JP6953159B2 - Polyolefin resin film and laminate - Google Patents

Description

The present invention relates to polyolefin resin films and laminates.

A method of attaching a decorative film to a base material in order to give a design to the base material is known and is used in many applications. Conventionally, for example, a film made of polyethylene terephthalate (PET) or vinyl chloride has been used as a decorative sheet, but in recent years, a polyolefin resin film has also been used in order to meet the demands for environmental friendliness and cost reduction. It is becoming possible to do so.

Polyolefin resin films are generally manufactured by molding a resin composition in which various additives such as antioxidants, light stabilizers, and inorganic fillers are mixed with resin components such as polypropylene and polyethylene into a film shape. be. Here, various types of antioxidants are known, and phenol-based, phosphorus-based, and sulfur-based antioxidants are generally used as antioxidants for polyolefin resins. Further, the light stabilizer is an additive compounded to improve the weather resistance of polyethylene or polypropylene, and for example, a hindered amine-based light stabilizer is used.

The conventional polyolefin resin film contains, for example, at least one of polyethylene and polypropylene, a phenolic antioxidant, and a hindered amine-based light stabilizer having a specific structure, and contains the above-mentioned hindered amine-based light stabilizer. Patent Document 1 discloses that the amount is 0.05 to 5% by weight based on the total amount of polyethylene and polypropylene. According to the polyolefin resin film of Patent Document 1, discoloration due to NOx gas can be prevented.

Japanese Unexamined Patent Publication No. 2011-236369

By the way, the conventional polyolefin resin film may be discolored depending on the mode of use. For example, in a test to confirm durability (weather resistance) against stimuli such as light, heat, and humidity, when exposed to light for a long period of time in a high-temperature and high-humidity environment of 40 ° C x 90%, or exposed to a NOx gas-rich environment. It is known that discoloration occurs when the color is changed, and it has been required to prevent these discolorations.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a polyolefin resin film having excellent weather resistance and suppressed NOx discoloration, and a laminate using the polyolefin resin film. ..

The present inventors have studied various methods for obtaining a polyolefin resin film without discoloration, and have formulated a phenolic antioxidant to suppress deterioration of the resin during molding and to impart durability as a film. Is the cause of discoloration, and it was thought that remarkable discoloration would occur when some stimulus conditions were met. Further, as the stimulating conditions, a photocatalytic reaction with titanium oxide compounded as a pigment, humidity (moisture), and a basic compound were considered. Therefore, the use of titanium oxide with low photocatalytic activity and the change of the type of antioxidant were further investigated. As a result of this study, titanium oxide, which has been surface-treated to bond at least one of Si, Zn, polyol and siloxane to the particle surface, improves weather resistance (suppresses yellowing due to stimuli such as light, heat and humidity). It was found to be effective, and it was found that the phosphorus-based antioxidant is effective in suppressing NOx discoloration. From the above, it was found that a polyolefin resin film having excellent weather resistance and suppressed NOx discoloration can be obtained by using a combination of titanium oxide and a phosphorus-based antioxidant which has been subjected to a specific surface treatment. , The present invention has been completed.

The polyolefin resin film of the present invention contains polyolefin, titanium oxide and a phosphorus-based antioxidant, and the titanium oxide has a surface treatment that binds at least one of Si, Zn, polyol and siloxane to the surface of titanium oxide particles. It is characterized by being given.

The polyolefin resin film of the present invention preferably further contains a hindered amine-based light stabilizer having a weight average molecular weight of 1000 or less.

The laminate of the present invention is characterized in that the polyolefin resin film of the present invention is attached to a base material.

According to the present invention, it is possible to realize a polyolefin resin film having excellent weather resistance and suppressed NOx discoloration, and a laminate using the polyolefin resin film. Further, the polyolefin resin film of the present invention is also excellent in ink peelability and moldability.

It is sectional drawing which shows typically an example of the laminated body using the polyolefin resin film of this invention.

The polyolefin resin film of the present invention contains polyolefin, titanium oxide and a phosphorus-based antioxidant, and the titanium oxide has a surface treatment that binds at least one of Si, Zn, polyol and siloxane to the surface of titanium oxide particles. It is characterized by being given. In this specification, "film" is synonymous with "sheet", and the two are not distinguished by the thickness.

