JP6846175B2 - Decorative film and decorative molded product - Google Patents

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.

Further, in Patent Document 2, 100 parts by weight of a vinyl chloride resin is described as 0.01 to 2 parts by weight of a calcium compound, 0.01 to 2 parts by weight of a zinc compound, and 0 of a hydrotalcite compound treated with decrystallized water. A rigid vinyl chloride sheet comprising a composition to which 0.01 to 5 parts by weight is added is disclosed.

Japanese Patent No. 3377754 Japanese Unexamined Patent Publication No. 2000-103872

Here, the decorative film used for decoration of the exterior of a two-wheeled vehicle or the interior of a four-wheeled vehicle has a design such that the red decorative film changes to a light pink color when it contains water due to rain or the like. It could make a difference. 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 water-absorbing whitening and the like. There was still room for improvement in suppressing design changes. Further, Patent Document 2 does not disclose a technique for suppressing water absorption and bleaching.

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.

The present inventors have conducted various studies on heat stabilizers used in decorative films and decorative molded products. As a result, by adding a barium-zinc-based heat stabilizer containing a barium compound having an aromatic group to the polyvinyl chloride-based resin, it is possible to suppress design changes such as water absorption and whitening of the film over a long period of time. We found what we could do and completed the present invention.

The decorative film of the present invention is composed of a single layer or a plurality of layers, has a resin layer containing a polyvinyl chloride-based resin and a barium-zinc-based heat stabilizer, and has the above-mentioned barium-zinc-based thermal stability. The agent is characterized by containing a barium compound having an aromatic group.

The barium compound having an aromatic group preferably has 6 or more and 30 or less carbon atoms.

The barium compound having an aromatic group is preferably a compound represented by the following chemical formula (B1).

（上記化学式（Ｂ１）中、Ｒは水素原子又は炭素数１〜４のアルキル基を表す。）

(In the above chemical formula (B1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

The barium compound having an aromatic group is preferably bis (3-methylbenzoic acid) barium.

The resin layer preferably further contains 5 parts by weight to 45 parts by weight of a plasticizer with respect to 100 parts by weight of the polyvinyl chloride resin.

The plasticizer preferably does not contain a structure derived from a fatty acid.

The resin layer preferably further contains a thermal stability aid.

The thermal stability aid is preferably an epoxy compound.

The resin layer preferably does not contain a tin-based heat stabilizer.

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 molded product of the present invention comprises 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 being.

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 showed 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.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. First, the decorative film of the present invention will be described.
The decorative film of the present invention is composed of a single layer or a plurality of layers, has a resin layer containing a polyvinyl chloride-based resin and a barium-zinc-based heat stabilizer, and has the above-mentioned barium-zinc-based thermal stability. The agent is characterized by containing a barium compound having an aromatic group.

[Polyvinyl chloride resin]
The decorative film of the present invention contains a polyvinyl chloride-based resin in the resin layer. 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 decorative film of the present invention contains a barium-zinc-based heat stabilizer in the resin layer, and the barium-zinc-based heat stabilizer contains a barium compound having an aromatic group. The barium-zinc-based heat stabilizer containing a barium compound having an aromatic group used in the present invention is difficult to absorb water, and various additives added to the polyvinyl chloride-based resin can suppress water absorption. Therefore, it is considered that the water absorption and whitening of the film can be suppressed for a long period of time.

The barium compound having an aromatic group preferably has 6 or more and 30 or less carbon atoms, more preferably 10 or more and 22 or less carbon atoms, and is a compound represented by the following chemical formula (B1). More preferably, it is bis (3-methylbenzoic acid) barium. Examples of the barium-zinc-based heat stabilizer containing a barium compound having an aromatic group include LBZ-2049 manufactured by Sakai Chemical Industry Co., Ltd.

