JP2021054908A - Decorative film and decorative molding - Google Patents

Abstract

To provide a decorative film and a decorative film molding capable of suppressing an ornamental design change such as water absorption whitening over a long term.SOLUTION: A decorative film comprising a resin layer containing a polyvinyl chloride resin, a barium-zinc-based thermal stabilizer, and a plasticizer, in which the resin layer contains 3 to 10 pts.wt. of the barium-zinc-based thermal stabilizer, and 10 to 45 pts.wt of the plasticizer, relative to 100 pts.wt. of the polyvinyl chloride-based resin, the barium-zinc-based thermal stabilizer contains 0.5 to 2.5 pts.wt. of zinc and 10 to 22 pts.wt. of a lubricant relative to 100 pts.wt. of the barium-zinc-based thermal stabilizer.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative film and a decorative molded product.

Halogen-containing resins such as polyvinyl chloride (PVC) -based resins are prone to thermal decomposition due to hydrogen dehalogenation during heat molding, so one or more types of heat stabilizers can be used as the above resins. Measures have been taken to suppress deterioration in the processing process by adding to.

For example, in the examples of Patent Document 1, 20 to 65 parts by weight of the plasticizer, 0.1 to 5 parts by weight of the epoxy resin, and 1 to 10 parts by weight of the acrylic processing aid are used with respect to 100 parts by weight of the PVC resin. And a transparent soft film or sheet to which various stabilizers are added is disclosed.

Here, the decorative film used for decoration of a wall surface or the like may undergo a design change such that the red decorative film turns light pink when it contains water due to rain or the like. That is, the design of the surface of the article decorated with the decorative film may be changed due to the water absorption and whitening of the decorative film.

Such changes in the design due to water absorption and whitening can be suppressed by incorporating a tin-based heat stabilizer in the decorative film. However, tin-based heat stabilizers have poor weather resistance and may cause other problems depending on the application in which they are used, so their applications are limited. In recent years, the use of chemical substances has been regulated in consideration of the environment, etc., and tin-based heat stabilizers have also been listed as subject to regulation or expected to be regulated in the future. It is difficult to use for.

The above-mentioned Patent Document 1 discloses a film and a sheet having excellent water-absorbing whitening resistance, but the film of the above-mentioned Patent Document 1 is not suitable as a decorative film because it is a soft film, and also has a design such as water-absorbing whitening. There was still room for improvement to curb change.

Further, as a decorative film (sheet) having water absorption and whitening resistance, for example, Patent Document 2, Patent Document 3, Patent Document 4 and Patent Document 5 include a resin layer containing a polyvinyl chloride resin and a heat stabilizer. The decorative film (sheet) to be used is disclosed, and a barium-zinc-based heat stabilizer is used as the heat stabilizer. However, there is still room for improvement in suppressing design changes such as water absorption and whitening.

Japanese Patent No. 3377754 JP-A-2018-83899 Japanese Unexamined Patent Publication No. 2016-86891 Japanese Unexamined Patent Publication No. 2015-78330 Japanese Unexamined Patent Publication No. 2000-103926

From the above, there has been a demand for a decorative film and a decorative molded product that can suppress design changes such as water absorption and whitening over a long period of time.

An object of the present invention is to provide a decorative film and a decorative molded product capable of suppressing design changes such as water absorption and whitening over a long period of time.
The present inventors have conducted various studies on heat stabilizers used in decorative films and decorative molded products. As a result, by using a barium-zinc-based heat stabilizer having a specific zinc content and a specific lubricant content as the heat stabilizer to be added to the polyvinyl chloride-based resin, the film absorbs water for a long period of time. The present invention has been completed by finding that it is possible to suppress design changes such as whitening.

The decorative film of the present invention has a resin layer containing a polyvinyl chloride-based resin, a barium-zinc-based heat stabilizer, and a plasticizer, and the resin layer is 100 parts by weight of the polyvinyl chloride-based resin. On the other hand, the barium-zinc-based heat stabilizer containing 3 to 10 parts by weight of the barium-zinc-based heat stabilizer and 10 to 45 parts by weight of the plasticizer is the barium-zinc-based heat stabilizer. It is characterized by containing 0.5 to 2.5 parts by weight of zinc and 10 to 22 parts by weight of a plasticizer with respect to 100 parts by weight of the heat stabilizer.

The resin layer preferably does not contain an epoxy-based plasticizer.