[Polyolefin]
The polyolefin is not particularly limited, but polyethylene, polypropylene, an ethylene-propylene copolymer, and a mixture thereof are preferably used. Examples of polyethylene include high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), ultra-low-density polyethylene (VLDPE), and the like. These may be used alone or in combination of two or more. Examples of polypropylene include homopolymerized polypropylene (h-PP), random copolymerized polypropylene (r-PP), block copolymerized polypropylene (b-PP), metallocene polypropylene resin and the like. These may be used alone or in combination of two or more.

The melt flow rate (temperature 230 ° C., load 2.16 kg) of the above polyolefin measured in accordance with JIS K 7210 is preferably 0.1 to 4.0 g / 10 min, and 0.4 to 2. More preferably, it is 0 g / 10 min. When the MFR is in the above range, it is suitable for forming a film by calendar processing.

The polyolefin resin film of the present invention may contain a resin component other than polyolefin, but preferably contains only polyolefin as the resin component.

[Titanium oxide]
The polyolefin resin film of the present invention contains titanium oxide. By blending the white pigment titanium oxide, the polyolefin resin film of the present invention protects and conceals the base material as a base material when it is attached to the base material, and improves durability and design. Can be done.

The titanium oxide is surface-treated to bond at least one of Si, Zn, polyol and siloxane to the surface of titanium oxide particles. By using the surface-treated titanium oxide, the effect of improving weather resistance (suppressing yellowing due to stimuli such as light, heat, and humidity) can be obtained. Further, the titanium oxide may be one in which another substance such as Al is bonded to the particle surface as long as at least one of Si, Zn, polyol and siloxane is bonded to the particle surface.

The above-mentioned surface treatment method is not particularly limited, and a conventionally known surface treatment method can be used. For example, a wet treatment method such as a method of depositing on the particle surface with a slurry system, a method of depositing on the particle surface due to a difference in solubility under high temperature and high pressure, a method of adding a surface treatment agent at the time of drying or pulverizing titanium oxide, a method of adding a surface treatment agent at high temperature. Examples thereof include a dry treatment method such as a method of adding a surface treatment agent in the state of steam, a method of mechanically kneading, and a method of treating by a chemical reaction on the particle surface. In the method of depositing on the particle surface with a slurry system, a slurry containing titanium oxide is prepared, and a surface treatment agent is added to the slurry in the form of a solution and adsorbed on titanium oxide, or deposited on the surface of titanium oxide by a chemical reaction. Is done.

The titanium oxide is preferably titanium oxide produced by the chlorine method. The chlorine method has been put into practical use as an industrial production method for titanium oxide for pigments. Specifically, the raw material (rutile ore) is reacted with coke chlorine to once make gaseous titanium tetrachloride, and then gaseous. This is a method of obtaining titanium oxide by cooling titanium tetrachloride to make it liquid and then reacting it with oxygen at a high temperature to separate chlorine gas. Since the titanium oxide particles produced by the chlorine method have a different surface condition from the titanium oxide particles produced by the sulfuric acid method, which is another industrial method for producing titanium oxide for pigments, Si, Zn, and polyols And at least one of the siloxanes can be suitably carried out by surface treatment in which the surface of the titanium oxide particles is bonded.

The content of the titanium oxide is not particularly limited and may be appropriately adjusted according to the desired color of the polyolefin resin film of the present invention, but it may be 20 to 50 parts by weight with respect to 100 parts by weight of the polyolefin. preferable.

[Phosphorus antioxidant]
The polyolefin resin film of the present invention contains a phosphorus-based antioxidant. By blending a phosphorus-based antioxidant, deterioration of the resin during molding can be prevented. In addition, the durability of the polyolefin resin film of the present invention can be improved. Furthermore, by selecting a phosphorus-based antioxidant as the antioxidant, NOx discoloration can be suppressed. The polyolefin resin film of the present invention uses a phosphorus-based antioxidant instead of a phenol-based antioxidant as an antioxidant, and at least the content of the phosphorus-based antioxidant is larger than the content of the phenol-based antioxidant. , It is preferable that the phenolic antioxidant is substantially not contained.

Specific examples of the phosphorus-based antioxidant include the following compounds. One of these may be used alone, or two or more thereof may be used in combination.