（上記化学式（Ｂ１）中、Ｒは水素原子又は炭素数１〜４のアルキル基を表す。）

(In the above chemical formula (B1), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

R in the chemical formula (B1) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group is a cyclic alkyl group regardless of whether it is a linear alkyl group or a branched alkyl group. There may be. R in the above chemical formula (B1) is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and an alkyl group having 1 carbon atom, that is, a methyl group. Is even more preferable.

The R in the above chemical formula (B1) is, for example, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group. And so on.

In the barium-zinc-based heat stabilizer containing a barium compound having an aromatic group, the barium compound having an aromatic group is preferably contained in an amount of 5% by weight or more and 40% by weight or less, preferably 10% by weight or more and 20% by weight. It is more preferably contained in an amount of 13% by weight or more, and further preferably contained in an amount of 13% by weight or more and 17% by weight or less. With such an embodiment, it is possible to further suppress water absorption bleaching.

The barium compound having an aromatic group is preferably contained in an amount of 0.1 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the polyvinyl chloride resin, and is 0.2 parts by weight or more and 0 parts by weight. It is more preferably contained in an amount of 9.9 parts by weight or less, and further preferably contained in an amount of 0.3 parts by weight or more and 0.7 parts by weight or less. With such an embodiment, it is possible to further suppress water absorption bleaching.

The barium-zinc-based heat stabilizer containing a barium compound having an aromatic group preferably further contains a zinc compound having an aromatic group. The zinc compound having an aromatic group is preferably contained in the barium-zinc-based heat stabilizer in an amount of 11% by weight or more and 25% by weight or less. With such an embodiment, it is possible to further suppress water absorption bleaching.

The zinc compound having an aromatic group is preferably contained in an amount of 0.1 part by weight or more and 2.0 parts by weight or less, preferably 0.2 parts by weight or more, based on 100 parts by weight of the polyvinyl chloride resin. , 2.5 parts by weight or less is more preferable. With such an embodiment, it is possible to further suppress water absorption bleaching.

Further, the barium-zinc-based heat stabilizer containing a barium compound having an aromatic group preferably further contains 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.

The amount of the barium-zinc-based heat stabilizer containing the barium compound having an aromatic group added to the resin layer is 0.1 part by weight to 20 parts by weight with respect to 100 parts by weight of the polyvinyl chloride-based resin. It is preferably 1 part by weight to 10 parts by weight, and further preferably 2.8 parts by weight to 4.5 parts by weight. By setting the addition amount of the barium-zinc-based heat stabilizer containing the barium compound having an aromatic group within the above range, water absorption bleaching can be further suppressed over a long period of time.

In the decorative film of the present invention, in addition to the barium-zinc-based heat stabilizer containing the barium compound having an aromatic group, a heat stabilizer usually used in the field of film can also be used in combination. 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.

The decorative film of the present invention preferably does not contain a tin-based heat stabilizer. Weather resistance can be improved by not containing a tin-based heat stabilizer.

Further, in the present invention, by using a barium compound having an aromatic group as a barium-zinc-based heat stabilizer, an action effect of suppressing a design change due to water absorption whitening or the like is obtained. The barium-zinc-based heat stabilizer may contain a barium compound having an aliphatic group or a zinc compound having an aliphatic group. In this case, the barium compound having an aromatic group and the aromatic group It is preferable that the total content (% by weight) of the zinc compound having an aliphatic group exceeds the total content (% by weight) of the barium compound having an aliphatic group and the zinc compound having an aliphatic group. The reason for this is that the barium-zinc-based heat stabilizer containing a barium compound having an aliphatic group or a zinc compound having an aliphatic group is compared with a barium-zinc-based heat stabilizer containing a barium compound having an aromatic group. It is thought that this is because it easily absorbs water.

[Plasticizer]
The decorative film of the present invention preferably contains a plasticizer. By adding a plasticizer to the decorative film of the present invention, a transparent hard to semi-hard decorative film can be obtained, 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 film, and as the plasticizer, those usually used in the field of film can be used. For example, phthalate diesters 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, epoxy plasticizers such as epoxidized soybean oil and epoxy resin, and high molecular weight polyester plasticizers. As the plasticizer, it is preferable to use DINP.

