JP7387362B2 - Decorative films and decorative molded products - Google Patents

Description

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

Halogen-containing resins such as polyvinyl chloride (PVC) resins tend to undergo thermal decomposition due to dehydrohalogenation during heat molding, so one or more types of heat stabilizers are added to the resin. Measures have been taken to suppress deterioration during the processing process.

For example, in the example of Patent Document 1, for 100 parts by weight of PVC resin, 20 to 65 parts by weight of plasticizer, 0.1 to 5 parts by weight of epoxy resin, 1 to 10 parts by weight of acrylic processing aid, Also, transparent flexible films or sheets to which various stabilizers are added are disclosed.

Here, when a decorative film used for decorating a wall surface or the like gets wet with water due to rain or the like, a change in design may occur, such as a red decorative film turning light pink. That is, the design of the surface of an article decorated with a decorative film may change due to water absorption and whitening of the decorative film.

Such changes in design due to water absorption and whitening can be suppressed by containing 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 intended use, so their uses are limited. In addition, in recent years, the use of chemical substances has been regulated in consideration of the environment, and tin-based heat stabilizers have been listed as being subject to regulation or are expected to be regulated in the future. difficult to use.

The above-mentioned Patent Document 1 discloses a film and sheet with excellent water absorption and whitening resistance, but since the film of the above Patent Document 1 is a soft film, it is not suitable as a decorative film. There was still room for improvement in suppressing changes.

Furthermore, 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 disclose a resin layer containing a polyvinyl chloride resin and a heat stabilizer. A decorative film (sheet) is disclosed in which a barium-zinc 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.

Patent No. 3377754 Japanese Patent Application Publication No. 2018-83899 JP2016-86891A Japanese Patent Application Publication No. 2015-78330 Japanese Patent Application Publication No. 2000-103926

In view of the above, there has been a need for decorative films and decorative molded products 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 that can suppress design changes such as water absorption and whitening over a long period of time.
The present inventors conducted various studies on heat stabilizers used in decorative films and decorative molded products. As a result, by using a barium-zinc heat stabilizer with a specific zinc content and a specific lubricant content as a heat stabilizer added to polyvinyl chloride resin, the water absorption of the film can be improved over a long period of time. The present invention was completed based on the discovery that design changes such as whitening can be suppressed.

The decorative film of the present invention has a resin layer containing a polyvinyl chloride resin, a barium-zinc heat stabilizer, and a plasticizer, and the resin layer contains 100 parts by weight of the polyvinyl chloride resin. 3 to 10 parts by weight of the barium-zinc heat stabilizer and 10 to 45 parts by weight of the plasticizer, and the barium-zinc heat stabilizer contains the barium-zinc 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 lubricant per 100 parts by weight of the heat stabilizer.

Preferably, the resin layer does not contain an epoxy plasticizer.

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

Preferably, the decorative film further includes an adhesive layer and a separator, and the resin layer, the adhesive layer, and the separator are laminated in this order.

The decorative film described above is preferably used for outdoor exterior wall decoration.

The decorative molded product of the present invention includes a base material and the decorative film of the present invention that covers the base material, and the base material and the decorative film are laminated with an adhesive layer interposed therebetween. It is characterized by

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

FIG. 1 is a cross-sectional view schematically showing an example of a decorative film of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which showed an example of the decorative molded product of this invention. FIG. 2 is a schematic diagram for explaining a method for evaluating calendering property in Examples and Comparative Examples.

The decorative film of the present invention is composed of a single layer or multiple layers, and has a resin layer containing a polyvinyl chloride resin, a barium-zinc heat stabilizer, and a plasticizer, and the resin layer includes: 100 parts by weight of the above polyvinyl chloride resin contains 3 to 10 parts by weight of the barium-zinc heat stabilizer and 10 to 45 parts by weight of the plasticizer; 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 lubricant based on 100 parts by weight of the barium-zinc heat stabilizer.

In this specification, "film" has the same meaning as "sheet", and the two are not distinguished by thickness.

As used herein, "X to Y" means "more than or equal to X and less than or equal to Y."

Embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to the forms 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, the decorative film 1a includes a resin layer 10, an adhesive layer 20, and a separator 30 laminated in this order. In this specification, "A and B are stacked" or "A and B are stacked" means that in addition to the case where A and B are in contact, another layer is placed between A and B. Including cases where

[Polyvinyl chloride resin]
The decorative film 1a contains a polyvinyl chloride resin in the resin layer 10. The polyvinyl chloride resin has good elongation when made into a film and is difficult to break, so 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 softens when heated by a dryer or the like.

