JP2021154730A - Multilayer film, adhesive film, decorative film, decorative adhesive film, and automobile protective film - Google Patents

Abstract

To provide a polyolefin-based resin film which has excellent scratch resistance, flexibility and followability to a molding having a three-dimensional shape.SOLUTION: A polyolefin-based resin multilayer film, which is a multilayer film having a plurality of layers containing a polyolefin-based resin, has a layer composed of a resin composition containing 0.20 pts.mass or more of a silicone-olefin copolymer with respect to 100 pts.mass of the polyolefin-based resin on at least one surface side of a surface and a rear face, and has a tensile elastic modulus of 400 MPa or less.SELECTED DRAWING: None

Description

The present invention is suitable for industrial adhesive films (tapes), decorative adhesive films (tapes) such as stickers, labels and marking films attached to impart design to automobiles, etc., decorative sheets, etc. The present invention relates to a multi-layer film having excellent scratch resistance used in the above, an adhesive film in which an adhesive layer is laminated on the film, and the like.

Conventionally, decorative adhesive films (tapes) such as stickers, labels and marking films, decorative sheets, etc., which are attached to give design to industrial adhesive films (tapes), signs, automobiles, etc., are colored. A film made of a polyvinyl chloride resin (hereinafter, also referred to as "PVC-based film") having excellent properties, processability, scratch resistance, weather resistance and the like is often used as a base material.
The PVC-based film has rigidity by itself, but a plasticizer is added for the purpose of imparting flexibility so that it can function as an adhesive film. However, depending on the plasticizer used, there is a problem that the compatibility with the adhesive is poor, the stability of the adhesive film is poor, and the bleed-out of the plasticizer becomes remarkable. There is also a tendency for regulations to be tightened on the use of plasticizers themselves.
Therefore, a polyolefin-based resin film has been widely used as an alternative material to the PVC-based film.

Adhesive films such as marking films that use polyolefin resin films as the base material are known, and in response to the demand for films with appropriate flexibility, the base material is blended with an elastomer component, and the base material is coated with acrylic-modified urethane. An adhesive film having improved scratch resistance and durability by laminating films is known (Patent Document 1).
Furthermore, we propose a laminated film suitable for various applications, including a marking film that uses a polyolefin-based resin with excellent flexibility, has high gloss, and has good scratch resistance, curved surface followability, and sticking workability. It has also been done (Patent Documents 2 and 3).
Further, for the purpose of obtaining a molded product having excellent antifouling properties, a film containing a silicone-olefin copolymer in a polyolefin resin has also been proposed (Patent Document 4).

However, since the techniques described in Patent Documents 1 to 3 are techniques for imparting performance by coating, there are problems such as environmental problems due to drying and volatilization of the solvent, management due to an increase in processes, and deterioration of economic efficiency. Further, since the coating films described in Patent Documents 1 to 3 have a crosslinked structure, there is also a problem that they are inferior in followability and elongation to the shape of the molded product to be bonded.
Regarding Patent Document 4, although the antifouling property and the slipperiness of the surface can be improved by using the silicone-olefin copolymer, the polyolefin resin used is hard and has a high melting point, so that the three-dimensional shape is obtained. There is a problem in the ability to follow the molded body.
Therefore, there is still room for improvement from the viewpoint of environmental problems, simplification of the process, and application to a molded product having a three-dimensional shape.

Japanese Unexamined Patent Publication No. 2004-2825 JP-A-2007-83530 Japanese Patent No. 5112646 JP-A-2017-206587

In view of such conventional problems, it is an object of the present invention to provide a polyolefin-based resin multilayer film having excellent scratch resistance, flexibility, and followability to a molded product having a three-dimensional shape.
Further, the present invention has the above-mentioned characteristics, and it is also possible to obtain an adhesive film or a decorative film by laminating an adhesive layer or a printing layer on the film, and these films are suitably used for automobile cosmetic applications. It is an object of the present invention to provide a polyolefin-based resin multilayer film capable of providing a capable film.

As a result of diligent studies, the present inventors have identified a multi-layer film having a layer composed of a resin composition containing a predetermined amount of a polyolefin resin and a silicone-olefin copolymer on at least one of the front and back surfaces. We have found that a polyolefin-based resin film having a tensile elasticity in the range of can solve the above problems, and have completed the present invention.

That is, the gist of the present invention is as follows.
[1] A multi-layer film having a plurality of layers containing a polyolefin-based resin.
A layer made of a resin composition containing 0.20 parts by mass or more of a silicone-olefin copolymer with respect to 100 parts by mass of a polyolefin resin is provided on at least one of the front and back surfaces.
The multilayer film is characterized in that the tensile elastic modulus of the multilayer film is 400 MPa or less.
[2] The multilayer film according to [1], wherein a silicone-olefin copolymer masterbatch containing the silicone-olefin copolymer is used as the silicone-olefin copolymer.
[3] The multilayer film according to [1] or [2], which is composed of at least two layers.
[4] The multilayer film according to any one of [1] to [3], wherein the polyolefin-based resin contains one or more of a polyethylene-based resin, a polypropylene-based resin, and an olefin-based elastomer. ..
[5] The item according to any one of [1] to [4], wherein each layer of the multilayer film contains 50 parts by mass or more of an olefin elastomer with respect to 100 parts by mass of a polyolefin resin. Multi-layer film.
[6] At least one layer of the multilayer film contains 50 parts by mass or more of an olefin elastomer with respect to 100 parts by mass of a polyolefin resin.
The item according to any one of [1] to [4], wherein the layer made of the resin composition contains 5 to 50 parts by mass of an olefin elastomer with respect to 100 parts by mass of the polyolefin resin. Multi-layer film.
[7] At least a surface layer, an intermediate layer and a back layer are provided, and the surface layer and the back layer contain 1 part by mass or more and 80 parts by mass or less of an olefin elastomer with respect to 100 parts by mass of the polyolefin resin, and the intermediate layer is: The olefin-based elastomer is contained in an amount of 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the polyolefin-based resin, and at least one layer of the surface layer and the back layer contains both silicone and olefin with respect to 100 parts by mass of the polyolefin-based resin. The multilayer film according to [6], which is a layer made of a resin composition containing 0.20 parts by mass or more of a polymer.
[8] The multilayer film according to any one of [1] to [7], wherein the 60 ° gloss value after the Gakushin wear test is 60 or more.
[9] An adhesive film obtained by laminating an adhesive layer on at least one surface of the film according to any one of [1] to [8].
[10] A decorative film obtained by laminating a printing layer on at least one side of the film according to any one of [1] to [8].
[11] A cosmetic adhesive film obtained by further laminating an adhesive layer on the print layer side of the decorative film according to [10].
[12] A protective film for automobiles using the film according to any one of [9] to [11].

In the present invention, by using a film having a layer composed of a resin composition containing a predetermined amount of a polyolefin resin and a silicone-olefin copolymer, a molded product having excellent scratch resistance, flexibility and a three-dimensional shape. It is possible to obtain a multilayer film having a followability to the above. Further, it is also possible to obtain an adhesive film, a decorative film or a cosmetic adhesive film by laminating an adhesive layer or a printing layer on the film, and these films can be suitably used for automobile cosmetic applications.