The plasticizer contained in the decorative film of the present invention preferably does not contain a structure derived from fatty acids. Examples of the plasticizer containing a structure derived from a fatty acid include epoxidized soybean oil and the like. The decorative film of the present invention preferably does not contain epoxidized soybean oil. This makes it possible to further suppress water absorption and bleaching.

The amount of the plasticizer added to the resin layer is preferably 5 parts by weight to 45 parts by weight, preferably 12 parts by weight to 20 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. More preferred. By setting the amount of the plasticizer added within the above range, a decorative film more suitable for decorative processing can be obtained. That is, if the amount of the plasticizer added is less than 5 parts by weight, it may become highly hard and unsuitable for decorative processing, and if the amount of the plasticizer added exceeds 45 parts by weight, it may become soft and the decorative function may not be satisfied. is there.

[Heat stability aid]
The decorative film of the present invention may contain a thermal stability aid. The thermal stability aid may be any one that can enhance the thermal stability of the film by using it in combination with the thermal stabilizer, and the thermal stability aid is usually used in the field of film. Can be used. For example, epoxy compounds, phosphite compounds, polyol compounds and the like can be mentioned. As the thermal stability aid, an epoxy compound is preferably used, and an epoxy resin is more preferably used.

The amount of the thermal stability aid added to the resin layer is preferably 0.1 part by weight to 10 parts by weight, preferably 0.5 parts by weight to 100 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. It is more preferably 10 parts by weight, further preferably 2 to 5 parts by weight. By setting the amount of the heat stability aid added within the above range, it is possible to exert the function as the heat stability aid and further suppress the water absorption bleaching without spending too much cost. That is, if the amount of the heat stability aid added is less than 0.1 parts by weight, the function as the heat stability aid may not be exhibited, and water absorption whitening may not be suppressed. Further, if the amount of the heat stability aid added exceeds 10 parts by weight, the cost may be significantly increased.

[Acrylic processing aid]
The decorative film of the present invention may contain an acrylic processing aid. The acrylic processing aid may be any as long as it can improve the moldability of the film, and as the acrylic processing aid, those usually used in the field of film 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 amount of the acrylic processing aid added to the resin layer is preferably 1 part to 10 parts by weight, preferably 1 part to 4 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. More preferably. By setting the amount of the acrylic processing aid added within the above range, workability can be ensured while suppressing costs. That is, if the amount of the acrylic processing aid added is less than 1 part by weight, it may be difficult to ensure workability, and if it exceeds 10 parts by weight, the cost may be significantly increased.

In the decorative film of the present invention, 0.1 part by weight to 20 parts by weight of a barium-zinc-based heat stabilizer containing a barium compound having an aromatic group is added to 100 parts by weight of the polyvinyl chloride resin. It is preferable to have a resin layer containing 0.1 part by weight to 10 parts by weight of an epoxy resin and 1 part to 10 parts by weight of an acrylic processing aid. More preferably, the decorative film of the present invention contains 1 part by weight of a barium-zinc-based heat stabilizer containing a barium compound having an aromatic group with respect to 100 parts by weight of the polyvinyl chloride-based resin. It has a resin layer containing 0.5 to 10 parts by weight of an epoxy resin and 1 to 4 parts by weight of an acrylic processing aid. By setting the addition amount of each component within the above range, the water absorption and whitening of the decorative film can be further suppressed, and the manufacturing cost of the decorative film can be suppressed.

[Other additives]
As described above, the decorative film of the present invention can contain an epoxy resin as a heat stability aid. However, the film containing the epoxy resin may turn yellow. In order to suppress this, when an epoxy resin is contained, etc., the decorative film of the present invention is made to contain an initial adhesion inhibitor, an ultraviolet absorber (light stabilizer), etc. to obtain a colorless and transparent film. Is preferable.

