JP7052275B2 - Cosmetic sheets and materials - Google Patents

Description

The present invention relates to a decorative sheet for an exterior material and an exterior decorative material using the decorative sheet.

Conventionally, as exterior building materials such as window frames, doors, gates, handrails and fences, interior building materials such as wall materials, floor materials and ceiling materials, and surface decorative materials for furniture such as tans, desks and cupboards, polyvinyl chloride, etc. A decorative sheet for exterior materials has been often used, in which a pattern is printed on a vinyl chloride resin sheet made of the above resin, embossed, and a plastic film having good weather resistance is laminated on the pattern (for example, patent). See Documents 1 and 2). These decorative sheets using a vinyl chloride resin sheet as a base material have excellent processability, thermoformability, embossing and the like. In addition, since it is excellent in transparency, weather resistance, and heat resistance, it is useful as the above-mentioned exterior building material and interior building material.

The above-mentioned decorative sheet for exterior material is usually attached to an adherend by wrapping or the like, but the invention of Patent Document 2 has the following problems in the wrapping-processed decorative sheet for exterior material. Is the solution.

That is, the wrapping-processed exterior decorative material causes repeated dimensional shrinkage and deterioration of the decorative sheet and the adherend base material due to outdoor exposure, and as a result, the end face of the decorative sheet that should have been closely attached at the beginning. Are separated from each other, and the adherend base material is exposed from the seam, which impairs the aesthetic effect of the decorative material for exterior use. Also, when the exposed adherend base material is a metal such as aluminum or iron, the adherend base material Is corroded, resulting in a decrease in strength and a decrease in the life of the decorative material for exterior use. Then, once the end portion of the decorative sheet is peeled off and corrosion, rust, etc. occur, the decorative sheet is further peeled off and deterioration is promoted.

In the invention described in Patent Document 2, in order to solve such a problem, the decorative sheet has a surplus portion when the decorative sheet is surrounded and attached around the adherend base material, and the decorative sheet has a surplus portion. The seam at the end of the sheet is overlapped with the surplus portion to form an exterior decorative material.

Special Publication No. 58-14321 Japanese Unexamined Patent Publication No. 6-297615

However, even if the exterior decorative material is wrapped with a decorative sheet having such a surplus portion and the seams at the ends are overlapped and attached, the inside of the decorative sheet for the exterior material is still after the rain in summer. Repeated exposure of the remaining water to direct sunlight for a long period of time may cause swelling on the surface of the decorative sheet, resulting in poor appearance, and such swelling impairs the design, especially the overlapping part. It also caused the peeling of the decorative sheet and significantly reduced the durability of the decorative sheet.
The present invention has been made under such circumstances, and the appearance is poor due to the occurrence of swelling caused by repeated exposure of the moisture remaining in the decorative sheet for exterior materials to direct sunlight after rainfall, especially after rain in summer. It is an object of the present invention to provide a decorative sheet for an exterior material that can suppress the above.

As a result of diligent studies, the present inventors have determined that in a decorative sheet having a plasticizer-containing vinyl chloride resin base sheet and a surface protective layer, the moisture permeability of the resin base sheet is kept below a certain value. , The present invention has been completed by finding that the above problems can be solved.

That is, the present invention is described below.
[1] A decorative sheet having a plasticizer-containing vinyl chloride-based resin base material sheet and a surface protective layer made of a transparent acrylic resin film on the surface of the vinyl chloride-based resin base material sheet, wherein the vinyl chloride-based resin base material is provided. A decorative sheet for exterior materials having a moisture permeability of 38 g / ^m for 2.24 hours or less as measured in accordance with the JIS Z0208: 1976 cup method of the sheet.
[2] An exterior decorative material obtained by attaching the decorative sheet for exterior material according to the above [1] and an adherend base material via an adhesive layer.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a decorative sheet for exterior materials that can suppress appearance defects due to swelling caused by repeated exposure of moisture remaining in the decorative sheet for exterior materials after rainfall in summer to direct sunlight. can.