The present invention will be described in detail below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof. In addition, when the expression "-" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

One embodiment of the present invention is a multi-layer film having a plurality of layers containing a polyolefin-based resin, and contains 0.20 parts by mass or more of a silicone-olefin copolymer with respect to 100 parts by mass of the polyolefin-based resin. A multi-layer film having a layer made of a resin composition on at least one of the front and back surfaces and having a tensile elasticity of 400 MPa or less (hereinafter, "multi-layer film of the present invention"). Also called).

<Polyolefin resin>
The resin composition used in the present invention contains a polyolefin-based resin and a silicone-olefin copolymer as essential components (hereinafter, this resin composition is referred to as "resin composition A").

Polyolefin-based resins are preferably used from the viewpoints of availability, flexibility, handleability, and economy of the resin.

Examples of the polyolefin-based resin include polyethylene-based resins, polypropylene-based resins, olefin-based elastomers, cyclic olefin-based resins, and the like.
Among the polyolefin-based resins, polyethylene-based resins, polypropylene-based resins, and olefin-based elastomers are preferable from the viewpoint of easy availability and imparting flexibility to the obtained film.

Examples of the polyethylene-based resin include homopolymers of ethylene, copolymers of ethylene containing ethylene as a main component and other monomers copolymerizable (low-density polyethylene (LDPE), high-pressure low-density polyethylene, and the like. Linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), ethylene-based copolymer (metallocene-based polyethylene) obtained by polymerization using a metallocene-based catalyst, ethylene-vinyl acetate copolymer, ethylene- (meth). ) Methyl acrylate copolymer, ethylene- (meth) ethyl acrylate copolymer, ethylene- (meth) butyl acrylate copolymer, ethylene- (meth) acrylate copolymer, ethylene- (meth) acrylate copolymer Examples thereof include a metal ion crosslinked resin (ionomer) of a polymer.
Among them, low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) are preferably used from the viewpoint of easy availability, handleability of the resin, and imparting flexibility to the obtained film.

Examples of the polypropylene-based resin include a homopolymer of propylene (homopolypropylene), a copolymer of propylene containing propylene as a main component and another monomer copolymerizable with the copolymer, and a mixture thereof.
Examples of the copolymer with the propylene containing propylene as a main component and another monomer copolymerizable with the propylene include a random copolymer (random polypropylene) of propylene and ethylene or another α-olefin, or a block copolymer. (Block polypropylene), a block copolymer containing a rubber component, a graft copolymer and the like can be mentioned.

The α-olefin used as the other monomer copolymerizable with propylene preferably has 4 to 12 carbon atoms, and is, for example, 1-butene, 1-pentene, 1-hexene, 1-hexene. , 1-octene, 4-methyl-1-pentene, 1-decene and the like, and one or a mixture of two or more thereof is used.

The olefin-based elastomer is a soft resin containing a polyolefin-based resin and a rubber component, and the rubber component may be dispersed in the polyolefin-based resin or may be copolymerized with each other.
Specific examples of the olefin-based elastomer include ethylene-propylene copolymer elastomer, ethylene-1-butene copolymer elastomer, ethylene-propylene-1-butene copolymer elastomer, and ethylene-1-hexene copolymer elastomer. , Ethylene-1-octene copolymer elastomer, ethylene-styrene copolymer elastomer, ethylene-norbornene copolymer elastomer, propylene-1-butene copolymer elastomer, ethylene-propylene-non-conjugated diene copolymer elastomer, ethylene Atypical elastic copolymers mainly composed of olefins such as -1-butene-non-conjugated diene copolymer elastomer and ethylene-propylene-1-butene-non-conjugated diene copolymer elastomer, derivatives thereof and acid modification. Derivatives and the like can be mentioned.
Depending on the method for producing the olefin elastomer, it is classified into a reactor type, a simple blend type, a dynamic cross-linking type, etc., but the reactor type can be used because the domain diameter of the dispersed rubber component is small and the transparency is high. preferable.
Specific examples of the reactor-type olefin-based elastomer include "Wellnex (manufactured by Japan Polypropylene Corporation)", "Zeras (manufactured by Mitsubishi Chemical Corporation)", "Cataloy (manufactured by SunAllomer Ltd.)" and the like.

The polyethylene-based resin, polypropylene-based resin, and olefin-based elastomer described above may be used alone or in combination of two or more. From the viewpoint of the flexibility of the obtained film and the film-forming property when processing the film, it is preferable to use two or more kinds in combination.

The melt flow rate of the polyolefin resin is appropriately selected depending on the molding method and application to which it is applied, but the value measured under a temperature condition of 190 ° C. or 230 ° C. under a load of 2.16 kg is 0.1 to 50 g / 10 minutes. Is preferable. When it is 0.1 g / 10 minutes or more, the moldability of the film is good, and when it is 50 g / 10 minutes or less, the thickness accuracy of the film can be kept good. It is more preferably 0.5 to 40 g / 10 minutes, and even more preferably 1.0 to 30 g / 10 minutes.

Regarding the strength of the polyolefin-based resin, it is preferable that the tensile elastic modulus of the film produced by the polyolefin-based resin alone is in the range of 100 to 2000 MPa. When the tensile elastic modulus is in the range of 100 to 2000 MPa, it is possible to impart appropriate flexibility to the film obtained from the resin composition of the present invention. It is more preferably in the range of 150 to 1900 MPa, still more preferably in the range of 200 to 1800 MPa. Further, from the viewpoint of the flexibility and processability of the obtained multilayer film, the elastic modulus of the polyolefin resin is preferably 400 MPa or less.

Each layer other than the layer made of the resin composition A of the multilayer film of the present invention is made of a polyolefin-based resin composition containing a polyolefin-based resin (hereinafter, also referred to as "polyolefin-based resin composition B"). The type of the polyolefin resin contained in each of these layers may be one type or two or more types. Further, the composition of the polyolefin-based resin composition B constituting each of these layers may be the same or different.

Further, from the viewpoint of imparting flexibility to the multilayer film of the present invention, the resin composition (that is, the resin composition A and the polyolefin-based resin composition B) used for each layer of the multilayer film contains an olefin-based elastomer. Is preferably added. Further, in order to impart sufficient flexibility to the multilayer film, the proportion of the olefin elastomer in the polyolefin resin used in each layer of the multilayer film is more preferably 50 parts by mass or more, more preferably 60 parts by mass. The above is more preferable.

Further, as another method for imparting flexibility, the proportion of the olefin-based elastomer added to the polyolefin-based resin composition B in at least one layer of the multilayer film is set to 50 parts by mass or more and 100 parts by mass or less. Moreover, by setting the proportion of the olefin-based elastomer added to the resin composition A to 1 part by mass or more and 80 parts by mass or less, flexibility can be imparted to the entire layer.
In one aspect of the multilayer film of the present invention, at least one layer of the multilayer film contains 50 parts by mass or more of an olefin elastomer with respect to 100 parts by mass of a polyolefin-based resin, and is a layer composed of the resin composition A. However, the polyolefin-based elastomer is contained in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of the polyolefin-based resin. It preferably contains 5 to 40 parts by mass. More preferably, it contains 5 to 30 parts by mass.

