = 85 parts by mass: Cellulose resin manufactured by Eastman Chemical CAB-381-20 = 10 parts by mass: Kuraray Co., Ltd. polyester-urethane resin Clamiron U8765 = 5 parts by mass / alkylene glycol compound (A): Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd. “polyethylene glycol diglycidyl ether” = 2 parts by mass / alkylene glycol compound (B): Tinuvin 213 manufactured by Ciba Specialty Chemicals Co., Ltd. “Condensate of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol having a molecular weight of 300” = 2 parts by mass / stabilizing aid: ADEKA Made by Co., Ltd. Dekasutabu 1500 = 0.5 part by mass Solvent: Mitsubishi Chemical Corp. tetrahydrofuran = 614 parts by weight

(Example 5)
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the addition amounts of Epolite 400E and Tinuvin 213 were each changed to 3 parts by mass with respect to 100 parts by mass of the base resin.

(Example 6)
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the addition amounts of Epolite 400E and Tinuvin 213 were each 0.3 parts by mass with respect to 100 parts by mass of the base resin.

(Example 7)
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the addition amounts of Epolite 400E and Tinuvin 213 were each changed to 0.5 parts by mass with respect to 100 parts by mass of the base resin.

(Example 8)
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the addition amounts of Epolite 400E and Tinuvin 213 were each changed to 1.0 part by mass with respect to 100 parts by mass of the base resin.

Example 9
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the addition amounts of Epolite 400E and Tinuvin 213 were changed to 4.0 parts by mass with respect to 100 parts by mass of the base resin.

(Example 10)
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the addition amounts of Epolite 400E and Tinuvin 213 were changed to 5.0 parts by mass with respect to 100 parts by mass of the base resin.

(Example 11)
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the addition amounts of Epolite 400E and Tinuvin 213 were changed to 5.5 parts by mass with respect to 100 parts by mass of the base resin.

[Evaluation]
About the film produced in Examples 1-11, it measured and evaluated by the following method. In addition, the material used for preparation of the film of Examples 1-11, its mass ratio, and the result of a measurement and evaluation are shown in following Table 1.

(1) Preparation of test sample Crosslinking agent CK-101 (Nippon Carbide Industries Co., Ltd.) 2 with respect to 100 parts by mass of acrylic ester PE-121 (Nihon Carbide Industries Co., Ltd.) 2 .5 parts by mass and 25 parts by mass of ethyl acetate were mixed to prepare an adhesive solution.
The adhesive solution was applied to release paper with a 200 μm gap paint applicator, dried at 90 ° C. for 2 minutes, and the films obtained in Examples 1 to 11 were bonded together to obtain an adhesive film.
Made of Nippon Carbide Industries Co., Ltd., a white vinyl chloride film with a pressure-sensitive adhesive layer, affixed to each 1 mm-thick aluminum plate with the product name HISCAL 5010 White, and then stuck each adhesive film on this vinyl chloride film. A sample was used.

(2) Evaluation of initial decontamination (before weathering test)-Decontamination test-
Carbon black MCF885 parts by mass produced by Mitsubishi Chemical Corporation was dispersed in 95 parts by mass of ion-exchanged water to prepare a 5% by mass lipophilic contaminant.
On the test sample prepared in the above (1), 1.2 ml of the contaminant was dropped and allowed to stand overnight to air dry. The contaminated portion was washed with running water, and lightly wiped with an industrial wiper and Bencott manufactured by Asahi Kasei Corporation.
− Decontamination evaluation −
Thereafter, the decontamination property of the test sample was visually confirmed according to the following evaluation criteria.
<Evaluation criteria>
○: No contamination (black) was observed in the test sample.
(Triangle | delta): The contamination (black) of the grade which is not a problem practically was confirmed to the test sample.
X: Contamination (black) was confirmed in the test sample.
− Lightness measurement −
Moreover, the lightness L * was measured with the D65 light source CIE method using the spectrocolorimeter CM-3600d by Konica Minolta Sensing Co., Ltd. for the test samples before and after the contamination removal test. Note that the smaller the change in the lightness L * before and after the decontamination test, the higher the decontamination performance.