The phosphorus-based antioxidant preferably contains a structure in which two tertiary butyl groups (tBu) are bonded to a benzene ring, and in the above specific examples, the compound represented by the following formula (1) (IUPAC name:: 3,9-Biz (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-terraoxa-3,9-diphosphaspiro [5.5] undecane), in the following formula (2) The compound shown (IUPAC name: 2,2'-Methylenebis (4,6-di-tert-butylphenyl) is applicable.

Among the compounds represented by the above formulas (1) and (2), the compound represented by the above formula (2) is particularly preferable because precipitation (bloom) on the film surface is unlikely to occur and there is no concern about hydrolyzability.

The content of the phosphorus-based antioxidant is not particularly limited and may be appropriately adjusted according to the desired color of the polyolefin resin film of the present invention. For example, 0.1 to 100 parts by weight of the polyolefin. It is considered to be 0.5 parts by weight.

[Hindered amine light stabilizer]
The polyolefin resin film of the present invention may further contain a hindered amine-based light stabilizer. Specific examples of the hindered amine-based light stabilizer include the following compounds. One of these may be used alone, or two or more thereof may be used in combination.

The hindered amine-based photostabilizer preferably has a structure in which an alkyl group or an alkoxyl group is bonded to a nitrogen atom of a piperidine ring (a 6-membered ring containing a nitrogen atom) in the molecule. The compound shown in (3) (IUPAC name: 1,2,3,4-Butanetetracarboxylic acid, tetramester, reaction products with 1,2,2,6,6-pentamethyl-4-piperidinol and β, β', β, β' β'-tetramethyl-2, 4,8,10-tellaoxaspiro [5.5] undecane-3,9-diethanol), a compound represented by the following formula (4) (IUPAC name: Bis (1-undecanoxy-2,2,2) 6,6-tetramethylpiperidin-4-yl) carbonate) and the like are applicable.

The hindered amine-based light stabilizer preferably has a weight average molecular weight of 1000 or less. By blending a hindered amine-based light stabilizer (low basicity) having a weight average molecular weight of 1000 or less, weather resistance is improved as compared with the case where a hindered amine-based light stabilizer (highly basic) having a weight average molecular weight of more than 1000 is blended. (Suppression of yellowing due to stimuli such as light, heat, and humidity) and suppression of NOx discoloration, which are the effects of the present invention, can be more fully exhibited. The weight average molecular weight is more preferably 500 to 1000.

As the weight average molecular weight (Mw), a polystyrene-equivalent measured value by GPC (gel permeation chromatography) measurement is used. The measurement conditions for the weight average molecular weight (Mw) are as follows.
Device name: HLC-8120 (manufactured by Tosoh)
Column: G7000HXL 7.8mm ID x 30cm 1 piece GMHXL 7.8mm ID x 30cm 2 pieces G2500HXL 7.8mm ID x 30cm 1 piece (manufactured by Tosoh Corporation)
Sample concentration: Dilute with tetrahydrofuran to 1.5 mg / ml Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml / min
Column temperature: 40 ° C

The content of the hindered amine-based light stabilizer is not particularly limited, but is, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyolefin.

Further, the polyolefin resin film of the present invention can be used as an ultraviolet absorber, a filler, a colorant (pigment), a flame retardant, an antistatic agent, a reinforcing agent, a lubricant, a modifier, an antifungal agent, and a foaming agent, if necessary. , Additives such as diluents may be included. As these additives, those generally blended in a polyolefin resin film can be used.

Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and the like. These may be used alone or in combination of two or more.

Examples of the filler include calcium carbonate, talc, carbon black, iron oxide, titanium oxide, antimony oxide, and nickel oxide solid solution. These may be used alone or in combination of two or more.

The surface of the polyolefin resin film of the present invention may be embossed, if necessary. By imparting an embossed shape (concave and convex shape) to the surface by embossing, the texture of the polyolefin resin film of the present invention can be improved. Further, the surface of the polyolefin resin film of the present invention may be subjected to a surface treatment for improving the adhesion to the base material and the layer to be laminated.

The thickness of the polyolefin resin film of the present invention is not particularly limited, but is preferably 35 to 200 μm. If the thickness is less than 35 μm, the polyolefin resin film of the present invention may become too flexible and the workability may be lowered, or the weather resistance may be lowered. On the other hand, if the thickness exceeds 200 μm, the followability to the surface shape of the base material may be insufficient. Further, reducing the thickness of the film is preferable in that the manufacturing cost of the film and the environmental load can be reduced.