Examples of the polyvinyl chloride-based resin include homopolymers of vinyl chloride and copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride. Other copolymerizable monomers include, for example, vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and styrene; methyl (meth)acrylate, ethyl (meth)acrylate, ( (meth)acrylic acid alkyl esters such as methyl meth)acrylate; maleic acid diesters such as dibutyl maleate and diethyl maleate; fumaric acid diesters such as dibutyl fumarate and diethyl fumarate; cyanide such as acrylonitrile and methacrylonitrile Vinyl; vinyl halides such as vinylidene chloride and vinyl bromide; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; and the like. These may be used alone or in combination of two or more. In addition, in this specification, "(meth)acrylic acid" represents "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 resins, vinyl chloride homopolymers are preferred because of their excellent dimensional stability.

The average degree of polymerization of the polyvinyl chloride resin is preferably 800 to 1,200. 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 "Testing method for vinyl chloride resins."

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

The barium-zinc heat stabilizer contains 0.5 to 2.5 parts by weight of zinc and 10 to 22 parts by weight of a lubricant, based on 100 parts by weight of the barium-zinc heat stabilizer. The barium-zinc heat stabilizer used in the present invention hardly absorbs water, and can prevent various additives added to polyvinyl chloride resin from absorbing water. Furthermore, since the zinc content is as low as 0.5 to 2.5 parts by weight per 100 parts by weight of the above-mentioned barium-zinc heat stabilizer, the formation of zinc chloride is suppressed and it lasts for a long time. Water absorption and whitening of the film can be suppressed. Furthermore, since the content of the lubricant is 10 to 22 parts by weight with respect to 100 parts by weight of the barium-zinc heat stabilizer, the lubricity is improved and the formation 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, but 0.75 to 2 parts by weight, based on 100 parts by weight of the barium-zinc heat stabilizer. Preferably, the content is .25 parts by weight. By adopting such an aspect, it becomes possible to further suppress water absorption and whitening.

In the above barium-zinc heat stabilizer, the lubricant may be contained in an amount of 10 to 22 parts by weight, but preferably 12 to 20 parts by weight, based on 100 parts by weight of the barium-zinc heat stabilizer. The content is preferably 13 to 15 parts by weight, and more preferably 13 to 15 parts by weight. By adopting such an aspect, it becomes possible to further suppress water absorption and whitening.

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

The decorative film 1a of the present invention contains a barium-zinc heat stabilizer having a specific zinc content and a specific lubricant content in the resin layer 10, thereby suppressing design changes due to water absorption and whitening. is obtained. It is also possible to contain a zinc compound having an aliphatic group or a barium compound having an aliphatic group in a barium-zinc heat stabilizer. It is also possible to contain. The barium-zinc heat stabilizer preferably contains a zinc compound having an aliphatic group.

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

In addition to the barium-zinc heat stabilizer, the resin layer 10 can also contain a heat stabilizer commonly used in the film field. For example, metal organic acid compounds containing lead (Pb), barium (Ba), zinc (Zn), calcium (Ca), tin (Sn), etc. 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 and a transparent semi-hard to hard decorative film can be obtained, and cold impact resistance, weather resistance, scratch resistance, etc. can be improved. The above-mentioned plasticizer may be any one that can make the polyvinyl chloride film easy to process, and those commonly used in the field of polyvinyl chloride films can be used as the above-mentioned plasticizer. For example, phthalic diesters such as octyl phthalate (di-2-ethylhexyl phthalate), dibutyl phthalate, dinonyl phthalate, diisononyl phthalate (DINP), aliphatic dibases such as dioctyl adipate, dioctyl sebacate, etc. Examples include acid diesters, phosphoric acid triesters such as tricresyl phosphate and trioctyl phosphate, and polymeric polyester plasticizers. As the plasticizer, it is preferable to use a polyester plasticizer.

The polyester plasticizer has good compatibility with vinyl chloride resin. Furthermore, the polyester plasticizer has a high molecular weight and is therefore difficult to dissolve and swell in gasoline, compared to the phthalic acid plasticizer that is generally used as a plasticizer for the vinyl chloride resin. Therefore, by using a polyester plasticizer, it is possible to impart flexibility to a polyvinyl chloride film and improve its cold impact resistance. As the polyester plasticizer, for example, Adekasizer PN7535 (manufactured by ADEKA), Adekasizer PN7230 (manufactured by ADEKA), etc. can be used.