(3) Evaluation of decontamination after 152 hours of weathering test-Weathering test-
The test sample prepared in (1) above was irradiated for 152 hours using a Suga Test Instruments Sunshine Weather Meter S80.
− Decontamination test −
On the test sample after the weather resistance test, 1.2 ml of the contaminant prepared in the above (2) was dropped, and left overnight to air dry. The contaminated portion was washed with running water, and lightly wiped with an industrial wiper and Bencott manufactured by Asahi Kasei Corporation.
− Decontamination evaluation −
Thereafter, the decontamination property of the test sample was visually confirmed according to the following evaluation criteria.
<Evaluation criteria>
○: No contamination (black) was observed in the test sample.
(Triangle | delta): The contamination (black) of the grade which is not a problem practically was confirmed to the test sample.
X: Contamination (black) was confirmed in the test sample.
− Lightness measurement −
Moreover, the lightness L * was measured with the D65 light source CIE method using the spectrocolorimeter CM-3600d by Konica Minolta Sensing Co., Ltd. for the test samples before and after the contamination removal test. Note that the smaller the change in the lightness L * before and after the decontamination test, the higher the decontamination performance.

(4) Evaluation of decontamination after 1000 hours of weathering test-Weathering test-
The test sample prepared in (1) above was irradiated for 1000 hours using a Suga Test Instruments Sunshine Weather Meter S80.
− Decontamination test −
On the test sample after the weather resistance test, 1.2 ml of the contaminant prepared in the above (2) was dropped, and left overnight to air dry. The contaminated portion was washed with running water, and lightly wiped with an industrial wiper and Bencott manufactured by Asahi Kasei Corporation.
− Decontamination evaluation −
Thereafter, the decontamination property of the test sample was visually confirmed according to the following evaluation criteria.
<Evaluation criteria>
○: No contamination (black) was observed in the test sample.
(Triangle | delta): The contamination (black) of the grade which is not a problem practically was confirmed to the test sample.
X: Contamination (black) was confirmed in the test sample.
− Lightness measurement −
Moreover, the lightness L * was measured with the D65 light source CIE method using the spectrocolorimeter CM-3600d by Konica Minolta Sensing Co., Ltd. for the test samples before and after the contamination removal test. Note that the smaller the change in the lightness L * before and after the decontamination test, the higher the decontamination performance.

  As shown in Table 1, in the films of Examples 1 to 11 to which both the alkylene glycol compound (A) and the alkylene glycol compound (B) were added, after the weather resistance test for 152 hours and after the weather resistance test for 1000 hours And had a high decontamination property. Especially the film of Examples 1-4 whose total content of alkylene glycol compound (A) and alkylene glycol compound (B) is 1 mass part or more with respect to 100 mass parts of mother resin, and Examples 7-11 This film was able to maintain the decontamination property better than Example 6 in which the total content of the resin was outside this range. Liquid exudation was confirmed in the film of Example 11 in which the total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) exceeds 10 parts by mass with respect to 100 parts by mass of the base resin. That is, if the total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the base resin, the occurrence of a change in appearance is reduced. As a result, the decontamination property can be maintained. Furthermore, the films of Examples 1 to 4 in which the total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is in the range of 2 to 10 parts by mass with respect to 100 parts by mass of the base resin, and As a result, the films of Examples 8 and 9 could maintain the decontamination property of the film more.

  Next, examples in which the alkylene glycol compound (A) and the alkylene glycol compound (B) have different mass ratios will be described.

(Example 12)
In Example 1, the same as in Example 1 except that the addition amount of Epolite 400E and 0.67 part by mass are changed to 3.33 parts by mass of Tinuvin 213 with respect to 100 parts by mass of the base resin. Thus, a film having a thickness of 50 μm was produced.