It is a conceptual diagram which shows the cross section of the decorative sheet for exterior materials of this invention. It is a conceptual diagram which shows the cross section of the exterior decorative material of this invention.

The decorative sheet of the present invention is a decorative sheet for exterior materials having a plasticizer-containing vinyl chloride resin base sheet and a surface protective layer made of a transparent acrylic resin film on the surface thereof, and is preferably the resin base sheet. It is a decorative sheet having a pattern layer on the surface side of the (see FIG. 1).
Further, the decorative sheet is suitably used as an exterior decorative material attached to a hard adherend base material via an adhesive layer (see FIG. 2).

As described above, the decorative sheet for exterior materials may cause poor appearance due to the occurrence of swelling caused by repeated exposure of the moisture remaining in the decorative sheet for exterior materials to direct sunlight after rain in summer.

The present inventor has investigated the cause of the generation of bubbles that cause such swelling, and both the plasticizer-containing vinyl chloride resin base sheet and the acrylic resin surface protective layer of the decorative sheet for exterior materials have some moisture permeability. Therefore, during and after rainfall in the summer, moisture permeates through these plastic sheets and films, and then the remaining moisture is heated by exposure to direct sunlight and vaporizes at the interface between both sheets (films). It was presumed that the sheet (film) was peeling off and swelling was occurring.
In addition, since the acrylic resin surface protective layer is an outer layer and is thin, it is released even if it has high hygroscopicity, and moisture does not easily accumulate. However, the plasticizer-containing vinyl chloride resin base sheet has an acrylic moisture absorption of polyvinyl chloride. Since it is lower than the hygroscopicity of the resin and is inside, it is difficult for moisture to enter and be retained, but it is thought that it is difficult for the contained moisture to escape due to its thickness.
In the wrapping process in which the seams at the ends of the decorative sheet are overlapped and attached, moisture invades the inside of the decorative sheet from the end of the excess portion of the decorative sheet or from the poorly adhered portion of the seam, and vinyl chloride. It was presumed that the moisture absorption and water absorption of the based resin base sheet became large and the moisture was hard to escape, so that the water vapor swelled easily at the interface with the acrylic resin surface protective layer.

Therefore, as a method for suppressing the occurrence of swelling, the present inventor has decided to lower the moisture permeability of the plasticizer-containing vinyl chloride resin base material sheet to make it more difficult for water to enter and to be retained. Specifically, by setting the moisture permeability of the vinyl chloride resin base material sheet measured in accordance with the JIS Z0208: 1976 cup method to 38 g / ^m for 2.24 hours or less, a constant temperature bath of 60 ° C. hot water was placed for 3 weeks. It was confirmed that the generation of swelling bubbles in the decorative sheet could be suppressed in the immersing acceleration test. That is, it is considered that a decorative sheet for exterior materials was produced in which the occurrence of swelling caused by repeated exposure of the moisture remaining in the decorative sheet for exterior materials after rainfall in summer to direct sunlight was suppressed.

Hereinafter, each component of the decorative sheet of the present invention will be described in detail with reference to FIGS. 1 and 2. However, the present invention is not limited to the following forms.

The vinyl chloride resin base sheet used for the decorative sheet of the present invention has a moisture permeability of 38 g / ^m for 2.24 hours or less as measured according to the JIS Z0208: 1976 cup method. When the moisture permeability is 38 g / ^m for 2.24 hours or less, the generation of swelling bubbles in the decorative sheet can be suppressed. The moisture permeability of the vinyl chloride resin base material sheet is preferably 30 g / ^m for 2.24 hours or less, and more preferably 25 g / ^m for 2.24 hours or less.
There is no lower limit to the moisture permeability of the vinyl chloride resin base sheet from the viewpoint that the generation of swelling bubbles can be suppressed, but as will be described later, the moisture permeability of the vinyl chloride resin base sheet changes depending on the plasticizer. Therefore, reducing the moisture permeability reduces the amount of plasticizer, and the moisture permeability should be 15 g / ^m for 2.24 hours or more from the viewpoint of maintaining the degree of processability as a base sheet. It is preferably ²⁰ g / m for 2.24 hours or more, more preferably.