Further, various additives may be added in an appropriate amount to the decorative film of the present invention, if necessary. 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. Can be mentioned.

[First arrival preventive agent]
The decorative film of the present invention may contain an initial adhesion inhibitor (also referred to as an initial colorant inhibitor). The initial adhesion inhibitor may be any as long as it can suppress coloring in the initial stage of the film, and those usually used in the field of film can be used.

Examples of the first-attachment preventive agent include AP-614 manufactured by ADEKA CORPORATION. AP-614 manufactured by ADEKA CORPORATION can also be used as a heat stabilizer by using it in combination with a barium-zinc-based heat stabilizer containing a barium compound having an aromatic group.

The amount of the initial adhesion inhibitor added to the resin layer is preferably 0.5 parts by weight to 1.6 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin.

[UV absorber]
The decorative film of the present invention may contain an ultraviolet absorber. The ultraviolet absorber may be any as long as it can absorb ultraviolet rays, and as the ultraviolet absorber, those usually used in the field of film can be used, for example, a benzophenone-based ultraviolet absorber or benzo. A triazole-based UV 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. 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 amount of the ultraviolet absorber added to the resin layer 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.

Next, the layer structure of the decorative film and the manufacturing method will be described.
The thickness of the decorative film of the present invention is preferably 150 μm to 500 μm, more preferably 200 μm to 400 μm. If the thickness of the decorative film is less than 150 μm, the decorative film may become too thin and the base may be transparent when the film is attached to the base material. If the thickness of the decorative film exceeds 500 μm, the followability of the decorative film may be insufficient when it is attached to the base material.

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

The pressure-sensitive adhesive layer is not particularly limited as long as it has a pressure-sensitive adhesive function (pressure-sensitive adhesiveness), and specifically contains a pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. Things 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 may be printed. Printing on the decorative film can be performed by, for example, inkjet printing, gravure printing, screen printing, rotary screen printing, flexo printing, offset printing, electrostatic printing, or the like.

The thickness of the pressure-sensitive adhesive layer is preferably 10 μm or more and 60 μm or less. A more preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 20 μm, and a more preferable upper limit is 50 μm.

[Separator]
The decorative film of the present invention preferably further has a separator. The separator is not particularly limited as long as the surface to be attached to the pressure-sensitive adhesive layer is subjected to a mold release treatment. Examples of the separator include a release film and a release paper. FIG. 1 is a schematic cross-sectional view showing an example of a decorative film of the present invention. As shown in FIG. 1, in the decorative film 1a, it is more preferable that the resin layer 10, the adhesive layer 20, and the separator 30 are laminated in this order from the surface. With such an embodiment, the resin layer 10 can be easily attached to the base material via the pressure-sensitive adhesive layer 20.

As the release film and the release paper, those usually used in the field of film 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 release film or the release paper may be surface-treated only on the surface on the pressure-sensitive adhesive layer side.

The decorative film may have a protective film layer. As the protective film, those usually used in the field of film can be used. Examples of the protective film include polyethylene terephthalate resin, polypropylene resin, polycarbonate resin and the like.

The method for producing the decorative film is not particularly limited, but for example, the resin layer can be formed by melt-kneading the polyvinyl chloride resin using a Banbury mixer or the like and then performing calendar processing or the like. .. When the decorative film has an adhesive layer, the adhesive layer can be a release film or a release paper by using a general-purpose film forming apparatus such as various coating devices, bar coats, doctor blades, or a film forming method. It can be formed by applying the above pressure-sensitive adhesive composition on top and then drying. By laminating the pressure-sensitive adhesive layer on the resin layer, a decorative film used for decorative molding can be obtained.