The thickness of the resin layer is preferably 50 to 500 μm.

It is preferable that the decorative film further has a pressure-sensitive adhesive layer and a separator, and the resin layer, the pressure-sensitive adhesive layer, and the separator are laminated in this order.

The decorative film is preferably used for outdoor exterior wall mounting.

The decorative molded product of the present invention includes a base material and the decorative film of the present invention covering the base material, and the base material and the decorative film are laminated via an adhesive layer. It is characterized by.

The decorative film and the decorative molded product of the present invention can suppress design changes such as water absorption and whitening over a long period of time.

It is sectional drawing which shows typically an example of the decorative film of this invention. It is sectional drawing which showed an example of the decorative molded article of this invention. It is a schematic diagram for demonstrating the evaluation method of the calender workability in an Example and a comparative example.

The decorative film of the present invention is composed of a single layer or a plurality of layers, and has a resin layer containing a polyvinyl chloride-based resin, a barium-zinc-based heat stabilizer, and a plasticizer. With respect to 100 parts by weight of the polyvinyl chloride resin, 3 to 10 parts by weight of the barium-zinc-based heat stabilizer and 10 to 45 parts by weight of the plasticizer are contained, and the barium-zinc-based heat is contained. The stabilizer is characterized by containing 0.5 to 2.5 parts by weight of zinc and 10 to 22 parts by weight of a plasticizer with respect to 100 parts by weight of the barium-zinc-based heat stabilizer.

In the present specification, "film" is synonymous with "sheet", and the two are not distinguished by the thickness.

In the present specification, "XY" means "X or more, Y or less".

Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the embodiments shown in the drawings. FIG. 1 is a cross-sectional view schematically showing an example of the decorative film of the present invention.

As shown in FIG. 1, in the decorative film 1a, the resin layer 10, the adhesive layer 20, and the separator 30 are laminated in this order. In the present specification, "A and B are laminated" and "A and B are laminated" mean that another layer is arranged between A and B in addition to the case where A and B are in contact with each other. Including the case where it is.

[Polyvinyl chloride resin]
The decorative film 1a contains a polyvinyl chloride-based resin in the resin layer 10. The polyvinyl chloride resin has good elongation when formed into a film and is hard to break, so that it can be easily attached to a three-dimensional curved surface. Further, a film containing a polyvinyl chloride resin is suitable as a decorative film because it has excellent printability and is softened by heat from a dryer or the like.

Examples of the polyvinyl chloride-based resin include a homopolymer of vinyl chloride and a copolymer of vinyl chloride with another monomer copolymerizable with vinyl chloride. Examples of the other copolymerizable monomer include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and styrene; methyl (meth) acrylate, ethyl (meth) acrylate, and the like. (Meta) Acrylic acid alkyl ester such as methyl acrylate; Maleic acid diester such as dibutyl maleate and diethyl maleate; Fumaric acid diester such as dibutyl fumarate and diethyl fumarate; Cyanization of acrylonitrile and methacrylonitrile Vinyl: Vinyl halides such as vinylidene chloride and vinyl bromide; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether can be mentioned. These may be used alone or in combination of two or more. In addition, in this specification, "(meth) acrylic acid" means "at least one of acrylic acid and methacrylic acid".

The content of the other copolymerizable monomer in the copolymer is usually 50% by weight or less, preferably 10% by weight or less. Among the above-mentioned polyvinyl chloride-based resins, a homopolymer of vinyl chloride is preferable from the viewpoint of excellent dimensional stability.

The average degree of polymerization of the polyvinyl chloride resin is preferably 800 to 1200. In the present invention, the average degree of polymerization of the polyvinyl chloride resin means the average degree of polymerization measured in accordance with JIS K 6721 “Vinyl chloride resin test method”.

[Heat stabilizer]
The resin layer 10 contains a barium-zinc-based heat stabilizer, and the content of the barium-zinc-based heat stabilizer with respect to 100 parts by weight of the polyvinyl chloride-based resin is 3 to 10 parts by weight. By setting the content of the barium-zinc-based heat stabilizer within the above range, water absorption bleaching can be suppressed for a long period of time. The content of the barium-zinc-based heat stabilizer with respect to 100 parts by weight of the polyvinyl chloride-based resin is preferably 3 to 7 parts by weight, and more preferably 4 to 6 parts by weight.