As the resin of the vinyl chloride resin base sheet used in the present invention, a polyvinyl chloride resin having good processability, thermoformability, etc., excellent transparency, weather resistance, heat resistance, and low cost is most preferable. ..

As the vinyl chloride resin, the following copolymer obtained by copolymerizing a vinyl chloride monomer can also be used.
Examples of the monomer copolymerizable with the vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid esters such as methyl acrylate and butyl acrylate; and methacrylate esters such as methyl methacrylate and ethyl methacrylate; butyl malate and the like. Maleic acid esters such as diethyl malate; Fumaric acid esters such as dibutyl fumarate and diethyl fumarate; Vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; Vinyl cyanide such as acrylonitrile and methacrylonitrile Olefins such as ethylene, propylene, butylene and styrene; Dienes such as isoprene and butadiene; Vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides; Allyl phthalates such as diallylphthalate , Etc. can be mentioned. These monomers may be used alone or in combination of two or more.

Further, as the vinyl chloride resin, a graft copolymer obtained by grafting a vinyl chloride monomer to the following polymer can also be used.
As the polymer to which the vinyl chloride monomer is grafted, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl acrylate-carbon monoxide copolymer , Ethylene-methylmethacrylate copolymer, ethylene-propylene copolymer and the like.

The average degree of polymerization of the vinyl chloride resin is preferably 500 to 4000, more preferably 700 to 3900, and even more preferably 1000 to 3800. When the average degree of polymerization is within the above range, excellent mechanical strength and excellent moldability can be obtained. The average degree of polymerization is an average degree of polymerization measured in accordance with JIS K6721.

A plasticizer is added to the vinyl chloride resin used as the resin base sheet in order to improve workability. The plasticizer is not particularly limited as long as it is compatible with the vinyl chloride resin, and is, for example, dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (Plasticizer). DIDP), phthalic acid-based plasticizers such as diundecyl phthalate (DUP); adipic acid-based plasticizers such as dibutyl adipate; phosphate-based plasticizers such as tributyl phosphate, tricresyl phosphate, triphenyl phosphate; Trimerit Trimellitic acid-based plasticizers such as tributyl acid and trioctyltrimellitic acid; various known polyester-based plasticizers such as adipic acid-based polyester; citrate esters such as acetyltributylcitrate and acetyltrioctylcitrate; and the like can be mentioned. .. These plasticizers may be used alone or in combination of two or more.

The content of the plasticizer is preferably 23 to 50 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. By setting the content of the plasticizer to 23 parts by mass or more, the vinyl chloride resin can be made flexible and the moisture permeability of the resin base sheet can be increased. On the other hand, when it is 50 parts by mass or less, the plasticizer does not bleed out, which is preferable. From the above viewpoint, the content of the plasticizer is more preferably 25 to 35 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

The thickness of the vinyl chloride resin base material sheet is preferably 80 to 180 μm. When it is 80 μm or more, it is usually used for various uneven patterns such as wood grain conduit groove, cloth texture, sand grain, satin finish, hairline, granite plate surface embossed surface, and leather grain used for this kind of decorative material. In the range, it is advantageous in that the influence on the back surface is small even in the embossing with a deep plate depth, and when it is 180 μm or less, it is advantageous in terms of bending workability such as wrapping. From the above viewpoint, the thickness of the vinyl chloride resin base material sheet is more preferably in the range of 90 to 160 μm, further preferably in the range of 100 to 140 μm.