The weight average molecular weight of the polyester plasticizer is preferably 2,000 to 6,000. If the weight average molecular weight is less than 2,000, the water absorption whitening resistance may deteriorate, while if the weight average molecular weight exceeds 6,000, the handleability may deteriorate. The weight average molecular weight of the polyester plasticizer is more preferably 3,000 to 5,000.

The weight average molecular weight (Mw) of the polyester plasticizer is measured by GPC (gel permeation chromatography). Note that the measurement conditions are as follows.
Device name: HLC-8120 (manufactured by Tosoh Corporation)
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: Diluted with tetrahydrofuran to 1.5 mg/ml Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 ml/min
Column temperature: 40℃

Preferably, the resin layer 10 does not contain an epoxy plasticizer. Examples of the epoxy plasticizer include epoxidized soybean oil and epoxidized isobutyl fatty acid. If the resin layer contains an epoxy plasticizer, the adhesive may be denatured and its adhesive properties may deteriorate, resulting in insufficient adhesion as a decorative film applied over a wide area (e.g. ^3m2 or more). This is because there is a possibility that

The resin layer 10 contains 10 to 45 parts by weight of the above plasticizer based on 100 parts by weight of the polyvinyl chloride resin. By setting the content of the plasticizer within the above range, a decorative film that is more suitable for decorative processing can be obtained. In other words, if the plasticizer content is less than 10 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin, it becomes too hard and may not be suitable for decorative processing. If it exceeds the amount, the plasticizer may bleed onto the surface of the decorative film or become soft, making it impossible to satisfy the decorative function. Note that the content of the plasticizer is preferably 20 to 30 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

[Thermal stability aid]
The resin layer 10 may further contain a thermal stability aid. The above-mentioned thermal stability aid may be any substance that can enhance the thermal stability of the film when used in combination with the above-mentioned barium-zinc-based heat stabilizer, and the technical field to which the present invention pertains (film field) Those commonly used can be used. Examples include phenolic antioxidants, β-diketones, phosphite compounds, polyol compounds, and among them, phenolic antioxidants are preferably used.

The resin layer 10 preferably contains 0.1 to 4 parts by weight, and preferably 0.5 to 3 parts by weight, of the thermal stability aid based on 100 parts by weight of the polyvinyl chloride resin. More preferably, it is contained in an amount of 0.5 to 2 parts by weight. When the content of the thermal stability aid is within the above range, it is possible to exhibit the function as a heat stability aid and further suppress whitening due to water absorption without incurring too much cost. That is, if the content of the thermal stability aid is less than 0.1 part by weight with respect to 100 parts by weight of the above-mentioned polyvinyl chloride resin, the function as a heat stability aid may not be exhibited, and water absorption and whitening may be suppressed. It may not be possible to do so. Furthermore, if the content of the thermal stability aid exceeds 4 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, the cost may increase significantly.

[Acrylic processing aid]
The resin layer 10 may further contain an acrylic processing aid. The acrylic processing aid may be anything that can improve the moldability of the decorative film, and the acrylic processing aid may include those commonly used in the technical field (film field) to which the present invention pertains. Can be used. For example, one type of (meth)acrylic acid ester can be used, or two or more types can be copolymerized.

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

The resin layer 10 preferably contains 1 to 10 parts by weight, and more preferably 1 to 6 parts by weight, of the acrylic processing aid based on 100 parts by weight of the polyvinyl chloride resin. By setting the content of the acrylic processing aid within the above range, processability can be ensured while reducing costs. That is, if the content of the acrylic processing aid relative to 100 parts by weight of the polyvinyl chloride resin is less than 1 part by weight, it may be difficult to ensure processability, and if it exceeds 10 parts by weight, the It may be costly. Examples of acrylic processing aids include Metablane P-530 and P-1901 manufactured by Mitsubishi Chemical Corporation.

[Other additives]
The resin layer 10 can contain various additives as long as they are within the range that provides the effects of the present invention. Examples of the above additives include impact strength modifiers, lubricants, antioxidants, colorants, flame retardants, antistatic agents, adjuvants, reinforcing agents, antifogging agents, fillers, diluents, antifungal agents, Examples include light stabilizers, ultraviolet absorbers, modifiers, etc., and those commonly added to polyvinyl chloride resins can be used.