(Example 13)
In Example 1, the same as Example 1 except that the addition amount of Epolite 400E and 1.33 parts by mass were changed to 2.67 parts by mass with respect to 100 parts by mass of the base resin. Thus, a film having a thickness of 50 μm was produced.

(Example 14)
In Example 1, the same as in Example 1 except that the addition amount of Epolite 400E and 2.67 parts by mass are changed to 1.33 parts by mass with respect to 100 parts by mass of the base resin. Thus, a film having a thickness of 50 μm was produced.

(Example 15)
In Example 1, the same as Example 1 except that the addition amount of Epolite 400E and 3.33 parts by mass are changed to 0.67 parts by mass with respect to 100 parts by mass of the base resin. Thus, a film having a thickness of 50 μm was produced.

[Evaluation]
About the film produced in Examples 12-15, it measured and evaluated by the method similar to the measurement and evaluation method of Examples 1-11. Table 2 below shows the materials used in the production of the films of Examples 12 to 15, their mass ratios, and the results of measurement and evaluation.

  As shown in Table 2, if the mass ratio of the alkylene glycol compound (A) to the alkylene glycol compound (B) is at least 1/5 to 5/1, the decontamination performance is maintained to such an extent that it does not cause a practical problem. It was confirmed. Moreover, the film of Example 13 and 14 whose mass ratio of alkylene glycol compound (A) and alkylene glycol compound (B) is 1 / 2-2 / 1 is Example 12 whose mass ratio is 1/5. And the film of Example 15 having a mass ratio of 5/1 were found to have better decontamination after a 1000 hour durability test. This is considered to be remarkable when the total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the base resin. Becomes more prominent when it is 2 to 10 parts by mass with respect to 100 parts by mass of the base resin.

  Next, examples in which the alkylene glycol compound (A) does not contain polyethylene glycol will be described.

(Example 16)
A film having a thickness of 50 μm was prepared in the same manner as in Example 1 except that the same amount of Epolite 200P “Tripropylene glycol diglycidyl ether” manufactured by Kyoeisha Chemical Co., Ltd. was used instead of Epolite 400E.

(Example 17)
In Example 12, a film having a thickness of 50 μm was produced in the same manner as in Example 12 except that the same amount of Epolite 200P was used instead of Epolite 400E.

(Example 18)
In Example 13, a film having a thickness of 50 μm was produced in the same manner as in Example 13 except that the same amount of Epolite 200P was used instead of Epolite 400E.

(Example 19)
In Example 14, a 50 μm-thick film was produced in the same manner as in Example 14 except that the same amount of Epolite 200P was used instead of Epolite 400E.

(Example 20)
In Example 15, a film having a thickness of 50 μm was produced in the same manner as in Example 15 except that the same amount of Epolite 200P was used instead of Epolite 400E.

[Evaluation]
About the film produced in Examples 16-20, it measured and evaluated by the method similar to the measurement of Example 1-11, and the method of evaluation. The materials used for the production of the films of Examples 16 to 20, their mass ratios, and the results of measurement and evaluation are shown in Table 3 below.

  As shown in Table 3, even in the films of Examples 16 to 20, the film of Example 1 was more durable than the film of Example 16 although it had a practical level of durability for contamination removal. The film of Example 12 is more durable in terms of decontamination, and the film of Example 12 is more durable in terms of decontamination than the film of Example 17, and the film of Example 13 is more decontaminating than the film of Example 18. The film of Example 14 is more durable for decontamination than the film of Example 19, and the film of Example 15 is more durable for decontamination than the film of Example 20. The result was high. That is, the film method in which both the alkylene glycol compound (A) and the alkylene glycol compound (B) contain polyethylene glycol has a higher durability in terms of decontamination than the film in which only the alkylene glycol compound (B) contains polyethylene glycol. It became. This is because in the films of Examples 12 to 15, the alkylene glycol compound (A) and the alkylene glycol compound (B) both contain polyethylene glycol, so that the alkylene glycol compound (A) and the alkylene glycol compound (B) The present inventors consider that the compatibility is improved.