Further, as another method for imparting flexibility, in a multi-layer film having at least a surface layer, an intermediate layer and a back layer, a composition (resin composition A, and optionally) used for the surface layer and the back layer of the multi-layer film. The proportion of the olefin-based elastomer added to the polyolefin-based resin composition B) is 1 part by mass or more and 80 parts by mass or less, and the composition used for the intermediate layer of the multilayer film (the above-mentioned polyolefin-based resin composition B). By setting the proportion of the olefin-based elastomer to be added to 50 parts by mass or more and 100 parts by mass or less, flexibility can be imparted to the entire layer. Here, at least one layer of the surface layer and the back layer is a layer made of the resin composition A containing 0.20 parts by mass or more of the silicone-olefin copolymer with respect to 100 parts by mass of the polyolefin-based resin.
It is more preferable that the proportion of the olefin-based elastomer in the front and back layers is 5 parts by mass or more and 70 parts by mass or less, and the proportion of the olefin-based elastomer in the intermediate layer is 60 parts by mass or more and 100 parts by mass or less. ..
Since the proportion of the polyolefin-based elastomer in the front and back layers is 80 parts by mass or less, it is possible to suppress sticking to the roll during production. Since the proportion of the polyolefin-based elastomer in the intermediate layer is 50 parts by mass or more, sufficient flexibility of the multilayer film can be imparted.

As a resin other than the above-mentioned polyethylene-based resin, polypropylene-based resin, and olefin-based elastomer, a styrene-based elastomer, cyclic olefin-based resin, and the like can be added, if necessary.

The styrene-based elastomer is preferably a block copolymer represented by the following formula (I) or (II).
X- (YX) n ... (I)
(XY) n ... (II)
X in the general formulas (I) and (II) is an aromatic vinyl polymer block typified by styrene, and in the formula (I), the degree of polymerization may be the same or different at both ends of the molecular chain. May be good. In addition, Y is a butadiene polymer block, an isoprene polymer block, a butadiene / isoprene copolymer block, a hydrogenated butadiene polymer block, a hydrogenated isoprene polymer block, and a hydrogenated butadiene / isoprene co-weight. It is at least one selected from a coalesced block, a partially hydrogenated butadiene polymer block, a partially hydrogenated isoprene polymer block and a partially hydrogenated butadiene / isoprene copolymer block. Further, n is an integer of 1 or more.

Examples of the cyclic olefin-based resin include norbornene-based polymers, vinyl alicyclic hydrocarbon polymers, and cyclic conjugated diene polymers. Among these, norbornene-based polymers are preferable. Examples of the norbornene-based polymer include a ring-opening polymer of a norbornene-based monomer, a norbornene-based copolymer obtained by copolymerizing a norbornene-based monomer and an α-olefin such as ethylene. Moreover, these hydrogenated additives can also be used.

<Silicone-olefin copolymer>
The resin composition A used for producing the multilayer film of the present invention contains a polyolefin resin and a silicone-olefin copolymer as essential components.
A silicone-olefin copolymer is used in order to impart excellent scratch resistance and slipperiness to the obtained multilayer film and to maintain good processability when forming the multilayer film.
Since the silicone-olefin copolymer is excellent in compatibility with the above-mentioned polyolefin resin, it is possible to impart defects due to bleeding out to the surface of the obtained film, and to impart long-term scratch resistance and slipperiness.

The silicone-olefin copolymer used in the present invention is a copolymer containing silicone (a polymer compound containing a siloxane bond) and an olefin (or polyolefin). The silicone-olefin copolymer used in the present invention may be a graft copolymer in which polyolefin is grafted on silicone or silicone is grafted on polyolefin, and the block of polyolefin and the block of silicone are covalently bonded. You may use the block copolymer which has been used. It is preferable to use a block copolymer from the viewpoint of easy availability and compatibility with polyolefin resins.

The amount of the silicone-olefin copolymer added to the resin composition A is preferably 0.20 parts by mass or more with respect to 100 parts by mass of the above-mentioned polyolefin resin. By setting the amount to 0.20 parts by mass or more, it is possible to impart excellent scratch resistance and slipperiness to the obtained multilayer film. It is more preferably 0.25 parts by mass or more, still more preferably 0.30 parts by mass or more.

Further, as a method for further improving the compatibility and dispersibility with the polyolefin-based resin, it is preferable to use a masterbatch in which the above-mentioned silicone-olefin copolymer is previously dispersed in the polyolefin-based resin at a high concentration.
As the polyolefin resin used in the masterbatch, the same polyolefin resin as described above can be used.

The content of the silicone-olefin copolymer in the masterbatch is preferably 5 parts by mass or more and 80 parts by mass or less. When the amount is 5 parts by mass or more, it is possible to provide a sufficient amount of the silicone-olefin copolymer for exhibiting scratch resistance, and when the amount is 80 parts by mass or less, when pelletizing the masterbatch. This is preferable because it does not impair the workability of the product. It is more preferably 10 parts by mass or more and 70 parts by mass or less, and further preferably 20 parts by mass or more and 60 parts by mass or less.

Specific examples of the masterbatch containing the silicone-olefin copolymer include "X-Fora (manufactured by Mitsui Chemical Fine Co., Ltd.)", "X-22-2101", "X-22-2125H", and "X-". "22-2138B" (all manufactured by Shin-Etsu Chemical Co., Ltd.), "BY27-001", and "BY27-201" (all manufactured by DuPont Toray Specialty Materials Co., Ltd.) ".

<UV absorber>
As the ultraviolet absorber, known ones can be used, and examples thereof include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber.
Examples of the benzophenone-based ultraviolet absorber include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, and the like. 2,2'-Dihydroxybenzophenone UV absorbers, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2- 2-Hydroxybenzophenone-based UV absorbers such as hydroxy-4-benzoyloxybenzophenone, 2-hydroxy-5-chlorobenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,4-dihydroxybenzophenone, bis- Examples thereof include (2-methoxy-4-hydroxy-5-benzoylphenyl) methane.
As a benzotriazole-based ultraviolet absorber, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidemethyl) -5'-methylphenyl] benzotriazole (molecular weight 388) , 2- [2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole (molecular weight 448), 2,2-Methylbis [4- (1,1,3,3-) Examples thereof include tetramethylbutyl-6- (2H-benzotriazole-2-yl) phenol) (molecular weight 659).
Examples of the triazine-based ultraviolet absorber include 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) 1,3,5-triazine and 2- (4,4). 6-Diphenyl-1,3,5-triazine-2-yl) -5-((hexyl) oxy) -phenol, 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazine-2-yl) -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- (octyloxy) phenol, 2- (4,6) -Bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5- (hexyloshiki) phenol, 2- (4,6-diphenyl-1,3,5-triazine-2- Il) -5-((methyl) oxy) phenol can be mentioned.
Of these, a triazine-based ultraviolet absorber having high energy and excellent ability to absorb low-wavelength ultraviolet rays is preferable.