The barium-zinc-based heat stabilizer contains 0.5 to 2.5 parts by weight of zinc and 10 to 22 parts by weight of lubricant with respect to 100 parts by weight of the barium-zinc-based heat stabilizer. The barium-zinc-based heat stabilizer used in the present invention is difficult to absorb water, and various additives added to the polyvinyl chloride-based resin can suppress water absorption. Further, since the zinc content is as low as 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the barium-zinc-based heat stabilizer, the production of zinc chloride is suppressed and the production of zinc chloride is suppressed for a long period of time. It is possible to suppress water absorption and whitening of the film. Further, since the content of the lubricant is 10 to 22 parts by weight with respect to 100 parts by weight of the barium-zinc-based heat stabilizer, the slipperiness is improved and the production of zinc chloride can be suppressed.

In the above barium-zinc heat stabilizer, zinc may be contained in an amount of 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the barium-zinc-based heat stabilizer, but 0.75 to 2 It is preferably contained in an amount of .25 parts by weight. With such an embodiment, it is possible to further suppress water absorption bleaching.

Further, in the barium-zinc heat stabilizer, the lubricant may be contained in an amount of 10 to 22 parts by weight with respect to 100 parts by weight of the barium-zinc-based heat stabilizer, but is contained in an amount of 12 to 20 parts by weight. It is preferable, and it is more preferable that it is contained in an amount of 13 to 15 parts by weight. With such an embodiment, it is possible to further suppress water absorption bleaching.

As the barium-zinc-based heat stabilizer, a barium-zinc-based heat stabilizer satisfying the specific zinc content and the specific lubricant content can be used, and specifically, for example, for example. QL-1133 and QL-1135 manufactured by ADEKA can be used.

The decorative film 1a of the present invention contains a barium-zinc-based heat stabilizer having a specific zinc content and a specific lubricant content in the resin layer 10, and thus has an effect of suppressing a design change due to water absorption whitening or the like. Has been obtained. It is also possible to contain a zinc compound having an aliphatic group or a barium compound having an aliphatic group in the barium-zinc-based heat stabilizer, and a zinc compound having an aromatic group and a barium compound having an aromatic group can be used. It can also be contained. The barium-zinc-based heat stabilizer preferably contains a zinc compound having an aliphatic group.

Further, the barium-zinc-based heat stabilizer may further contain a phosphorus compound. When the phosphorus compound is contained in the barium-zinc-based heat stabilizer, the content of the phosphorus compound is preferably higher than that of the barium compound having an aromatic group.

In addition to the barium-zinc-based heat stabilizer, the resin layer 10 can also be used in combination with a heat stabilizer usually used in the field of film. For example, a metal organic acid compound containing lead (Pb), barium (Ba), zinc (Zn), calcium (Ca), tin (Sn) and the like can also be used.

[Plasticizer]
The decorative film 1a of the present invention contains a plasticizer in the resin layer 10. By adding a plasticizer, the hardness of the resin layer can be adjusted to obtain a transparent semi-hard to hard decorative film, and cold impact resistance, weather resistance, scratch resistance and the like can be improved. The plasticizer may be any one that can easily process the polyvinyl chloride film, and as the plasticizer, those usually used in the field of the polyvinyl chloride film can be used. For example, phthalates such as octyl phthalate (di-2-ethylhexyl phthalate), dibutyl phthalate, dinonyl phthalate, diisononyl phthalate (DINP), dioctyl adipate, dioctyl sevacinate and other aliphatic dibasins. Examples thereof include phosphoric acid triesters such as acid diester, tricresyl phosphate and trioctyl phosphate, and high molecular weight polyester plasticizers. As the plasticizer, it is preferable to use a polyester-based plasticizer.

The polyester-based plasticizer has good compatibility with vinyl chloride resin. Further, since the polyester-based plasticizer is a polymer as compared with the phthalic acid-based plasticizer generally used as the plasticizer for the vinyl chloride resin, it is difficult to dissolve and swell in gasoline. Therefore, by using a polyester-based plasticizer, it is possible to impart flexibility to the polyvinyl chloride film and enhance cold impact resistance. As the polyester-based plasticizer, for example, ADEKA Sizer PN7535 (manufactured by ADEKA), ADEKA Sizer PN7230 (manufactured by ADEKA), and the like can be used.