Next, the decorative molded article of the present invention will be described. The decorative molded product of the present invention comprises 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. There is. 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 release film or the decorative film from which the release paper is 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 method of applying the decorative film is, for example, a release film or a decorative film from which the release paper has been peeled off is laminated on a base material, and vacuum forming, pressure molding, vacuum / pressure molding, in-mold molding, film insert molding, etc. Examples thereof include a method of construction using a method such as laminating. Of these, it is preferable to use vacuum / compressed air molding.

Vacuum / compressed air forming is also referred to as TOM (Three dimension Overlay Method), and can be performed using, for example, a vacuum / compressed air forming apparatus. To explain an example of vacuum / compressed air molding, first, a decorative film obtained by peeling a release film or a release paper from a decorative film and a base material are set in a molding chamber under atmospheric pressure. Next, after the molding chamber is made airtight, vacuum suction is performed using a vacuum tank to put the molding chamber in a vacuum state. Subsequently, while maintaining the vacuum state, the decorative film is softened by heating to a desired molding temperature using a heater. After the base material is brought into contact with the softened decorative film, the vacuum in the molding chamber is released to create an atmospheric pressure state, and compressed air is introduced into the molding chamber from a compressed air tank to make the decorative film a base material. And stick it along its shape. Then, if necessary, the excess film protruding from the base material is trimmed. As a result, it is possible to obtain a decorative molded product in which the decorative film is attached to the base material via an adhesive layer.

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 base material is not particularly limited, but for example, vehicles such as bicycles, motorcycles, automobiles, buses and trains; helmets; ships; aircraft such as airplanes and helicopters; household items such as furniture and home appliances; cabinets and office desks. , Office supplies such as personal computers; wall surfaces, floors, ceilings, roofs, pillars, signs, doors, gates of buildings; or building materials at construction sites, or these parts.

The decorative film of the present invention is a decorative film used for parts and exteriors of motorcycles; exteriors and interiors of four-wheeled vehicles; exteriors of mobile phones, smartphones and information equipment terminals; and housing materials such as kitchens and sanitary. It is preferable that it is a decorative film used for the exterior of a two-wheeled vehicle and the interior of a four-wheeled vehicle, and further preferably it is a decorative film used for the exterior of a two-wheeled vehicle.

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.

[Examples / Comparative Examples]
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)
First, for 100 parts by weight of a polyvinyl chloride resin having an average degree of polymerization of 800, 3.3 parts by weight of a barium-zinc-based heat stabilizer containing a barium compound having an aromatic group and an acrylic processing aid were added. 1.5 parts by weight, impact strength modifier 5.0 parts by weight, stabilizer 0.5 parts by weight, plasticizer (diisononyl phthalate: DINP) 25.0 parts by weight, thermal stability aid 3.0 parts by weight was added, melt-kneaded with a barnary mixer, and then subjected to calendar processing to obtain a decorative film of Example 1. The thickness of the film was 110 μm. In the barium-zinc-based heat stabilizer used in Example 1, the total content (% by weight) of the barium compound having an aromatic group and the zinc compound having an aromatic group is the barium compound having an aliphatic group. And the total content (% by weight) of the zinc compound having an aliphatic group was exceeded.

(Examples 2 to 8)
As shown in Table 1 below, decorative films of Examples 2 to 8 were obtained in the same manner as in Example 1 except that the blending amount was changed.

(Comparative Example 1)
First, for 100 parts by weight of a polyvinyl chloride-based resin having an average degree of polymerization of 800, 4.0 parts by weight of a barium-zinc-based heat stabilizer, 1.5 parts by weight of an acrylic processing aid, and impact strength improvement Add 5.0 parts by weight of pledge, 0.5 parts by weight of stabilizer, 15.0 parts by weight of plasticizer (DINP), 3.0 parts by weight of plasticizer (epoxidized soybean oil), and Banbury mixer. After melt-kneading in, a decorative film of Comparative Example 1 was obtained by calendar processing. The thickness of the film was 110 μm. In the barium-zinc-based heat stabilizer used in Comparative Example 1, the total content (% by weight) of the barium compound having an aliphatic group and the zinc compound having an aliphatic group is the barium compound having an aromatic group. And the total content (% by weight) of the zinc compound having an aromatic group was exceeded.