The ultraviolet absorber may be added to all the layers of the multilayer film, or may be added only to a part of the layers (for example, the front and back layers).
The amount of the ultraviolet absorber to be blended is not particularly limited as long as it does not blow out from the film, and is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyolefin resin composition in each layer of the multilayer film. It is contained, preferably 0.05 to 9 parts by mass, and particularly preferably 0.1 to 0.5 parts by mass. By containing 0.01 part by mass or more of the ultraviolet absorber, deterioration of the multilayer film of the present invention due to ultraviolet rays can be prevented, so that excellent scratch resistance and slipperiness can be maintained for a long period of time. Further, by setting the upper limit value to 10 parts by mass or less, deterioration due to sufficient ultraviolet rays can be prevented without bleeding out of the ultraviolet absorber from the multi-layer film, so that excellent scratch resistance is provided while maintaining the appearance of the film. The sex and slipperiness can be maintained for a long period of time.

Examples of the ultraviolet absorber include BASF's "Tinuvin 326", "Tinuvin 234", "Tinuvin 1600", ADEKA's "LA31RG", etc., and from the viewpoint of low wavelength ultraviolet absorption ability, BASF's "Tinuvin 1600" Is preferable.
Master batches to which an ultraviolet absorber is added are also commercially available, and examples include "TX1897D" manufactured by Japan Polypropylene and "MKV7722" manufactured by Dainichiseika. "MKV7722" manufactured by MKV7722 is preferable.

<Light stabilizer>
As the light stabilizer, known ones can be used, and examples thereof include hindered amine-based light stabilizers.
Examples of hindered amine photostabilizers include 2,2,6,6-tetramethylpiperidinyl-4-benzoate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and tris (2,2). , 6,6-tetramethyl-4-piperidinyl) phosphite (BASF Co., Ltd. "Kimasoap 944"), 1,3,8-triaza-7,7,9,9-tetramethyl-3-n-octylpyro [4,5] Decane-2,4-dione (“Tinubin 144” manufactured by BASF Co., Ltd.), 1,2,3,4-tetra (4-carbonyloxy-2,2,6,6-tetramethylpi) Peridinyl) -butane, 1,3,8-triaza-7,7,9,9-tetramethyl-2,4-dioxo-spiro [4,5] decane, tri (4-acetoxy-2,2,6) , 6-Tetramethylpiperidinyl) amine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenylcarbamoyloxy -2,2,6,6 tetramethylpiperidin, 4-p-toluenesulfonyloxy-2,2,6,6-tetramethylpiperidin, bis (2,2,6,6-tetramethyl-4-piperidinyl) terephthalate Etc., and these may be used alone or in combination of two or more.

The hindered amine-based light stabilizer may be added to all layers of the multilayer film, or may be added to only a part of the layers (for example, the front and back layers).
The blending amount of the hindered amine-based light stabilizer is preferably 0.01 to 10 parts by mass per 100 parts by mass of the resin in each layer. If the blending amount is 0.01 parts by mass or more, the stabilizing effect can be easily obtained, and if it is 10 parts by mass or less, the effect commensurate with the blending amount can be obtained, and there is no risk of causing bloom.

Master batches to which a light stabilizer is added are also commercially available, and examples thereof include "MBU10A" made by Japan Polypropylene, "LX1004" made by Japan Polyethylene, "XJ100H" made by Japan Polyethylene, and polypropylene resins and olefin elastomers. From the viewpoint of dispersibility with, "MBU10A" manufactured by Japan Polypropylene is preferable.
The light stabilizer can be used in combination with an ultraviolet absorber. It is preferable to use them in combination, and due to the synergistic effect of the combined use, the effect of imparting weather resistance can be expected as compared with the case where the light stabilizer and the ultraviolet absorber are added alone.

<Other ingredients>
In addition to the above-mentioned polyolefin-based resin and silicone-olefin copolymer, various additives can be added to the resin composition used for the multilayer film of the present invention in order to impart heat resistance, weather resistance, and the like.
Specific examples include, for example, antistatic agents, antioxidants, neutralizers, lubricants, antiblocking agents, plasticizers, heat stabilizers, dye pigments, crystal nucleating agents, fillers, inorganic fillers that impart rigidity, and In order to impart flexibility, elastomers and the like other than those described above may be used as long as the effects of the present invention are not impaired.

Known antistatic agents can be used, but polymer antistatic agents may be used in order to impart long-term antistatic properties to the film and suppress defects caused by bleeding out to the surface. preferable. As a specific example of the polymer type antistatic agent, known ones can be used. For example, a block copolymer of a hydrophobic block and a hydrophilic block can be used, and the hydrophobic block and the hydrophilic block can be used. Examples thereof include those in which a block copolymer is formed by an ester bond, an ether bond, an amide bond, an imide bond, a urethane bond, a urea bond, or the like.

<Multi-layer film>
The multilayer film of the present invention has a layer made of a resin composition A containing 0.20 parts by mass or more of a silicone-olefin copolymer with respect to 100 parts by mass of a polyolefin-based resin on at least one of the front and back surfaces. It is a multi-layer film. Further, from the viewpoint of handleability of the obtained film, it is necessary that the tensile elastic modulus of the multilayer film is 400 MPa or less.
By using a multi-layer film instead of a single layer, it is possible to add a silicone-olefin copolymer to either or both of the front and back layers, and the front and back layers can be suppressed while suppressing excessive addition of the silicone-olefin copolymer. Scratch resistance and slipperiness can be imparted to either or both of the above, which is also effective from the viewpoint of economy.

Further, the multilayer film of the present invention is preferably a film composed of at least three layers including front and back layers and an intermediate layer. By adding the silicone-olefin copolymer to one of the front and back layers, it is possible to impart scratch resistance and slipperiness to only one surface. Further, by adding a silicone-olefin copolymer to the front and back layers, it becomes possible to impart scratch resistance and slipperiness to both surfaces of the multilayer film. Whether to add the silicone-olefin copolymer to only one of the front and back layers or to the front and back layers can be appropriately selected in consideration of the use and processability of the multilayer film to be used. When an adhesive layer, a printing layer, or the like is provided on one surface of the obtained multilayer film, the surface layer on the side where the adhesive layer or printing layer of the multilayer film is provided is provided from the viewpoint of adhesion between these layers and the multilayer film. Alternatively, it is preferable not to add a silicone-olefin copolymer to the back layer.

The multilayer film of the present invention uses a test piece (JIS K 6732) collected from the film in accordance with JIS K 7161, and is used in a tensile tester at 23 ° C. and 50% RH at a tensile speed of 50 mm / min. It is required that the tensile elastic modulus at the time of measurement is 400 MPa or less. By setting the pressure to 400 MPa or less, the processability when laminating the adhesive layer or the printing layer on the multi-layer film and the handling when the multi-layer film having the adhesive layer is attached to an article having a three-dimensional shape such as an automobile exterior. It is possible to maintain good sex. It is more preferably 380 MPa or less, still more preferably 360 MPa or less. The tensile elastic modulus of the obtained multilayer film can be adjusted by adjusting the polyethylene-based resin, polypropylene-based resin, olefin-based elastomer, styrene-based elastomer, cyclic olefin-based resin, and the like described above.