The weight average molecular weight of the polyester plasticizer is preferably 2000 to 6000. If the weight average molecular weight is less than 2000, the water absorption and whitening resistance may be deteriorated, while if the weight average molecular weight exceeds 6000, the handleability may be deteriorated. The weight average molecular weight of the polyester plasticizer is more preferably 3000 to 5000.

The weight average molecular weight (Mw) of the polyester plasticizer is measured by GPC (gel permeation chromatography). The measurement conditions 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 resin layer 10 preferably does not contain an epoxy-based plasticizer. Examples of the epoxy-based plasticizer include epoxidized soybean oil and epoxidized fatty acid isobutyl. If the resin layer contains an epoxy-based plasticizer, the adhesive may be denatured and the adhesive properties may be deteriorated, and the adhesive ability is insufficient as a decorative film applied to a ^{wide area (for example, 3 m 2 or more).} This is because there is a possibility that

The resin layer 10 contains 10 to 45 parts by weight of the plasticizer with respect to 100 parts by weight of the polyvinyl chloride resin. By setting the content of the plasticizer in the above range, a decorative film more suitable for decorative processing can be obtained. That is, if the content of the plasticizer is less than 10 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin, it may become highly hard and unsuitable for decorative processing, and the content of the plasticizer is 45 parts by weight. If it exceeds, the plasticizer may bleed on the surface of the decorative film or become soft and the decorative function may not be satisfied. The content of the plasticizer with respect to 100 parts by weight of the polyvinyl chloride resin is preferably 20 to 30 parts by weight.

[Heat stability aid]
The resin layer 10 may further contain a thermal stability aid. The thermal stability aid may be any one that can enhance the thermal stability of the film by being used in combination with the barium-zinc-based thermal stabilizer, and the technical field to which the present invention belongs (film field). The ones normally used in can be used. For example, phenolic antioxidants, β-diketones, phosphite compounds, polyol compounds and the like can be mentioned, and among them, phenolic antioxidants are preferably used.

The resin layer 10 preferably contains the above thermal stability aid in an amount of 0.1 to 4 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. More preferably, it is further preferably contained in an amount of 0.5 to 2 parts by weight. When the content of the heat stability aid is in the above range, the function as the heat stability aid can be exhibited without excessive cost, and water absorption bleaching can be further suppressed. That is, if the content of the thermal stability auxiliary agent with respect to 100 parts by weight of the polyvinyl chloride resin is less than 0.1 parts by weight, the function as the thermal stability auxiliary agent may not be exhibited, and water absorption bleaching is suppressed. You may not be able to do it. Further, if the content of the thermal stability aid with respect to 100 parts by weight of the polyvinyl chloride resin exceeds 4 parts by weight, the cost may be significantly increased.

[Acrylic processing aid]
The resin layer 10 may further contain an acrylic processing aid. The acrylic processing aid may be any as long as it can enhance the moldability of the decorative film, and the acrylic processing aid usually used in the technical field (film field) to which the present invention belongs. Can be used. For example, one type of (meth) acrylic acid ester may be polymerized or two or more types may be copolymerized.

Examples of polymerized or copolymerized (meth) acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, isobutyl. Examples thereof include acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and tridecyl methacrylate. In addition to the above, (meth) acrylic acid and (meth) acrylic acid ester containing a hydroxy group can also be mentioned.

The resin layer 10 preferably contains 1 to 10 parts by weight, more preferably 1 to 6 parts by weight of the acrylic processing aid with respect to 100 parts by weight of the polyvinyl chloride resin. By setting the content of the acrylic processing aid within the above range, workability can be ensured while suppressing costs. That is, if the content of the acrylic processing aid with respect to 100 parts by weight of the polyvinyl chloride resin is less than 1 part by weight, it may be difficult to secure processability, and if it exceeds 10 parts by weight, it is significantly increased. It may be costly. Examples of the acrylic processing aid include Metabrene P-530 and P-1901 manufactured by Mitsubishi Chemical Corporation.

[Other additives]
The resin layer 10 can contain various additives as long as the effects of the present invention are exhibited. Examples of the additives include impact strength modifiers, lubricants, antioxidants, colorants, flame retardants, antistatic agents, auxiliary agents, reinforcing agents, antifogging agents, fillers, diluents, fungicides, and the like. Examples thereof include a light stabilizer, an ultraviolet absorber, a modifier, and the like, and those generally blended with a polyvinyl chloride resin can be used.