(Comparative Examples 2 to 4)
As shown in Table 1 below, decorative films of Comparative Examples 2 to 4 were obtained in the same manner as in Comparative Example 1 except that the blending amount was changed.

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

(Evaluation of decorative film)
With respect to the decorative films produced in Examples and Comparative Examples, (1) measurement of water absorption whitening index, (2) evaluation of design change, and (3) evaluation of appearance were performed by the following methods.

(1) Measurement of Water Absorption Whitening Index After immersing the obtained decorative film in water at 40 ° C. for 24 hours, the whiteness WI (water absorption whitening index) of the decorative film is determined by a method according to ASTM E313-96. It 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.

(2) Evaluation of design change Based on the results of the water absorption bleaching index measured above, those having a water absorption bleaching index of 14.0 or less were evaluated as ◯, and those exceeding 14.0 were evaluated as x.

(3) Appearance evaluation The decorative films produced in Examples and Comparative Examples were marked with ◯, and those that could be visually confirmed to be colorless and transparent were marked with x.

The evaluation results of the decorative films of Examples and Comparative Examples are shown in Table 1 below.

From the results of Examples and Comparative Examples, by combining a polyvinyl chloride-based resin and a barium-zinc-based heat stabilizer containing a barium compound having an aromatic group, design changes such as water absorption and whitening can be achieved over a long period of time. It was found that a decorative film that can be suppressed can be obtained.

Further, the decorative film of the example was attached to the base material by the following method to prepare a decorative molded product, and (4) the moldability was evaluated.

(4) Evaluation of Moldability A hot melt adhesive (Hybon 7663, manufactured by Hitachi Kasei Polymer Co., Ltd.) was applied onto a release film so that the thickness of the pressure-sensitive adhesive layer was 40 μm, and this was obtained as described above. The film was transferred to the decorative film to obtain a decorative film provided with an adhesive layer and a release film. Subsequently, the decorative film from which the release film was peeled off was attached to the base material at 120 ° C. to prepare a decorative molded product. The moldability in producing a decorative molded product was evaluated.

The decorative films of Examples 1 to 4 and 6 to 8 were superior in molding processability to the decorative films of Example 5. In particular, the decorative films of Examples 1 and 2 have appropriate elongation and strength in the decorative films, can be attached to the base material without any problem, and have higher molding processability as compared with other examples. Was particularly good at. The decorative films of Examples 3, 4 and 6 to 8 were slightly inferior in strength of the decorative films, but could be attached to the base material without any problem.

1a, 1b: Decorative film 2: Decorative molded product 10: Resin layer 20: Adhesive layer 30: Separator 40: Base material

Claims (8)

Consists of single layer or multiple layers
It has a resin layer containing a polyvinyl chloride-based resin and a barium-zinc-based heat stabilizer.
The barium-zinc-based heat stabilizer is a decorative film containing bis (3-methylbenzoic acid) barium. The decorative film according to claim 1 , wherein the resin layer further contains 5 parts by weight to 45 parts by weight of a plasticizer with respect to 100 parts by weight of the polyvinyl chloride resin. The decorative film according to claim 2 , wherein the plasticizer does not contain a structure derived from a fatty acid. The decorative film according to any one of claims 1 to 3 , wherein the resin layer further contains a heat stability aid. The decorative film according to claim 4 , wherein the thermal stability aid is an epoxy compound. The decorative film according to any one of claims 1 to 5 , wherein the resin layer does not contain a tin-based heat stabilizer. The decorative film further has an adhesive layer and a separator, and
The decorative film according to any one of claims 1 to 6 , wherein the resin layer, the pressure-sensitive adhesive layer, and the separator are laminated in this order. The base material and the decorative film according to any one of claims 1 to 6 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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