From the viewpoint of scratch resistance and slipperiness, the multilayer film of the present invention preferably has a 60 ° gloss value of 60 or more after the Gakushin wear test. When the 60 ° gloss value is 60 or more, it can be judged that the product has good scratch resistance and slipperiness because it maintains a sufficient gloss even after the test. It is more preferably 65 or more, still more preferably 70 or more. Further, it is preferable that the maintenance rate of the 60 ° gloss value before and after the Gakushin wear test represented by the following formula is 60% or more. When the maintenance rate of the 60 ° gloss value is 60% or more, it can be determined that the product has good scratch resistance and slipperiness as described above. More preferably, the retention rate of the 60 ° gloss value is 65% or more, still more preferably 70% or more.

The condition of the Gakushin wear test of the present invention is that a cotton cloth is attached to a 20 mm square friction element, a load of 500 g is applied, and then the surface of the multilayer film is reciprocated 10 times with reference to JISK5701-1.

As a film molding method, a known method can be used, but it is preferable to use a melt extrusion molding method. Among the melt extrusion molding methods, the T die molding method in which a molten resin is extruded from an extruder having a T die and cooled and solidified to obtain a film is more preferable.
In order to obtain a multi-layer film, it is preferable to use a coextrusion T-die molding method using a plurality of extruders. As a coextrusion T-die molding method, a method of forming a plurality of resin layers into a film by using a multi-manifold die and then contacting the resin layers in the T-die to obtain a film, and a molten state called a feed block. A method of obtaining a multi-layer film after merging and adhering a plurality of resins using a device for merging the resins of the above can be mentioned.

If necessary, the multilayer film may be surface-treated on one or both sides by a method such as plasma treatment, corona treatment, ozone treatment, or flame treatment. Depending on the application of the obtained film, it is possible to select whether to perform surface treatment on one side or both sides.

The thickness of the multilayer film is not particularly limited, but is preferably 30 to 400 μm. Within the above range, the handleability of the film and the subsequent processability can be maintained satisfactorily. It is more preferably 50 to 350 μm, still more preferably 70 to 300 μm.
Further, it is preferable that the thickness of the surface layer or the back layer of the multilayer film is within the range of 5 to 40% with respect to the thickness of the entire multilayer film. When the content is 5% or more, the scratch resistance and slipperiness of the above-mentioned silicone-olefin copolymer can be sufficiently imparted to the surface layer or the back layer. When it is 40% or less, it is preferable from the viewpoint of film forming property and economic efficiency when obtaining a multilayer film. It is more preferably in the range of 5 to 35%, still more preferably in the range of 5 to 30%.

As the elongation of the film, a test piece (JIS K 6732) collected from the film was used according to JIS K 7161, and measured at a tensile speed of 300 mm / min with a tensile tester at 23 ° C. and an atmosphere of 50% RH. It is preferable that the tensile elongation at break is 100% or more.
When the tensile elongation at break is 100% or more, it is possible to suppress defects due to film breakage when the film is taken up during melt extrusion molding, and also in the subsequent step of laminating the printing layer and the adhesive layer. It is preferable because the same defect can be suppressed. It is more preferably 150% or more, still more preferably 200% or more.

The multilayer film of the present invention has a haze value when measured by a method conforming to JIS K7136 by applying liquid paraffin to eliminate unevenness of the film using Haze Meter NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. When it is set to 8% or less, the transparency is high, and the appearance when attached to an article such as an outer layer of an automobile is good. It is more preferably 6% or less, still more preferably 4% or less.

Multilayer film of the present invention is required to weathering for use in the bonded article such as an automobile outer irradiance 0.53 W / m 2 in Suga Test Instruments Co. metering Vertical Weather Meter ^MV3000, irradiation ( Repeated treatment at 63 ° C., 50%) for 102 minutes and irradiation + rainfall (40 ° C., 95%) for 18 minutes, preferably embrittlement time of 200 hours or more. It is more preferably 250 hours or more, still more preferably 300 hours or more.
The embrittlement of the multi-layer film is evaluated based on whether or not it breaks when bent at 180 °. A case of less than 200 hours was judged as x.

<Adhesive film>
The multilayer film of the present invention can be made into an adhesive film by laminating an adhesive layer on at least one surface (hereinafter, also referred to as "adhesive film of the present invention").

The pressure-sensitive adhesive used as the pressure-sensitive adhesive layer is not particularly limited, and for example, various pressure-sensitive adhesives such as natural rubber-based resin, acrylic-based resin, styrene-based resin, silicon-based resin, and polyvinyl ether-based resin are used. Further, a functional layer such as an adhesive layer or a thermosetting resin layer may be further provided on the pressure-sensitive adhesive layer.
In the pressure-sensitive adhesive film of the present invention, one or both sides of the film before laminating the pressure-sensitive adhesive layer may be subjected to the above-mentioned surface treatment. Further, a primer layer may be provided between the multilayer film of the present invention as the base film and the adhesive layer, if necessary.
The thickness of the adhesive layer and the primer layer can be appropriately determined as needed.

<Cosmetic film>
In the multilayer film of the present invention, a printing layer may be laminated on at least one side to obtain a decorative film (hereinafter, also referred to as "decorative film of the present invention").
The print layer constituting the decorative film can be formed by a known method. For example, a known printing method such as an offset printing method, a gravure rotary printing method, and a screen printing method, a known coating method such as a roll coating method and a spray coating method, a flexographic printing method, and the like can be mentioned. Moreover, the vapor deposition method can also be used.
Examples of the printed pattern include a pattern consisting of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, solid surface, metallic, and the like.
The thickness of the print layer can be appropriately determined as needed.
In the decorative film of the present invention, the above-mentioned surface treatment may be applied to one or both sides of the film before laminating the print layer. Further, a primer layer may be provided between the multilayer film of the present invention as the base film and the printing layer, if necessary.
The thickness of the print layer and the primer layer can be appropriately determined as needed.

<Adhesive film for cosmetics>
The decorative film of the present invention may be obtained by further laminating an adhesive layer on the printing layer to obtain a cosmetic adhesive film (hereinafter, also referred to as "cosmetic adhesive film of the present invention").
By attaching the cosmetic adhesive film to the adherend, it is possible to give the adherend a beautiful appearance, and it is used for cosmetics for interior and exterior of automobiles, other molded bodies and laminates, and for interior and exterior of buildings. It can be used for such purposes.
That is, one aspect of the present invention is the adhesive film of the present invention, the decorative film of the present invention, or the protective film for automobiles using the cosmetic adhesive film of the present invention.

The multilayer film of the present invention has excellent scratch resistance, flexibility, and followability to a molded product having a three-dimensional shape. Further, it is also possible to obtain an adhesive film or a decorative film by laminating an adhesive layer or a printing layer on the film, and these films can be suitably used for automobile cosmetic applications.