[UV absorber]
The resin layer 10 may contain an ultraviolet absorber. The ultraviolet absorber may be any as long as it has an ability to absorb ultraviolet rays, and those usually used in the technical field (film field) to which the present invention belongs can be used. As the ultraviolet absorber, for example, a benzophenone-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber can be used. A benzophenone-based ultraviolet absorber is preferably used from the viewpoint of obtaining a colorless and transparent film in which yellowness is suppressed. Specifically, examples of the benzophenone-based ultraviolet absorber include ADEKA 1413 manufactured by ADEKA Corporation, and examples of the benzotriazole-based ultraviolet absorber include LA-29 manufactured by ADEKA Corporation.

The content of the ultraviolet absorber in the resin layer 10 is preferably 0.5 parts by weight to 2.0 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin.

The thickness of the resin layer 10 is preferably 50 to 500 μm. If the thickness is less than 50 μm, the ink absorption capacity may be insufficient, the color development property (design sharpness) at the time of printing may be lowered, and the decorative film may be too flexible, resulting in poor workability. Sometimes. Furthermore, the weather resistance is also inferior. On the other hand, if it exceeds 500 μm, the followability to the base material may decrease. Furthermore, the flexibility may be poor and the texture of the decorative film may be hard. The thickness of the resin layer 10 is more preferably 60 to 200 μm.

[Adhesive layer]
The decorative film 1a may have an adhesive layer 20. By having the pressure-sensitive adhesive layer 20, the decorative film 1a can be easily attached to the base material, and can be suitably used as the decorative film 1a.

The pressure-sensitive adhesive layer 20 is not particularly limited as long as it has a pressure-sensitive adhesive function (pressure-sensitive adhesiveness), and for example, one containing a pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or a silicone-based pressure-sensitive adhesive. Can be mentioned. Among them, an acrylic pressure-sensitive adhesive is preferably used because it is excellent in adhesiveness, processability, heat aging resistance, moisture aging resistance, and weather resistance, and is relatively inexpensive.

The decorative film 1a may have a print layer. The printing layer is preferably laminated on the side opposite to the pressure-sensitive adhesive layer 20 of the resin layer 10 of the decorative film 1a. The printing layer is formed by printing on the resin layer 10 of the decorative film 1a, and can be performed by, for example, inkjet printing, gravure printing, screen printing, rotary screen printing, flexo printing, offset printing, electrostatic printing, or the like. it can. The decorative film 1a may have other layers such as a base film and a primer layer in addition to the printing layer.

The thickness of the pressure-sensitive adhesive layer 20 is not particularly limited, but is preferably 10 to 60 μm, and more preferably 20 to 50 μm.

[separator]
The decorative film 1a of the present invention may further have a separator 30. The separator 30 is not particularly limited as long as the surface to be attached to the pressure-sensitive adhesive layer 20 is subjected to a mold release treatment.

As the separator 30, a release film or a release paper usually used in the technical field (film field) to which the present invention belongs can be used. Examples of the release film include those in which the surface of a polyethylene terephthalate (PET) film or the like is coated with a silicone-based, alkyd-based, fluorine-based release agent or the like. Examples of the release paper include those in which the surface of high-quality paper is coated with a silicone-based, alkyd-based, fluorine-based release agent, or the like.

The decorative film 1a may have a protective film layer on the side opposite to the pressure-sensitive adhesive layer 20 of the resin layer 10. As the protective film layer, those usually used in the technical field (film field) to which the present invention belongs can be used, and are formed of, for example, a polyethylene terephthalate resin, a polypropylene resin, a polycarbonate resin, or the like.

That is, in the decorative film of the present invention, the resin layer, the pressure-sensitive adhesive layer, and the separator are preferably laminated in this order, and further, a printing layer is placed on the opposite side of the resin layer 10 from the pressure-sensitive adhesive layer 20. , Protective layer, primer layer and other layers may be included.

As a method for producing the decorative film 1a, for example, the resin layer 10 is melt-kneaded with the above-mentioned polyvinyl chloride-based resin using a Banbury mixer or the like to obtain a polyvinyl chloride-based resin composition, and then the polyvinyl chloride-based resin is obtained. The vinyl-based resin composition can be formed into a film by calendar processing. According to the calendering process, even a thin film can be produced with excellent thickness accuracy.