The decorative sheet 10 of the present invention further has a surface protective layer 13 on the surface side of the resin base sheet 11. The surface protective layer plays a role of protecting the resin base material sheet and also protecting the pattern layer 12 described later.
The surface protective layer in the decorative sheet of the present invention is an acrylic resin film because it is highly transparent from the viewpoint of designability, has high weather resistance and durability, and has high adhesiveness to the resin base sheet and the pattern layer. Is used.
Examples of the acrylic resin constituting the acrylic resin film include polymethyl methacrylate, a methyl methacrylate-ethyl methacrylate copolymer, and a butyl methacrylate-methyl methacrylate copolymer. Further, it is also preferable to use an acrylic resin matrix in which particles composed of a crosslinked rubber core and a graft polymer shell are dispersed in an acrylic resin matrix having improved brittleness and fragility of the acrylic resin to improve processability and weather resistance. Hereinafter, the acrylic resin having such a form is also referred to as "acrylic resin-based core-shell polymer".

In the present invention, the acrylic resin film used as the surface protective layer is JIS Z0208 so that the residual moisture derived from the acrylic resin film does not evaporate at the interface between the resin base sheet and the surface protective layer to generate swelling bubbles. : It is preferable that the moisture permeability measured according to the 1976 cup method is ²⁰⁰ g / m for 2.24 hours or less. The moisture permeation is ^more preferably 180 g / ^m for 2.24 hours or less, and further preferably 130 g / m for 2.24 hours or less.

The thickness of the surface protective layer is preferably in the range of 20 to 100 μm. When the thickness is 20 μm or more, the resin base sheet and the pattern layer can be sufficiently protected, and the bleed-out of the plasticizer of the vinyl chloride resin used as the resin base sheet can be sufficiently prevented. On the other hand, when the thickness of the surface protective layer is 100 μm or less, the bending processability such as the wrapping process of the decorative sheet is not hindered.
From the above viewpoint, the thickness of the surface protective layer is more preferably in the range of 30 to 80 μm, further preferably in the range of 40 to 70 μm.

The decorative sheet 10 of the present invention can have a pattern layer 12 between the resin base sheet 11 and the surface protective layer 13. The pattern layer is for imparting design to the decorative sheet. The pattern layer is formed, for example, by printing various patterns using ink and a printing machine. The patterns include wood grain patterns, stone patterns that imitate the surface of rocks such as marble patterns (for example, travertine marble patterns), fabric patterns that imitate cloth textures and cloth-like patterns, leather squeezing (texture) patterns, and tiled patterns. There are brick patterns, letters, figures, etc. These patterns are formed by various printing methods such as ordinary gravure printing, offset printing, silk screen printing, flexographic printing, and ink jet printing.
Further, a colored layer (solid layer) formed with a single color may be provided over the entire surface, or may be combined with the above-mentioned pattern layer.
The thickness of these pattern layers and the like is usually in the range of 1 to 5 μm.

The decorative material 20 obtained by attaching the decorative sheet 10 of the present invention to the adherend base material 15 via the adhesive layer 14 on the resin base material sheet 11 side is also within the scope of the present invention.
The adhesive constituting the adhesive layer is not particularly limited as long as it can adhere the resin base material sheet of the present invention to the adherend base material, but a solvent-based adhesive is preferable from the viewpoint of adhesiveness. Specifically, phenol-based resin, vinyl acetate-based resin, vinyl chloride-based resin, cellulose-based resin such as nitrocellulose, thermoplastic, two-component curable type, or moisture-curable type urethane resin, epoxy resin, solvent-based Examples thereof include emulsions of vinyl acetate resin and acrylic resin.
Further, a material in which residual solvent does not easily remain is preferable, and a one-component curing type or a two-component curing type may be used.