Hereinafter, examples and comparative examples of the present invention will be shown and specifically described, but the present invention is not limited to these examples. The materials used in the following examples and comparative examples, the method for measuring the evaluated characteristics, and the like are as follows.

[Material used]
<Polyolefin-based resin (PO-based resin)>
Random polypropylene (A):
"FW4B" manufactured by Japan Polypropylene Corporation (random polypropylene, melt flow rate at 230 ° C., 2.16 kg = 8.0 g / 10 minutes, melting point = 136 ° C., tensile elastic modulus of a single film = 600 MPa)
Random polypropylene (B):
"PC630A" manufactured by SunAllomer Ltd. (Random polypropylene, melt flow rate at 230 ° C., 2.16 kg = 7.5 g / 10 minutes, melting point = 142 ° C., tensile elastic modulus of a single film = 600 MPa)
Linear low density polyethylene:
"0540F" manufactured by Ube-Maruzen Polyethylene Co., Ltd. (metallocene-catalyzed linear low-density polyethylene, melt flow rate at 190 ° C., 2.16 kg = 4 g / 10 minutes, melting point = 87 ° C. and 111 ° C., tensile elastic modulus of a single film = 100MPa)
Olefin elastomer:
"Wellnex RFX4V" manufactured by Japan Polypropylene Corporation (olefin elastomer, melt flow rate at 230 ° C., 2.16 kg = 6.0 g / 10 minutes, melting point = 127 ° C., tensile elastic modulus of a single film = 230 MPa)
Using a differential scanning calorimetry device (DSC823e manufactured by METTLER TOLEDO), about 5 mg of each polyolefin resin is heated from 25 ° C to 230 ° C at a heating rate of 10 ° C / min.
The melting peak temperature of the chart measured when the temperature was lowered to 25 ° C. at a cooling rate of 10 ° C./min and again raised to 230 ° C. at a heating rate of 10 ° C./min was taken as the melting point.

<Silicone-olefin copolymer masterbatch>
"Exfora PP2000" manufactured by Mitsui Kagaku Fine Co., Ltd. (master batch consisting of 30 parts by mass of silicone-olefin copolymer (block copolymer of silicone component and polyolefin component) and 70 parts by mass of homopolypropylene, 230 Melt flow rate at 2.16 kg at ° C = 20.0 g / 10 minutes)

<Slip agent masterbatch>
"MBS05A" manufactured by Japan Polypropylene Corporation (polypropylene slip agent masterbatch containing 5 parts by mass of fatty acid amide)

<Ethylene-HALS copolymer high molecular weight light stabilizer>
"XJ100H" manufactured by Japan Polyethylene Corporation (polyethylene-based light stabilizer containing 5 parts by mass of hindered amine-based light stabilizer)

<Light stabilizer masterbatch>
"MBU10A" manufactured by Japan Polypropylene Corporation (polypropylene light stabilizer masterbatch containing 10 parts by mass of hindered amine light stabilizer)

<UV absorber masterbatch A>
"TX1897D" manufactured by Japan Polypropylene Corporation (polypropylene UV absorber masterbatch containing 5 parts by mass of benzotriazole UV absorber)
<UV absorber masterbatch B>
"MKV7722" manufactured by Dainichiseika Co., Ltd. (polypropylene UV absorber masterbatch containing 5 parts by mass of triazine UV absorber)

<Preparation of resin composition>
A total of 100 parts by mass of the above-mentioned polyolefin-based resin was used, and the other raw materials and addition amounts were used as shown in Table 1, and they were dry-blended and mixed. It was visually confirmed that the mixture was uniformly mixed, and a resin composition for film molding was obtained.

<Method of forming a multi-layer film>
Each of the three Toshiba Machine single-screw extruders (for front and back layers: 35φ mm, L / D = 25 mm, for intermediate layer: 50φ mm, L / D = 32, for front and back layers: 35φ mm, L / D = 25 mm) The dry-blended raw material is put into the hopper, the extruder temperature for each of the outer layer and the intermediate layer is set to 200 to 230 ° C., and the extruder is merged into the three-layer structure of the surface layer / intermediate layer / back layer at the feed block portion. , Extruded from a 650 mm wide T-die (temperature setting 230 ° C., lip opening 0.5 mm). The thickness configuration was set to each extruder rotation speed so as to be 9 μm / 157 μm / 9 μm.
The extruded molten resin is cooled and solidified by a winder equipped with a cooling roll (cooling roll 700 mm width × φ350 mm, roll temperature about 30 ° C.), and then corona-treated on the surface containing no silicone-olefin copolymer. Was carried out and wound up to obtain a multi-layer film composed of 3 types and 3 layers having a thickness of about 175 μm.

[Appearance of film]
The surface of the obtained multilayer film on the side of the layer containing the silicone-olefin copolymer was visually observed and evaluated according to the following criteria.
◎: No stains or irregularities are transferred to the film, and the appearance is good. ○: The film has slight stains or irregularities, but it can be used.

[Tension modulus]
A No. 1 dumbbell test piece was collected from the obtained multi-layer film, and a tensile elastic modulus was obtained at a tensile modulus of 50 mm / min using an autograph (AGS-X manufactured by Shimadzu Corporation) in an atmosphere of 23 ° C. and 50% RH. (MPa) was measured.
The tensile elastic modulus was measured in the extrusion direction (MD) of the film.

[Tension breaking elongation]
A No. 1 dumbbell test piece was collected from the obtained film and stretched at a tensile speed of 300 mm / min using a small tabletop tester (EZ-L manufactured by Shimadzu Corporation) in an atmosphere of 23 ° C. and 50% RH. The degree (%) was measured.
The tensile elongation at break was measured in the extrusion direction (MD) of the film.

[60 ° gloss value]
Using the obtained multi-layer film, the surface on the side of the layer containing the silicone-olefin copolymer using a portable gloss meter (GMX-203 manufactured by Murakami Color Technology Research Institute) in accordance with JIS K7105. The 60 ° gloss value of was measured.
Table 1 shows the values measured in each state before and after the Gakushin wear test, which will be described later.
In addition, the value calculated by the following formula was used as the maintenance rate of the 60 ° gloss value before and after the Gakushin wear test.

[Gakushin wear test]
The obtained multi-layer film was installed in a "Gakushin-type friction fastness tester" manufactured by Tester Sangyo Co., Ltd. so that the side surface of the layer containing the silicone-olefin copolymer could be tested. Next, referring to JISK5701-1, attach a cotton cloth of Kanakin No. 3 to a 20 mm square friction element in contact with the film, apply a load of 500 g, and then apply a load of 500 g to the side of the multi-layer film containing the silicone-olefin copolymer. The surface of the surface was reciprocated 10 times (reciprocating speed: 3.6 m / min, reciprocating distance: 120 mm) to perform the test.
The Gakushin wear test was measured in the extrusion direction (MD) of the film.