The calendar format used for the above calendar processing is not particularly limited, and conventionally known formats such as an inverted L type, a Z type, an upright two-line type, an L-type, and an inclined three-line type can be adopted.

When the decorative film 1a has the pressure-sensitive adhesive layer 20, the pressure-sensitive adhesive layer 20 uses a separator 30 (release film or a release film or a film-forming method using a general-purpose film forming apparatus such as various coating devices, bar coats, and doctor blades, and a film forming method. It can be formed by applying the pressure-sensitive adhesive composition on the release paper) and then drying it. The decorative film 1a is manufactured by laminating the pressure-sensitive adhesive layer 20 on the resin layer 10 obtained by calendar processing or the like.

Next, the decorative molded article of the present invention will be described. The decorative molded product of the present invention includes a base material and the decorative film of the present invention covering the base material, and the base material and the decorative film are laminated via an adhesive layer. FIG. 2 is a schematic cross-sectional view showing an example of a decorative molded product of the present invention. As shown in FIG. 2, in the decorative molded product 2, the surface of the base material 40 is covered with the decorative film 1b. The base material 40 and the decorative film 1b are adhered to each other via the pressure-sensitive adhesive layer 20.

The decorative film is used by attaching the decorative film from which the separator 30 has been peeled off to a base material. Since the decorative film of the present invention follows a three-dimensional curved surface, it is also suitably used for a base material having a three-dimensional curved surface.

The decorative film can be attached at room temperature, and can be attached while being heated by a dryer or the like. In this case, it can be attached to the base material by hand or squeegee. Further, as a method for constructing the decorative film, a method usually used in the technical field to which the present invention belongs can be adopted. Further, the decorative film from which the separator has been peeled off can be laminated on the base material, and can be applied by a method such as vacuum forming, pressure forming, vacuum / pressure forming, in-molding, film insert molding, and laminating.

The material of the base material is not particularly limited, and is, for example, a resin such as a polycarbonate resin, an acrylic resin, or a styrene resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin); a metal such as iron, copper, or aluminum. ; Examples include alloys.

The use of the decorative film of the present invention is not particularly limited, but it is preferably used for indoor / outdoor wall mounting, for example. Specific examples thereof include decorative boards (wall covering materials) to be attached to the wall surface, interior doors, closet and kitchen doors, furniture, and interior materials such as flooring. Further, it is suitably used for wall covering around water such as bathrooms, kitchens, washrooms, and toilets. According to the decorative film of the present invention, a design equivalent to that of a painted product can be obtained by a method simpler and safer than painting.

The decorative film of the present invention can be used, for example, for decoration, protection, advertising, etc. on the surface of a base material. In addition, characters, patterns, etc. can be transferred to the surface of the decorative film and attached to the base material to be used as an advertisement.

Further, the decorative film of the present invention is preferably applied to a base material having a relatively wide area, for example, preferably applied to a base material of 1 to 3.5 m ² . The decorative film of the present invention preferably does not contain an epoxy-based plasticizer in the resin layer, and when it does not contain an epoxy-based resin, the adhesive strength is reduced even when used on a base material having a relatively wide area. Because it is difficult.

[Examples / Comparative Examples]
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

(Example 1)
For 100 parts by weight of a polyvinyl chloride resin having an average degree of polymerization of 800, 4.0 parts by weight of a barium-zinc heat stabilizer (QL-1133) and a polyester plasticizer (ADEKA) having a weight average molecular weight of 4500 are added. 24.0 parts by weight of Sizer PN7535 (manufactured by ADEKA Corporation) was added and melt-kneaded with a Banbury mixer to prepare a vinyl chloride resin composition. Next, the vinyl chloride resin composition was supplied to a four inverted L-shaped roll type 24-inch calendar, and the thickness was 80 μm under the conditions of the calendar roll equipment temperature of 170 to 190 ° C. and the temperature of the resin composition of 180 to 210 ° C. The decorative film of Example 1 was obtained by forming a calendar on the surface. In the barium-zinc-based heat stabilizer (QL-1133) used in Example 1, the zinc content with respect to 100 parts by weight of the heat stabilizer was 0.75 to 2.25 parts by weight, and the lubricant was contained. The amount was 13-15.

The zinc content and lubricant content of the barium-zinc heat stabilizer used in Examples and Comparative Examples are shown in Table 1 below.

(Example 2)
A decorative film of Example 2 was obtained in the same manner as in Example 1 except that the type of barium-zinc heat stabilizer was changed to the heat stabilizer shown in Table 2 below.