The polyolefin resin film of the present invention can be produced by, for example, conventionally known molding methods such as calender molding, extrusion molding, and injection molding. Specifically, it can be produced by melting and kneading a predetermined amount of each raw material to form a resin composition, and then forming a film by calendar processing. Specifically, after blending a resin component such as polyolefin, chlorine-based titanium oxide, a phosphorus-based antioxidant, and, if necessary, a hindered amine-based light stabilizer and various other additives, a continuous kneader is used. , A Banbury mixer, a kneader, an extruder or the like, usually heated and kneaded at a temperature of 150 to 200 ° C. and melted to prepare a resin composition (kneaded product). Subsequently, this kneaded product is supplied to a calendar roll having a roll temperature of 150 to 220 ° C., preferably 160 to 190 ° C. and rolled, so that a film having a required thickness can be obtained by calendar processing. According to the calendering process, it can be formed as a film having excellent surface smoothness and high thickness accuracy.

Further, the polyolefin resin film of the present invention may be subjected to various surface treatments after production. Examples of the surface treatment include corona treatment (corona discharge treatment), plasma treatment, ultraviolet treatment, electron beam treatment (electron beam radiation treatment), and the like.

The polyolefin resin film of the present invention is further subjected to processing such as cutting and winding into a roll, if necessary.

The use of the polyolefin resin film of the present invention is not particularly limited, and it can be used by being attached to various substrates, but it is preferably used for wall covering around water such as bathrooms, kitchens, washrooms, and toilets. According to the polyolefin resin film of the present invention, excellent durability and design can be imparted to the base material by a method simpler and safer than painting.

The laminate of the present invention is characterized in that the polyolefin resin film of the present invention is attached to a base material. FIG. 1 is a cross-sectional view schematically showing an example of a laminate using the polyolefin resin film of the present invention. The laminate shown in FIG. 1 has a structure in which a transparent film 11, a printing layer 12, a polyolefin resin film (base film) 13 of the present invention, a primer layer 14, an adhesive layer 15, and a base material 16 are arranged in this order.

The transparent film 11 is, for example, a film formed of a transparent resin. Examples of the transparent resin include acrylic resin. The thickness of the transparent film 11 is not particularly limited, but is, for example, in the range of 100 to 1000 μm. The transparent film 11 is provided for the purpose of improving the scratch resistance of the printed surface.

The print layer 12 may cover the entire surface of the base film 13 or may partially cover the surface of the base film 13. For example, when the print layer has a planar shape corresponding to an arbitrary pattern, information, or the like, the print layer partially covers the surface of the base film 13.

The printing method for forming the print layer 12 is not particularly limited, and for example, inkjet printing is used. The print layer 12 is formed by fixing the ink on the surface of the base film 13. As the ink, conventionally known inks can be used, and examples thereof include inks containing a solvent, a pigment, a vehicle, and the like.

The primer layer 14 is, for example, a layer containing a silane coupling agent and a reaction product of a silane compound and a polyolefin as main components. The type of the silane coupling agent used is not particularly limited, and a conventionally known silane coupling agent suitable for improving the adhesiveness with the polyolefin can be used. The primer layer 14 is formed by applying a primer composition using various applicators and usually drying at room temperature. As a coating method, for example, a brush coating method, a spray coating method, a wire bar method, a blade method, a roll coating method and the like can be used for coating. The thickness of the primer layer 14 is not particularly limited, but is, for example, in the range of 2 to 40 μm.

The adhesive layer 15 is a layer obtained by curing the adhesive applied to the surfaces of the primer layer 14 and / or the base material 16. As the adhesive, a conventionally known adhesive can be used and may be appropriately selected depending on the material of the base material and the like.

The base material 16 is not particularly limited, but for example, a building material such as a kitchen door is suitable. That is, the laminate of the present invention is preferably used for lining a kitchen door. The material of the base material 16 is not particularly limited, and examples thereof include plywood.