[Workability of adhesive film]
The workability when the pressure-sensitive adhesive film having the pressure-sensitive adhesive layer on the surface of the obtained multi-layer film not containing the silicone-olefin copolymer was evaluated according to the following criteria.
⊚: The film has excellent flexibility and good workability ○: The film has sufficient flexibility and can be worked ×: The film has poor flexibility and is inferior in workability

[Weatherability]
The obtained multi-layer film was subjected to irradiance of 0.53 W / m ² with Suga Test Instruments Co., Ltd. Metering Vertical Weather Meter MV3000, irradiation (63 ° C, 50%) for 102 minutes, irradiation + rainfall (40 ° C, 95%). ) Was repeated for 18 minutes, and the time until embrittlement was evaluated.
◯: Embrittlement treatment time is 300 hours or more Δ: Embrittlement treatment time is 200 hours or more and less than 300 hours ×: Embrittlement treatment time is less than 200 hours

[Example 1]
By using linear low-density polyethylene and olefin elastomer as the PO resin used for the front and back layers and the intermediate layer, and by containing a silicone-olefin copolymer masterbatch as a lubricant on one side of the front and back layers, the front and back layers can be formed. A multi-layer film composed of 3 types and 3 layers containing a silicone-olefin copolymer on one side was obtained. The amounts of the PO resin and the lubricant were set as shown in Table 1, respectively.
The appearance of this film was not deteriorated due to the ejection of the silicone-olefin copolymer onto the surface, the tensile elastic modulus of the film was 200 MPa, and the film was excellent in appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 74 after the test, and the maintenance rate of the gloss value before and after the test was 80%. It was confirmed that it has excellent scratch resistance and slipperiness.
Further, an acrylic pressure-sensitive adhesive (SK Dyne 1502C manufactured by Soken Kagaku Co., Ltd.) is applied onto the separator by a copolymer coating method so that the thickness of the pressure-sensitive adhesive layer after drying is 25 μm, and dried with hot air at 80 ° C. After drying for 5 minutes on the machine, an adhesive layer was formed, and the adhesive layer was attached to the surface of the multi-layer film not containing the silicone-olefin copolymer to obtain an adhesive film.
When the separator was peeled off from this adhesive film and attached to the exterior of an automobile, it was confirmed that the film has excellent flexibility, so it can be easily attached and has excellent workability and workability. bottom.

[Example 2]
The same procedure as in Example 1 was carried out except that the content of the silicone-olefin copolymer was set to the blending amount shown in Table 1.
The appearance of this film was not deteriorated due to the ejection of the silicone-olefin copolymer onto the surface, the tensile elastic modulus of the film was 200 MPa, and the film was excellent in appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 88 after the test, and the maintenance rate of the gloss value before and after the test was 95%. It was confirmed that it has excellent scratch resistance and slipperiness.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of an automobile, it was possible to attach it easily because the film had excellent flexibility, and workability and processing. It was confirmed that it was excellent in sex.

[Example 3]
The procedure was the same as in Example 2 except that the PO resin was only an olefin elastomer.
The appearance of this film was not deteriorated due to the ejection of the silicone-olefin copolymer onto the surface, and the tensile elastic modulus of the film was 230 MPa, which was an excellent appearance and good flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 88 after the test, and the maintenance rate of the gloss value before and after the test was 95%. It was confirmed that it has excellent scratch resistance and slipperiness.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of an automobile, the film had good flexibility, so it could be attached without problems, and sufficient workability was achieved. , It was confirmed that it has workability.

[Example 4]
The same procedure as in Example 2 was carried out except that the PO-based resin was used as the blending amount shown in Table 1.
The appearance of this film was not deteriorated due to the ejection of the silicone-olefin copolymer onto the surface, the tensile elastic modulus of the film was 200 MPa, and the film was excellent in appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 88 after the test, and the maintenance rate of the gloss value before and after the test was 95%. It was confirmed that it has excellent scratch resistance and slipperiness.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of an automobile, it was possible to attach it easily because the film had excellent flexibility, and workability and processing. It was confirmed that it was excellent in sex.

[Example 5]
The same procedure as in Example 4 was carried out except that the blending amount of the silicone-olefin copolymer was as shown in Table 1.
The appearance of this film was not deteriorated due to the ejection of the silicone-olefin copolymer onto the surface, the tensile elastic modulus of the film was 200 MPa, and the film was excellent in appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 90 after the test, and the maintenance rate of the gloss value before and after the test was 97%. It was confirmed that it has excellent scratch resistance and slipperiness.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of an automobile, it was possible to attach it easily because the film had excellent flexibility, and workability and processing. It was confirmed that it was excellent in sex.

[Example 6]
The same procedure as in Example 4 was carried out except that the blending amount of the silicone-olefin copolymer was as shown in Table 1.
The appearance of this film was good, although stains and uneven transfer were slightly observed on the surface of the silicone-olefin copolymer. Further, the tensile elastic modulus of the film was 200 MPa, and the film was excellent in good appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 89 after the test, and the maintenance rate of the gloss value before and after the test was 96%. It was confirmed that it has excellent scratch resistance and slipperiness.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of an automobile, it was possible to attach it easily because the film had excellent flexibility, and workability and processing. It was confirmed that it was excellent in sex.

[Example 7]
The same procedure as in Example 4 was carried out except that the amounts of the silicone-olefin copolymer and the olefin elastomer were set as shown in Table 1.
The appearance of this film was good, although stains and uneven transfer were slightly observed on the surface of the silicone-olefin copolymer. The tensile elastic modulus of the film was 230 MPa, which was excellent in appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 90 after the test, and the maintenance rate of the gloss value before and after the test was 97%. It was confirmed that it has excellent scratch resistance and slipperiness.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of an automobile, the film had good flexibility, so it could be attached without problems, and sufficient workability was achieved. , It was confirmed that it has workability.

[Example 8]
Random polypropylene, an olefin-based elastomer, a silicone-olefin copolymer, a light stabilizer, and an ultraviolet absorber were blended in the amounts shown in Table 1, and the same procedure as in Example 7 was carried out.
The appearance of this film was good, although stains and uneven transfer were slightly observed on the surface of the silicone-olefin copolymer. The tensile elastic modulus of the film was 270 MPa, which was excellent in appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 89 before wear, 85 after the test, and the maintenance rate of the gloss value before and after the test was 96. It was confirmed that it had excellent scratch resistance and slipperiness.
Since the polyolefin-based resin used for the masterbatch of the light stabilizer and the masterbatch of the ultraviolet absorber is a polypropylene-based resin, this multilayer film has a haze of 2% and has good transparency.
Since the ultraviolet absorber is a benzotriazole-based ultraviolet absorber, the weather-resistant embrittlement time is about 250 hours, and it was judged that there is no problem in practical use.
Further, since the amount of random polypropylene (B) added to the front and back layers was 80 parts by mass and the amount of the olefin elastomer was 20 parts by mass, the film-forming property of the film was improved.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of an automobile, the film had good flexibility, so it could be attached without problems, and sufficient workability was achieved. , It was confirmed that it has workability.