[Ultraviolet absorber]
The resin layer 10 may contain an ultraviolet absorber. The UV absorber may be any UV absorber as long as it has the ability to absorb UV rays, and those commonly used in the technical field (film field) to which the present invention pertains can be used. As the ultraviolet absorber, for example, a benzophenone-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber can be used. From the viewpoint of obtaining a colorless and transparent film with suppressed yellow tinge, benzophenone-based ultraviolet absorbers are preferably used. Specifically, examples of benzophenone-based ultraviolet absorbers include ADEKA 1413 manufactured by ADEKA Corporation, and examples of benzotriazole-based ultraviolet absorbers 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 based on 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 will be insufficient, the color development during printing (the clarity of the design) may decrease, and the decorative film will become too flexible, resulting in poor workability. Sometimes. Furthermore, the weather resistance is also poor. On the other hand, if it exceeds 500 μm, the followability to the base material may deteriorate. Furthermore, flexibility may be poor and the texture of the decorative film may become 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 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 adhesive layer 20 is not particularly limited as long as it has an adhesive function (pressure-sensitive adhesive property), and for example, it may contain an adhesive such as an acrylic adhesive, a rubber adhesive, or a silicone adhesive. Can be mentioned. Among these, acrylic pressure-sensitive adhesives are preferably used because they are excellent in adhesiveness, processability, heat aging resistance, moisture aging resistance, and weather resistance, and are relatively inexpensive.

The decorative film 1a may have a printed layer. The printed layer is preferably laminated on the opposite side of the resin layer 10 of the decorative film 1a from the adhesive layer 20. The printing layer is formed by printing on the resin layer 10 of the decorative film 1a, and can be formed by, for example, inkjet printing, gravure printing, screen printing, rotary screen printing, flexo printing, offset printing, electrostatic printing, etc. can. In addition, 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 adhesive layer 20 is not particularly limited, but is preferably 10 to 60 μm, more preferably 20 to 50 μm.

[separator]
The decorative film 1a of the present invention may further include a separator 30. The separator 30 is not particularly limited as long as the surface to be adhered to the adhesive layer 20 has been subjected to a mold release treatment.

For the separator 30, a release film or release paper commonly used in the technical field (film field) to which the present invention pertains can be used. Examples of the release film include a polyethylene terephthalate (PET) film whose surface is coated with a silicone-based, alkyd-based, or fluorine-based release agent. Examples of the release paper include those obtained by coating the surface of high-quality paper with a silicone-based, alkyd-based, or fluorine-based release agent.

The decorative film 1a may have a protective film layer on the opposite side of the resin layer 10 from the adhesive layer 20. As the protective film layer, those commonly used in the technical field (film field) to which the present invention pertains can be used, and are formed of, for example, polyethylene terephthalate resin, polypropylene resin, polycarbonate resin, etc.

That is, the decorative film of the present invention preferably has a resin layer, an adhesive layer, and a separator laminated in this order, and further includes a printed layer on the opposite side of the resin layer 10 from the adhesive layer 20. , a protective layer, a primer layer, and the like.

As for the method for manufacturing the decorative film 1a, for example, the resin layer 10 is prepared by melt-kneading the polyvinyl chloride resin using a Banbury mixer or the like to obtain a polyvinyl chloride resin composition, and then melting and kneading the polyvinyl chloride resin composition using a Banbury mixer or the like. A film can be formed by calendering a vinyl resin composition. By calendering, even a thin film can be produced with excellent thickness accuracy.

The calender format used in the above calendering process is not particularly limited, and conventionally known formats such as an inverted L-shape, a Z-shape, an upright 2-shape type, an L-shape, and a slanted 3-shank type can be adopted.

When the decorative film 1a has an adhesive layer 20, the adhesive layer 20 is coated with a separator 30 (release film or It can be formed by coating an adhesive composition on a release paper (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 calendering or the like.

Next, the decorative molded product of the present invention will be explained. The decorative molded product of the present invention includes a base material and the decorative film of the present invention that covers the base material, and the base material and the decorative film are laminated with an adhesive layer interposed therebetween. FIG. 2 is a schematic cross-sectional view showing an example of the 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 a decorative film 1b. The base material 40 and the decorative film 1b are bonded to each other via the adhesive layer 20.