(Comparative Example 1)
A film having a thickness of 50 μm was prepared in the same manner as in Example 1 except that tinuvin 213 was not added.

(Comparative Example 2)
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that Epolite 400E was not added.

(Comparative Example 3)
A film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the amount of Epolite 400E was changed to 4 parts by mass and Tinuvin 213 was not added.

(Comparative Example 4)
A film having a thickness of 50 μm was produced in the same manner as in Example 1 except that the amount of tinuvin 213 added in Example 1 was changed to 4 parts by mass and that Epolite 400E was not added.

(Comparative Example 5)
In Example 1, a film having a thickness of 50 μm was produced in the same manner as in Example 1 except that Epolite 400E and Tinuvin 213 were not added.

(Comparative Example 6)
A film having a thickness of 50 μm was prepared in the same manner as in Example 1 except that the same amount of Adeka Sizer EP-13 “Bisphenol A diglycidyl ether” manufactured by Adeka Corporation was used instead of Epolite 400E. .

(Comparative Example 7)
In Example 1, instead of Tinuvin 213, Tinuvin 571 “2- (2H-benzotriazol-2-yl) -6-dositol-4-” manufactured by Ciba Specialty Chemicals Co., Ltd., which is a non-alkylene glycol-based benzotriazole compound. Methylphenol
Adeka Sizer EP-13 manufactured by Adeka Co., Ltd. A film having a thickness of 50 μm was prepared in the same manner as in Example 1 except that the same amount of “bisphenol A diglycidyl ether” was used.

[Evaluation]
About the film produced by Comparative Examples 1-7, it measured and evaluated by the method similar to the measurement of Example 1-11 and the method of evaluation. The materials used for the production of the films of Comparative Examples 1 to 7, their mass ratios, and the results of measurement and evaluation are shown in Table 4 below.

  In the films of Comparative Examples 1 to 7 in which neither the alkylene glycol compound (A) nor the alkylene glycol compound (B) is added, the decontamination property is low even before the weather resistance test, and the decontamination property after each weather resistance test is low. The result was further reduced, resulting in impractical results.

  From the above, it was confirmed that a film to which both the alkylene glycol compound (A) and the alkylene glycol compound (B) were added can exhibit excellent decontamination for a long period of time.

  As described above, the present invention can be suitably used for marking films, protective films, and the like.

DESCRIPTION OF SYMBOLS 1 ... Film 2 ... Adhesive film 10 ... Film layer 21 ... Adhesive layer

Claims (9)

A base resin containing at least one of vinyl chloride resin and acrylic resin;
An alkylene glycol compound (A) having a glycidyl group;
An alkylene glycol compound (B) having a benzotriazole group;
Containing film.   The film according to claim 1, wherein both the alkylene glycol compound (A) and the alkylene glycol compound (B) contain polyethylene glycol.   The film according to claim 2, wherein the alkylene glycol compound (A) is polyethylene glycol diglycidyl ether.   The alkylene glycol compound (B) is a reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol. The film according to claim 3.   5. The total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is 1 to 10 parts by mass with respect to 100 parts by mass of the base resin. Film.   The film according to claim 5, wherein a total content of the alkylene glycol compound (A) and the alkylene glycol compound (B) is 2 to 10 parts by mass with respect to 100 parts by mass of the base resin.   The film according to claim 5 or 6, wherein a mass ratio of the alkylene glycol compound (A) to the alkylene glycol compound (B) is from 1/5 to 5/1.   The film according to claim 7, wherein a mass ratio of the alkylene glycol compound (A) to the alkylene glycol compound (B) is 1/2 to 2/1. The film according to any one of claims 1 to 8,
An adhesive layer disposed on at least one surface of the film;
An adhesive film comprising

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