As the adherend base material 15, various shapes such as a flat plate, a curved plate, a columnar body having various cross-sectional shapes used for a handrail and a window frame, and the like are used depending on the intended use.
When the adherend is made of resin, the resin constituting the adherend may be a polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate-isophthalate copolymer, polyallylate; or ethylene-vinyl alcohol. Copolymer; Polymethylene resin; Polycarbonate resin; Polyimide resin; Polystyrene resin; Polyamide resin; ABS (Acrylonitrile-butadiene-styrene copolymer) resin; AS (Acrylonitrile-styrene copolymer); Cellulous resin; Polyamide resin, etc. However, a hard one is preferable. The adherend base material may be a single layer made of these resins, or may be a laminate of two or more layers made of two or more different resin layers selected from these resins.
When the adherend base material is made of metal, the metal used is iron, an iron alloy such as carbon steel or stainless steel, an aluminum alloy such as aluminum or duralumin, copper, brass, titanium or the like. When the adherend is made of wood, the wood used is veneer, plywood, particle board, fiber slab, laminated lumber, etc. made of various tree species such as cedar, cypress, oak, pine, lauan, and teak. When the adherend base material is a ceramic-based inorganic material, examples thereof include cement-based materials, calcium silicate, ceramics, glass, and various ceramics.

The decorative sheet and decorative material of the present invention are produced, for example, by the following methods.
For example, in the case of the decorative sheet shown in FIG. 1, the pattern layer 12 is first formed on the resin base sheet 11 by a printing method or the like. Next, the surface protective layer 13 is heat-laminated on the pattern layer side of the resin base material sheet and embossed to produce the decorative sheet shown in FIG. 1.
Further, in the case of the decorative material shown in FIG. 2, it is a method of applying a solvent-based adhesive to the back surface of the decorative sheet 10 to form an adhesive layer 14, and then attaching the adherend base material 15.

The decorative sheet of the present invention is useful as a heat-bonding processing sheet for wrapping processing and the like disclosed in Japanese Patent Publication No. 61-5895, Japanese Patent Application Laid-Open No. 5-3330013, and the like. Here, the heat-bonding process includes a mode of bonding while heating, a mode of bonding at room temperature and then heat-processing, a mode of simultaneously performing bonding and processing while heating, and the like.
Further, in the wrapping process, the decorative sheet has a surplus portion, and it is preferable that the seam at the end portion of the decorative sheet is overlapped and attached at the surplus portion.

As a specific application of the decorative sheet of the present invention, it is useful as a surface decorative material for exterior building materials, interior building materials, and furniture to be post-processed by heating. More specifically, it is extremely useful as an exterior building material such as window frames, doors, gates, handrails and fences, interior building materials such as wall materials, floor materials and ceiling materials, and surface decorative materials for furniture such as porcelain, desks and cupboards. be.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(Evaluation method)
1. 1. Measurement of moisture permeability Measured according to JIS Z0208: 1976 cup method.
2. 2. Hot water swelling test After immersing four 10 cm x 2.5 cm decorative sheet test pieces in a constant temperature bath of 60 ° C hot water for 3 weeks, take them out and allow them to dry sufficiently, then observe the appearance of the test pieces and observe the following evaluation criteria. The degree of hot water swelling was evaluated by (the number of swelling bubbles on one side surface of the average test piece).
Hot water swelling degree 1: The number of swelling bubbles is 0 Hot water swelling degree 2: The number of swelling bubbles is 1 to 10 Hot water swelling degree 3: The number of swelling bubbles is 11 to 20 Hot water swelling degree 4: The number of swelling bubbles is 20 to 40 Hot water swelling degree 5: Number of swelling bubbles is 40 or more

Example 1
A resin composition obtained by adding 38 parts by mass of a phthalic acid-based plasticizer (Undecyl phthalate (DUP)) as a plasticizer to 100 parts by mass of a polyvinyl chloride resin is extruded to obtain a polyvinyl chloride resin base sheet. (Thickness: 120 μm). The moisture permeability of the resin base sheet was measured by the above method. The results are shown in Table 1.
Next, a wood grain pattern layer is printed on the surface of this base material sheet, and an acrylic resin-based core-shell polymer 1 is heat-laminated on the surface protective layer (thickness: 50 μm, moisture permeability: 189 g) made of a transparent acrylic resin film. / M ^2.24 hours) was formed, and a decorative sheet was obtained. The degree of hot water swelling of the obtained decorative sheet was measured by the above method. The results are shown in Table 1.
Next, a solvent-based adhesive was applied to the back surface of the decorative sheet to form an adhesive layer (thickness; 50 μm). A hard vinyl chloride resin plate was adhered onto the adhesive layer as an adherend base material to obtain a decorative material.