The method for attaching the polyolefin resin film of the present invention to the substrate is not particularly limited, and examples thereof include wrapping, thermoforming, and vacuum forming. As a specific example of wrapping, there is a method of sticking the film along the base material while warming the film with a dryer to soften it. Further, as a specific example of vacuum forming, there is a method of using a TOM forming machine as a vacuum / pressure air forming machine and attaching a film to a base material at a heating temperature of 80 to 140 ° C. of a heater. According to vacuum forming, it is possible to effectively prevent air from entering between the film and the base material.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1)
55 parts by weight of polyethylene resin (“T-4005” manufactured by Sun Aroma), 45 parts by weight of polyethylene resin (“T-8150” manufactured by Keiyo Polyethylene), and phosphorus-based antioxidant (“T-8150” manufactured by ADEKA). Adecastab PEP-36 ", a compound represented by the above formula (1)) 0.3 parts by weight, and a very low basic hindered amine light stabilizer (made by ADEKA) having a weight average molecular weight of 681 including a NO-alkyl structure. Adecastab LA-81 ”, 0.2 parts by weight of the compound represented by the above formula (4)), 42 parts by weight of titanium oxide (“PO-CB089” manufactured by Nikko Bics Co., Ltd.) manufactured by the chlorine method, and calcium carbonate. 16 parts by weight of (filler) and a small amount of plate-out inhibitor (adhesion inhibitor), hydrotalcite (heat stabilizing aid) and benzophenone-based ultraviolet absorber are mixed with a Banbury mixer and melted at 180 ° C. Kneaded. Next, the obtained kneaded product was supplied to a common head type mixing roll and rolled at a roll temperature of 165 to 190 ° C. to produce a polyolefin resin film having a thickness of 60 μm. The titanium oxide "PO-CB089" was surface-treated to bond Si, Zn, polyol, siloxane and Al to the surface of titanium oxide particles.

(Example 2)
55 parts by weight of the polyethylene-based resin "T-4005", 45 parts by weight of the polyethylene-based resin "T-8150", and a phosphorus-based antioxidant ("Adecastab HP-10" manufactured by ADEKA, shown in the above formula (2). Compound) 2-ethylhexyl phophite) 0.1 part by weight and a very low basic hindered amine light stabilizer containing a NO-alkyl structure and a weight average molecular weight of 681 (“Adecastab LA-81” manufactured by ADEKA) 0. 5 parts by weight, 42 parts by weight of titanium oxide "PO-CB089" manufactured by the chlorine method, 16 parts by weight of calcium carbonate (filler), and trace amounts of plate-out inhibitor (adhesion inhibitor) and hydrotalcite, respectively. (Heat-stabilizing processing aid) and a benzotriazole-based ultraviolet absorber were mixed with a Banbury mixer, and melt-kneaded at 180 ° C. Next, the obtained kneaded product was supplied to a common head type mixing roll and rolled at a roll temperature of 165 to 190 ° C. to produce a polyolefin resin film having a thickness of 60 μm.

(Comparative Example 1)
55 parts by weight of polyethylene resin "T-4005", 45 parts by weight of polyethylene resin "T-8150", and "ADEKA STUB 2112" and "ADEKA STAB AO-60" manufactured by ADEKA were blended in a ratio of 1: 1. 0.2 parts by weight of a phenolic antioxidant ("ADEKA STAB A-611" manufactured by ADEKA) and a highly basic hindered amine light stabilizer ("ADEKA STAB LA-63P" manufactured by ADEKA) with a molecular weight of about 2000 0 .2 parts by weight, 44 parts by weight of titanium oxide (“PO-CB0076” manufactured by Nikko Bics Co., Ltd.) manufactured by the sulfuric acid method, 16 parts by weight of calcium carbonate (filler), and a small amount of plate-out inhibitor, respectively. (Adhesion inhibitor), hydrotalcite (heat stabilizing aid) and benzophenone-based ultraviolet absorber were mixed with a Banbury mixer and melt-kneaded at 180 ° C. Next, the obtained kneaded product was supplied to a common head type mixing roll and rolled at a roll temperature of 165 to 190 ° C. to produce a polyolefin resin film having a thickness of 60 μm. The titanium oxide "PO-CB0076" was surface-treated to bond Al to the surface of the titanium oxide particles.

(Evaluation test 1)
The polyolefin resin films produced in Examples 1 and 2 and Comparative Example 1 were evaluated by the following methods. The results are shown in Table 1 below.