The above decorative film is used by attaching the decorative film from which the separator 30 has been removed to a base material. Since the decorative film of the present invention also follows three-dimensional curved surfaces, it can be suitably used for base materials having three-dimensional curved surfaces.

The above-mentioned decorative film can be applied at room temperature, or can be applied while being heated with a hair dryer or the like. In this case, it can be attached to the substrate by hand or using a squeegee. Moreover, as a construction method for the above-mentioned decorative film, a method commonly used in the technical field to which the present invention pertains can be adopted. Alternatively, the decorative film from which the separator has been removed can be stacked on a base material and applied using methods such as vacuum forming, pressure forming, vacuum/pressure forming, in-mold forming, film insert molding, and lamination.

The material of the base material is not particularly limited, and examples include resins such as polycarbonate resin, acrylic resin, and styrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin); metals such as iron, copper, and aluminum. ;Alloys etc. are mentioned.

Although the use of the decorative film of the present invention is not particularly limited, it is preferably used for interior and exterior wall coverings, for example. Specific examples include decorative boards (wall covering materials) attached to walls, interior doors, closet and kitchen doors, furniture, flooring, and other interior materials. In addition, it is suitably used for wall coverings around water areas 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 using a method that is simpler and safer than painting.

The decorative film of the present invention can be used, for example, to decorate the surface of a base material, protect it, advertise it, and the like. In addition, characters, designs, etc. can be transferred onto the surface of the decorative film, and the film can be used as an advertisement by pasting it on the base material.

Further, the decorative film of the present invention is preferably applied to a substrate having a relatively wide area, for example, it is preferably applied to a substrate having an area of 1 to 3.5 m ² . It is preferable that the decorative film of the present invention does not contain an epoxy plasticizer in the resin layer. If the decorative film does not contain an epoxy resin, the adhesive strength may decrease even when used on a relatively wide base material. This is because it is difficult.

[Example/Comparative example]
EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
For 100 parts by weight of polyvinyl chloride resin with an average degree of polymerization of 800, 4.0 parts by weight of a barium-zinc heat stabilizer (QL-1133) and a polyester plasticizer with a weight average molecular weight of 4500 (Adeka 24.0 parts by weight of Sizer PN7535 (manufactured by ADEKA) were added and melt-kneaded using a Banbury mixer to prepare a vinyl chloride resin composition. Next, the vinyl chloride resin composition was fed into a 24-inch calender with four inverted L-shaped rolls, and was heated to a thickness of 80 μm under the conditions of a calender roll equipment temperature of 170 to 190°C and a resin composition temperature of 180 to 210°C. The decorative film of Example 1 was obtained by calender molding. In addition, in the barium-zinc heat stabilizer (QL-1133) used in Example 1, the content of zinc is 0.75 to 2.25 parts by weight per 100 parts by weight of the heat stabilizer, and the content of lubricant is 0.75 to 2.25 parts by weight. The amount was 13-15.

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

(Example 2)
A decorated 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 one shown in Table 2 below.

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

(Comparative example 1)
A decorated 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 one shown in Table 2 below.

(Comparative example 2)
To 100 parts by weight of polyvinyl chloride resin, 3.5 parts by weight of epoxidized soybean oil (W100: manufactured by DIC) was added, and the content of 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 Comparative Example 1 except that the amount was changed to .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 content of plasticizer and epoxidized soybean oil was changed to the content shown in Table 2 below. A decorated film of Comparative Example 3 was obtained in the same manner as in Example 2.

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

(Comparative Examples 5 and 6)
Decorated 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 to 9)
Decorated 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 heat stabilizer was changed to the content shown in Table 2 below.

The materials used in the 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 processability, (2) water absorption and whitening resistance, (3) adhesive strength, and (4) weather resistance using the following methods. Ta.

(1) Calendarability Calenderability 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 calendering 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 at a roll temperature of 180°C and a roll gap (distance between rolls) of 0.2 mm, and After kneading the resin composition 52 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 with a thickness of 0.2 mm P1. was identified. Thereafter, a horizontal line passing through the center P0 of the roll 51b was defined as a reference line L0, and an angle θ between this reference line L0 and a line segment L1 connecting the film peeling position P1 and the center P0 of the roll 51b was calculated. . Then, calendering workability was evaluated based on the above value of θ. Note that θ is a positive value when the position P1 is located above the reference line L0, and is a negative value when the position P1 is located below the reference line L0. In addition, in this evaluation, the smaller the absolute value of the value of θ (the closer it is to 0°), the better the calendering property is.