Example 2
A polyester-based plasticizer (adipic acid-based polyester) was used as the plasticizer, and the content of the plasticizer was the same as in Example 1 except that 22 parts by mass was added to 100 parts by mass of the polyvinyl chloride resin. A decorative sheet and a decorative material were obtained. The results of the evaluation in the same manner as in Example 1 are shown in Table 1.

Comparative Example 1
The decorative sheet and cosmetics are the same as in Example 1 except that the content of the plasticizer (polyester-based plasticizer (adipic acid-based polyester)) is 40 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. I got the wood. The results of the evaluation in the same manner as in Example 1 are shown in Table 1.

Comparative Example 2
The decorative sheet and cosmetics are the same as in Example 1 except that the content of the plasticizer (polyester-based plasticizer (adipic acid-based polyester)) is 33 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. I got the wood. The results of the evaluation in the same manner as in Example 1 are shown in Table 1.

Comparative Example 3
The decorative sheet and cosmetics are the same as in Example 1 except that the content of the plasticizer (polyester-based plasticizer (adipic acid-based polyester)) is 30 parts by mass with respect to 100 parts by mass of the polyvinyl chloride resin. I got the wood. The results of the evaluation in the same manner as in Example 1 are shown in Table 1.

As shown in Table 1, the decorative sheets of Examples 1 and 2 using the polyvinyl chloride resin base sheet having a moisture permeability of 38 g / ^m for 2.24 hours or less generate very little hot water swelling bubbles. It has a good appearance. On the other hand, the decorative sheets of Comparative Examples 1 to 3 using the polyvinyl chloride resin base sheet having a moisture permeability of 38 g / m for more ^than 2.24 hours often generate hot water swelling bubbles and have a poor appearance.

The decorative sheet and decorative material of the present invention have excellent processability, thermoformability, embossing property, etc., and are also excellent in transparency, weather resistance, and heat resistance. Therefore, it is extremely useful as an exterior building material for window frames, doors, gates, handrails, fences, and the like.

10 Decorative sheet 11 Resin base sheet 12 Picture layer 13 Surface protective layer 14 Adhesive layer 15 Adhesive base material 20 Exterior decorative material

Claims (7)

A decorative sheet having a plasticizer-containing vinyl chloride resin base sheet and a surface protective layer made of a transparent acrylic resin film on the surface of the vinyl chloride resin base sheet, wherein the vinyl chloride resin base sheet is JIS. Z0208: A decorative sheet for exterior materials having a moisture permeability of 38 g / ^m for 2.24 hours or less measured according to the 1976 cup method. The plasticizer contained in the vinyl chloride resin base sheet consists of a group consisting of a phthalic acid-based plasticizer, an adipic acid-based plasticizer, a phosphoric acid-based plasticizer, a trimellitic acid-based plasticizer, and a polyester-based plasticizer. The decorative sheet for an exterior material according to claim 1, which is at least one selected. The decorative sheet for exterior materials according to claim 1 or 2, wherein the acrylic resin film of the surface protective layer is formed by dispersing particles composed of a crosslinked rubber core and a graft polymer shell in an acrylic resin matrix. The decorative sheet for an exterior material according to any one of claims 1 to 3, wherein the vinyl chloride resin base sheet has a thickness of 80 to 180 μm and the acrylic resin film has a thickness of 20 to 100 μm. The moisture permeability of the acrylic resin film of the surface protective layer measured in accordance with JIS Z0208: 1976 cup method is 200 g / m. ² -The decorative sheet for exterior materials according to any one of claims 1 to 4, which is 24 hours or less. An exterior decorative material obtained by attaching the decorative sheet for exterior material according to any one of claims 1 to 5 and an adherend base material via an adhesive layer. The window frame which is the exterior decorative material according to claim 6 .

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