[Example 9]
Random polypropylene, an olefin-based elastomer, a silicone-olefin copolymer, a light stabilizer, and an ultraviolet absorber were blended in the amounts shown in Table 1, and the same procedure as in Example 7 was carried out.
The appearance of this film was good, although stains and uneven transfer were slightly observed on the surface of the silicone-olefin copolymer. The tensile elastic modulus of the film was 270 MPa, which was excellent in appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film before wear was 88, after the test was 85, and the maintenance rate of the gloss value before and after the test was 97. It was confirmed that it had excellent scratch resistance and slipperiness.
Since the polyolefin-based resin used for the masterbatch of the light stabilizer and the masterbatch of the ultraviolet absorber is a polypropylene-based resin, this multilayer film has a haze of 2% and has good transparency.
Since the ultraviolet absorber is a triazine-based ultraviolet absorber, the weather resistance embrittlement time was 300 hours or more, and excellent weather resistance was confirmed.
Further, since the amount of random polypropylene (B) added to the front and back layers was 80 parts by mass and the amount of the olefin elastomer was 20 parts by mass, the film-forming property of the film was improved.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of an automobile, the film had good flexibility, so it could be attached without problems, and sufficient workability was achieved. , It was confirmed that it has workability.

[Comparative Example 1]
The same procedure as in Example 3 was carried out except that the content of the silicone-olefin copolymer was set to the blending amount shown in Table 1.
The appearance of this film was not deteriorated due to the ejection of the silicone-olefin copolymer onto the surface, and the tensile elastic modulus of the film was 230 MPa, which was excellent in appearance and flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 55 after the test, and the maintenance rate of the gloss value before and after the test was 59%. Met.
It was confirmed that this multi-layer film is inferior in scratch resistance and slipperiness because the content of the silicone-olefin copolymer is small.

[Comparative Example 2]
The procedure was the same as in Example 3 except that the PO resin was only random polypropylene.
The appearance of this film was good, although stains and uneven transfer were slightly observed on the surface of the silicone-olefin copolymer. The tensile elastic modulus of the film was 600 MPa, which was a film showing a good appearance but inferior in flexibility.
In addition, the 60 ° gloss value of the surface on the side of the layer containing the silicone-olefin copolymer of this double glazing film was 93 before vibration wear, 88 after the test, and the maintenance rate of the gloss value before and after the test was 95%. It was confirmed that it has excellent scratch resistance and slipperiness.
When the separator was peeled off from the adhesive film using this multi-layer film and attached to the exterior of the automobile, the film was inferior in flexibility, so the film did not follow the shape of the exterior of the automobile, and the work was done. It was confirmed that it was inferior in properties and workability.

[Comparative Example 3]
The same procedure as in Example 4 was carried out except that the slip agent masterbatch was used as the lubricant in the blending amounts shown in Table 1.
It was confirmed that the fatty acid amide contained in the slip agent masterbatch was ejected onto the surface of this film, and it was confirmed that the film was inferior in appearance from the time when the film was whitened.

[Example 10]
The ink manufactured by DIC Graphics Co., Ltd. described below is applied to the surface of the multilayer film obtained in Example 1 that does not contain the silicone-olefin copolymer, and the gravure manufactured by Kurashiki Spinning Co., Ltd. The multi-layer film was coated using the printing tester "GP-2" and the printing plate "54L6 gradation". The coated film was aged at 40 ° C. for 5 days to obtain a decorative film in which a printing layer with ink was laminated.

<Ink manufactured by DIC Graphics Corporation>
An ink was prepared by mixing and stirring 95 parts by mass of "VTP-NT40 yellow (A)" and 5 parts by mass of "AT-NT solvent".
"VTP-NT40 Yellow (A)": Paint consisting of a mixture of vinyl chloride / vinyl acetate copolymer and acrylic resin and methyl isobutyl ketone as a solvent "AT-NT solvent": Mixture of butyl acetate / ethyl acetate / methyl ethyl ketone

Further, a cosmetic adhesive film was obtained by laminating an adhesive layer on the printed layer of the obtained decorative film by the method described in Example 1. When the separator was peeled off from the cosmetic adhesive film and attached to the exterior of the automobile, the film had excellent flexibility and could be easily attached to the exterior of the automobile. Therefore, it was confirmed that the cosmetic adhesive film is excellent in workability and processability.

By using a film having a layer made of the resin composition of the present invention, it is possible to obtain a polyolefin-based resin film having excellent scratch resistance, flexibility, and followability to a molded product having a three-dimensional shape. Further, it is also possible to obtain an adhesive film or a decorative film by laminating an adhesive layer or a printing layer on the film, and these films can be suitably used for automobile cosmetic applications.

Claims (12)

A multi-layer film having a plurality of layers containing a polyolefin resin.
A layer made of a resin composition containing 0.20 parts by mass or more of a silicone-olefin copolymer with respect to 100 parts by mass of a polyolefin resin is provided on at least one of the front and back surfaces.
The multilayer film is characterized in that the tensile elastic modulus of the multilayer film is 400 MPa or less. The multilayer film according to claim 1, wherein a silicone-olefin copolymer masterbatch containing the silicone-olefin copolymer is used as the silicone-olefin copolymer. The multilayer film according to claim 1 or 2, characterized in that it is composed of at least two layers. The multilayer film according to any one of claims 1 to 3, wherein the polyolefin-based resin contains one or more of a polyethylene-based resin, a polypropylene-based resin, and an olefin-based elastomer. The multilayer film according to any one of claims 1 to 4, wherein each layer of the multilayer film contains 50 parts by mass or more of an olefin elastomer with respect to 100 parts by mass of a polyolefin resin. At least one layer of the multilayer film contains 50 parts by mass or more of an olefin elastomer with respect to 100 parts by mass of a polyolefin resin.
The multilayer layer according to any one of claims 1 to 4, wherein the layer made of the resin composition contains 5 to 50 parts by mass of an olefin-based elastomer with respect to 100 parts by mass of a polyolefin-based resin. the film. At least a surface layer, an intermediate layer and a back layer are provided, and the surface layer and the back layer contain 1 part by mass or more and 80 parts by mass or less of an olefin elastomer with respect to 100 parts by mass of the polyolefin resin, and the intermediate layer is a polyolefin resin. The olefin-based elastomer is contained in an amount of 50 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass, and at least one layer of the surface layer and the back layer contains 0 parts by mass of the silicone-olefin copolymer with respect to 100 parts by mass of the polyolefin-based resin. The multilayer film according to claim 6, which is a layer made of a resin composition containing 20 parts by mass or more. The multilayer film according to any one of claims 1 to 7, wherein the 60 ° gloss value after the Gakushin wear test is 60 or more. An adhesive film obtained by laminating an adhesive layer on at least one surface of the film according to any one of claims 1 to 8. A decorative film obtained by laminating a printing layer on at least one surface of the film according to any one of claims 1 to 8. A cosmetic adhesive film obtained by further laminating an adhesive layer on the print layer side of the decorative film according to claim 10. An automobile protective film using the film according to any one of claims 9 to 11.