(Evaluation criteria for calendering workability)
If θ (absolute value) is between -10° and 20°, it will be evaluated as "○".
If θ (absolute value) is greater than 20° and less than 50°, the evaluation is “△”.
If θ (absolute value) is larger than 50°, it is evaluated as “×”.
If the angle is 60° or more, it is considered "unprocessable".

(2) Water absorption whitening resistance After immersing the decorative films obtained in the Examples and Comparative Examples in water at 40°C for 4 days (96 hours), the whiteness of the decorative films was measured in accordance with ASTM E313-96. WI (water absorption whitening index) was measured. Note that whiteness WI is the degree of "whiteness" of an object, and if a perfectly diffuse reflective surface (ideal white) is 100, the whiteness value increases as it moves away from this ideal white. It gets lower. Note that 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, it is evaluated as "○".
If the HAZE difference is between 3 and less than 7, it will be evaluated as "△".
If the HAZE difference is 7 or more, it is evaluated as "x".

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

(Measurement of adhesive strength)
Measured according to JIS Z0237. Specifically, the decorative film with a separator was cut into 25 mm width x 150 mm length, and then the paper separator was peeled off to obtain a decorative film with the adhesive layer exposed. Then, while the surface of the decorative film on the pressure-sensitive adhesive layer side is in contact with the outermost surface of the decorative film, a pressure roller having a mass of 2 kg is moved back and forth once on the base film to apply pressure. A decorative film was pasted on. Then, after leaving it for 24 hours at a temperature of 23°C and a relative humidity of 50%, the adhesive strength was determined when the decorative film was peeled off from the outermost surface at a pulling speed of 300 mm/min and a pulling angle of 180°. (Unit: N/25mm) was measured. The adhesive strength was measured twice for each of the Examples and Comparative Examples, and the average of the two measured values 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 the Examples and Comparative Examples were placed in an accelerated weather resistance tester (Sunshine Weather Meter) for 2000 hours. After the test was completed, it was visually confirmed whether or not the surface of the decorative film had changed color.

(Lightfastness 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, it was found that a heat stabilizer for polyvinyl chloride resin was obtained by combining a polyvinyl chloride resin and a barium-zinc heat stabilizer having a specific zinc content and a specific lubricant content. By setting the content and plasticizer content to specific amounts, a decorative film with excellent water absorption and whitening resistance and excellent performance required for a decorative film (processability, adhesive strength, weather resistance) can be obtained. I understand.

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 (8)

It has a resin layer containing a polyvinyl chloride resin, a barium-zinc heat stabilizer having an aliphatic group , and a plasticizer,
The resin layer contains 3 to 10 parts by weight of the barium-zinc heat stabilizer having an aliphatic group and 10 to 45 parts by weight of the plasticizer, based on 100 parts by weight of the polyvinyl chloride resin. including;
The barium-zinc heat stabilizer having an aliphatic group contains 0.5 to 2.5 parts by weight of zinc per 100 parts by weight of the barium-zinc heat stabilizer having an aliphatic group; 10 to 22 parts by weight of a lubricant ,
A decorative film characterized in that the barium-zinc heat stabilizer having an aliphatic group contains a zinc compound having an aliphatic group and does not contain a zinc compound having an aromatic group. 2. The decorative film according to claim 1, wherein the barium-zinc heat stabilizer having an aliphatic group does not contain a barium compound having an aromatic group. The plasticizer is a polyester plasticizer,
3. The decorative film according to claim 1, wherein the content of the polyester plasticizer is 20 to 30 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. 4. The decorative film according to claim 1, wherein the resin layer does not contain an epoxy plasticizer. The decorative film according to any one of claims 1 to 4, wherein the resin layer has a thickness of 50 to 500 μm. The decorative film further includes an adhesive layer and a separator, and the resin layer, the adhesive layer, and the separator are laminated in this order. 5. The decorative film according to any one of 5 . The decorative film according to any one of claims 1 to 6 , which is used for interior and exterior wall coverings. comprising a base material and the decorative film according to any one of claims 1 to 7 that covers the base material,
The decorative molded product is characterized in that the base material and the decorative film are laminated with an adhesive layer interposed therebetween.

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