(Example 3)
A decorative film of Example 3 was obtained in the same manner as in Example 2 except that the content of the barium-zinc-based heat stabilizer was changed from 4.0 parts by weight to 3.0 parts by weight.

(Comparative Example 1)
A decorative film of Comparative Example 1 was obtained in the same manner as in Example 1 except that the type of barium-zinc heat stabilizer was changed to the heat stabilizer shown in Table 2 below.

(Comparative Example 2)
To 100 parts by weight of the polyvinyl chloride resin, 3.5 parts by weight of epoxidized soybean oil (W100: manufactured by DIC) was further added, and the content of the polyester plasticizer (PN7535) was increased from 24 parts by weight to 23 parts by weight. A decorative film of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that the weight was changed to 5.5 parts by weight.

(Comparative Example 3)
Comparison except that the type of barium-zinc heat stabilizer was changed to the heat stabilizer shown in Table 2 below, and the contents of plasticizer and epoxidized soybean oil were changed to the contents shown in Table 2 below. A decorative film of Comparative Example 3 was obtained in the same manner as in Example 2.

(Comparative Example 4)
A decorative film of Comparative Example 4 was obtained in the same manner as in Comparative Example 1 except that the type of the barium-zinc heat stabilizer was changed to the heat stabilizer shown in Table 2 below.

(Comparative Examples 5 and 6)
The decorative films of Comparative Examples 5 and 6 were obtained in the same manner as in Example 2 except that the content of the plasticizer was changed to the content shown in Table 2 below.

(Comparative Examples 7-9)
The decorative films of Comparative Examples 7 to 9 were obtained in the same manner as in Example 2 except that the content of the barium-zinc-based heat stabilizer was changed to the content shown in Table 2 below.

The materials used in Examples and Comparative Examples are shown in Table 2 below.

(Evaluation of decorative film)
The decorative films produced in Examples and Comparative Examples were evaluated for (1) calendar workability, (2) water absorption and whitening resistance, (3) adhesive strength, and (4) weather resistance by the following methods. It was.

(1) Calendar workability The calendar workability of each vinyl chloride resin composition used in Examples and Comparative Examples was evaluated by the following method.

FIG. 3 is a schematic diagram for explaining a method for evaluating calender workability in Examples and Comparative Examples. As shown in FIG. 3, in this evaluation, two 16-inch rolls (a pair of rolls) 51a and 51b were set to a roll temperature of 180 ° C. and a roll gap (distance between rolls) of 0.2 mm, and vinyl chloride. After the based resin composition 52 is kneaded on the roll for 5 minutes, the kneaded vinyl chloride resin composition is peeled off from the surface of the roll 51b as a vinyl chloride resin film having a thickness of 0.2 mm P1. Was identified. After that, the horizontal line passing through the center P0 of the roll 51b was set as the reference line L0, and the angle θ formed by the reference line L0 and the line segment L1 connecting the film peeling position P1 and the center P0 of the roll 51b was calculated. .. Then, the calendar workability was evaluated based on the value of θ. The θ is a positive value when the position P1 is located above the reference line L0, and a negative value when the position P1 is located below the reference line L0. Further, in this evaluation, the smaller the absolute value of the value of θ (the closer to 0 °), the better the calender workability.

(Evaluation criteria for calendar workability)
When θ (absolute value) is -10 ° to 20 °, the evaluation is “○”.
When θ (absolute value) is greater than 20 ° and less than 50 °, it is evaluated as “Δ”.
When θ (absolute value) is larger than 50 °, it is evaluated as “x”.
If the temperature is 60 ° or more, it is considered as "unprocessable".

(2) Water absorption and whitening resistance The decorative films obtained in Examples and Comparative Examples were immersed in water at 40 ° C. for 4 days (96 hours), and then the whiteness of the decorative film was determined by a method in accordance with ASTM E313-96. WI (water absorption whitening index) was measured. The whiteness WI is the degree of expressing the "whiteness" of an object, and when the perfect diffuse reflection surface (ideal white) is set to 100, the value of the whiteness increases as the distance from the ideal white increases. It gets lower. The ASTM standard is a standard set and published by ASTM International, formerly known as the American Society for Testing and Materials.