(1-1) Breaking strength and elongation at break JIS K6732, vertical direction (length direction of film, that is, flow direction at the time of film forming) and under the conditions of tensile speed 200 mm / min and measurement temperature 23 ° C. ± 2. The breaking strength (N) and the elongation at break (%) in the horizontal direction (the width direction of the film) were measured.

(1-2) Heat expansion / contraction ratio According to JIS K6732, the expansion / contraction ratio (%) in the vertical direction and the horizontal direction when heated at 100 ° C. for 30 minutes was measured.

As can be seen from Table 1 above, the polyolefin resin films of Examples 1 and 2 and Comparative Example 1 all exceed the target values in breaking strength, elongation at break and heat expansion / contraction rate, and have good durability and moldability. Was to have.

(Example 3 and Comparative Examples 2 to 7)
A polyolefin resin film was produced in the same manner as in Example 1 except that the types of antioxidant, hindered amine-based light stabilizer, and titanium oxide were changed as shown in Table 2 below.

(Evaluation test 2)
The polyolefin resin films prepared in Examples 1 and 3 and Comparative Examples 2 to 7 were evaluated by the following methods. The results are shown in Table 2 below.

(2-1) NOx Evaluation The degree of discoloration of the polyolefin resin film by NOx gas was evaluated by the following method with reference to JIS L 0855 (Dyeing fastness test method for nitrogen oxides). As evaluation samples, three test pieces obtained by cutting the polyolefin resin films of Examples 1 and 3 and Comparative Examples 2 to 7 into 30 mm × 60 mm were prepared.

(1) After cleaning the inside of the desiccator, an evaluation sample was placed in the desiccator.
(2) A beaker containing 100 ml of distilled water was placed in a desiccator.
(3) 0.1 g of sodium nitrite was placed in 10 g (98%) of sulfuric acid, and the desiccator lid was immediately closed.
(4) The desiccator was placed in an oven set at 60 ° C. and left for 20 hours.
(5) The degree of discoloration (ΔE) of the taken-out evaluation sample was measured using a spectrophotometer (SPECTROPHOTO METER CM-3600d, manufactured by Konica Minolta Holdings Co., Ltd.).

(2-2) Evaluation of yellowing in a dark place Place a test piece in a constant temperature and humidity chamber (dark place), and attach a light bulb (Panasonic's "Palook Ball Premier EFA10ED / 7H2 / 2T") 200 mm away from the test piece. The test piece was left for 20 days in an environment of 40 ° C. × 90%, and the change in color tone was measured.

As can be seen from Table 2 above, the polyolefin resin films of Examples 1 and 3 gave good results in both the NOx evaluation and the dark yellowing evaluation. On the other hand, since the polyolefin resin films of Comparative Examples 2 to 5 used a phenolic antioxidant, the degree of discoloration was higher than that of the polyolefin resin films of Examples 1 and 3 in both the NOx evaluation and the dark yellowing evaluation. It was big. Although the polyolefin resin films of Comparative Examples 6 and 7 used a phosphorus-based antioxidant, sulfuric acid titanium oxide was used. Therefore, in the evaluation of yellowing in the dark, the degree of discoloration was higher than that of the polyolefin resin films of Examples 1 and 3. Was big.

11 Transparent film 12 Printing layer 13 Polyolefin resin film (base film)
14 Primer layer 15 Adhesive layer 16 Base material

Claims (5)

Contains polyolefins, hindered amine light stabilizers, titanium oxide and phosphorus antioxidants,
The hindered amine-based light stabilizer has a structure in which an alkoxyl group is bonded to a nitrogen atom of a piperidine ring.
The titanium oxide is a polyolefin resin film which has been subjected to a surface treatment in which at least one of Si, Zn, polyol and siloxane is bonded to the surface of titanium oxide particles. The polyolefin resin film according to claim 1, wherein the hindered amine-based light stabilizer is a compound represented by the following chemical formula.

A decorative film using the polyolefin resin film according to claim 1 or 2. The decorative film according to claim 3, wherein the decorative film is used for wall covering around water. A laminate characterized in that the polyolefin resin film according to claim 1 or 2 or the decorative film according to claim 3 or 4 is attached to a base material.

Images