(Evaluation criteria for water absorption and whitening resistance)
If the HAZE difference is less than 3, the evaluation is "○".
If the HAZE difference is less than 3 to 7, it is evaluated as "Δ".
When the HAZE difference is 7 or more, it is evaluated as "x".

(3) Adhesive strength A pressure-sensitive adhesive mixed solution was applied on a silicon-treated layer of a paper separator (manufactured by Lintec Corporation, trade name "EV130R") having a thickness of 130 μm with a comma bar coater to form a coating film. The pressure-sensitive adhesive mixed solution was obtained by adding a curing agent (manufactured by Soken Chemical Co., Ltd., L-45) to an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., SK Dyne 1506) as a main ingredient. The amount of the pressure-sensitive adhesive mixed solution applied was adjusted so that the weight of the pressure-sensitive adhesive layer obtained after heating and drying was 45 g / m ^2. The coating film was dried by heating in a drying oven at 110 ° C. for 1 minute to obtain a laminate of an adhesive layer and a paper separator. Next, the decorative films obtained in Examples and Comparative Examples and the above-mentioned laminate were bonded together via an adhesive layer to obtain a decorative film with a paper separator.

(Measurement of adhesive strength)
It was measured according to JIS Z0237. Specifically, the decorative film with a separator was cut into a width of 25 mm and a length of 150 mm, and then the paper separator was peeled off to obtain a decorative film with an exposed adhesive layer. Then, while the surface of the decorative film on the adhesive layer side is in contact with the outermost surface of the decorative film, a pressure-bonding roller having a mass of 2 kg is reciprocated once on the base film to pressurize the outermost surface of the decorative film. A decorative film was attached to. Then, after leaving it for 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, the adhesive force when the decorative film is peeled off from the outermost surface of the decorative film under the conditions of a tensile speed of 300 mm / min and a tensile angle of 180 °. (Unit: N / 25 mm) was measured. The adhesive strength was measured twice for each of Examples and Comparative Examples, and the average of the two measured values obtained was taken as the adhesive strength of each Example and Comparative Example.
◯: 14N / 25mm or more ×: less than 14N / 25mm

(4) Weather resistance The decorative films obtained in Examples and Comparative Examples were put into an accelerated weather resistance tester (Sunshine Weather Meter) for 2000 hours. It was visually confirmed whether or not the surface of the decorative film taken out after the test was discolored.

(Light resistance test criteria)
〇: No significant discoloration occurred ×: Significant discoloration occurred

The evaluation results of the decorative films of Examples and Comparative Examples are shown in Table 2 below.

From the results of Examples and Comparative Examples, a polyvinyl chloride-based resin and a barium-zinc-based heat stabilizer having a specific zinc content and a specific lubricant content were combined to form a heat stabilizer for the polyvinyl chloride-based resin. By setting the content and the plasticizer content to specific amounts, it is possible to obtain a decorative film having excellent water absorption and whitening resistance and excellent performance (processability, adhesive strength, weather resistance) required for the decorative film. I found out.

1a, 1b: Decorative film 2: Decorative molded product 10: Resin layer 20: Adhesive layer 30: Separator 40: Base material 51a, 51b: Roll 52: Vinyl chloride resin composition

Claims (6)

It has a resin layer containing a polyvinyl chloride-based resin, a barium-zinc-based heat stabilizer, and a plasticizer.
The resin layer contains 3 to 10 parts by weight of the barium-zinc heat stabilizer and 10 to 45 parts by weight of the plasticizer with respect to 100 parts by weight of the polyvinyl chloride resin.
The barium-zinc-based heat stabilizer contains 0.5 to 2.5 parts by weight of zinc and 10 to 22 parts by weight of lubricant with respect to 100 parts by weight of the barium-zinc-based heat stabilizer. A decorative film characterized by that. The decorative film according to claim 1, wherein the resin layer does not contain an epoxy-based plasticizer. The decorative film according to claim 1 or 2, wherein the thickness of the resin layer is 50 to 500 μm. The decorative film further has a pressure-sensitive adhesive layer and a separator, and the resin layer, the pressure-sensitive adhesive layer, and the separator are laminated in this order. The decorative film according to any one of 3. The decorative film according to any one of claims 1 to 4, wherein the decorative film is used for indoor / outdoor wall mounting. The base material and the decorative film according to any one of claims 1 to 5 covering the base material are provided.
A decorative molded product, wherein the base material and the decorative film are laminated via an adhesive layer.

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