JP2019064097A - Decorative sheet and decorative material - Google Patents

Abstract

To provide a decorative sheet for exterior material which can suppress poor appearance caused by occurrence of swelling generated by repeating of exposure to direct sunlight of moisture remained in the decorative sheet for exterior material after rainfall, particularly, after rainfall in summer.SOLUTION: A decorative sheet 10 has a resin base material sheet 11 and a surface protective layer 13 formed of a transparent acrylic resin film on the surface of the resin base material sheet 11, where moisture vapor permeability measured according to JIS Z0208:1976 cup method of the acrylic resin film 13 is 180 g/m24 hours or less.SELECTED DRAWING: Figure 1

Description

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

  Traditionally, polyvinyl chloride, as a surface covering material for furniture such as windows, doors, gates, handrails, fences, interior materials such as wall materials, floor materials, and ceiling materials, furniture such as bags, desks, and cabinets, A decorative sheet for exterior material has often been used in which a pattern is printed on the surface of a thermoplastic resin sheet such as polyolefin and embossed, and a plastic film with good weather resistance is laminated thereon (for example, a patent) Reference 1 and 2). These decorative sheets using a thermoplastic resin as a substrate sheet are excellent in processability, and have good thermoforming properties, embossing properties, and the like. Moreover, since it is excellent also in transparency, a weather resistance, and heat resistance, it is useful as the above-mentioned exterior construction material and an interior construction material.

  The decorative sheet for exterior material described above is usually attached to an adherend by lapping, etc. However, the invention of Patent Document 2 has the following problems in the lapping exterior decorative material up to that point. Solution.

  That is, as a result of repeated dimensional contraction and deterioration of the decorative sheet and the adherend substrate due to outdoor exposure, the wrapping cosmetic material for exteriors is exposed to the end face of the end surface of the decorative sheet that should be closely attached at first. Separate from each other, exposing the coated substrate from the joint and impairing the aesthetic effect of the exterior decorative material, and when the exposed coated substrate is a metal such as aluminum or iron, the coated substrate Is corroded to cause a reduction in strength, and the life as an exterior cosmetic material is reduced. Then, once the end of the decorative sheet peels off and corrosion, rust or the like occurs, the decorative sheet further peels off, and deterioration is promoted.

  In the invention described in Patent Document 2, in order to solve such problems, when the decorative sheet is surrounded and adhered around the adherend substrate, the decorative sheet has an extra portion, and the cosmetic sheet is made up. A seam of an end portion of the sheet is used as an exterior cosmetic material which is pasted and stuck at the surplus portion.

Japanese Patent Publication No. 58-14312 JP-A-6-297615

However, even if it is an exterior decorative material which is lapped with a decorative sheet having such an extra part and the seams of the end portions are overlapped and attached, the inside of the decorative sheet for the external material is after summer rainfall. The repeated exposure of the remaining water to direct sunlight for a long period of time may cause the surface of the decorative sheet to blister and cause appearance defects, and such blistering impairs the design, and in particular, overlaps. Also, the durability of the decorative sheet is significantly reduced due to the peeling of the sheet.
The present invention has been made under such circumstances, and appearance defects due to the occurrence of blisters caused by repeated exposure to direct sunlight of moisture remaining in the decorative sheet for exterior material after rainfall, especially after summer rainfall It aims at providing a decorative sheet for exterior material which can control

  The inventors of the present invention conducted intensive studies, and as a result, in the decorative sheet having a resin base sheet and a surface protective layer, the above-mentioned problems can be solved by using an acrylic resin film having a moisture permeability of a predetermined value or less as the surface protective layer. The inventors found that they could solve, and completed the present invention.

That is, the present invention is as described below.
[1] A decorative sheet having a resin base sheet and a surface protective layer made of a transparent acrylic resin film on the surface of the resin base sheet, which is measured according to the JIS Z0208: 1976 cup method of the acrylic resin film A decorative sheet for exterior material having a moisture permeability of 180 g / m ² · 24 hours or less.
[2] A cosmetic material for exteriors formed by sticking the decorative sheet for exterior material described in the above [1] and the adherend substrate via an adhesive layer.

  According to the present invention, it is possible to provide a decorative sheet for exterior material that can suppress appearance defects due to the occurrence of blistering caused by repeated exposure to direct sunlight of moisture remaining in the decorative sheet for exterior material especially after rainfall in summer. it 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 decoration material of this invention.

The decorative sheet of the present invention is a decorative sheet for exterior material having a resin base sheet and a surface protective layer made of a transparent acrylic resin film on its surface, and preferably, a picture layer is formed on the surface side of the resin base sheet. (See FIG. 1).
In addition, the decorative sheet is suitably used as an exterior cosmetic material attached to a hard adherend substrate via an adhesive layer (see FIG. 2).

  As described above, the exterior material decorative sheet may cause appearance defects and the like due to the occurrence of blisters caused by repeated exposure to direct sunlight of water remaining in the exterior material decorative sheet after summer rainfall.

The present inventor examined the cause of the generation of air bubbles that cause such swelling, and since both the resin base sheet of the decorative sheet for exterior material and the acrylic resin surface protective layer have some moisture permeability, during summer rainfall. After raining, water permeates into these plastic sheets and films, and then the remaining water is heated by exposure to direct sunlight, and is vaporized at the interface between both sheets (films), peeling both sheets (films) It was guessed that it had caused
Since the resin base sheet is an inner side, moisture is difficult to enter, and polyvinyl chloride and polyolefin frequently used for the resin base sheet have lower hygroscopicity than acrylic resins often used for the surface protective layer. However, when an acrylic resin film is used for the surface protective layer, it is an outer layer and has high hygroscopicity, so water can easily enter and the accumulated water evaporates at the interface between the resin substrate sheet and the surface protective layer to cause bubble swelling. Was considered.

Therefore, as a method for suppressing the occurrence of swelling, the present inventor decided to lower the moisture permeability of the acrylic resin film in the surface protective layer to make it difficult for moisture to enter and to be difficult to be retained. Specifically, an accelerated test in which the acrylic resin film is immersed in a thermostatic bath at 60 ° C. for 2 weeks by setting the moisture permeability of the acrylic resin film to 180 g / m ² · 24 hours or less measured in accordance with the JIS Z0208: 1976 cup method. In the above, it was confirmed that generation of blistering bubbles of the decorative sheet could be suppressed. That is, it is considered that a decorative sheet for exterior material is formed in which the occurrence of swelling caused by repeated exposure to direct sunlight of moisture remaining in the decorative sheet for exterior material after rainfall in summer is suppressed.

  Hereinafter, each component of the decorative sheet of this invention is demonstrated in detail, referring FIG.1 and FIG.2. However, the present invention is not limited to the following embodiments.

  The resin of the resin substrate sheet used in the present invention is not particularly limited as long as it is a thermoplastic resin having good processability, thermoformability, transparency, weatherability, etc., but it is a general-purpose resin with low cost. Polyvinyl chloride, polycarbonate, polyolefin and the like having low moisture permeability are preferably used. Among them, polyvinyl chloride resins are particularly preferable in that they have high merits.

Further, as the vinyl chloride resin, a copolymer obtained by copolymerizing a vinyl chloride monomer can also be used.
As monomers copolymerizable with the vinyl chloride monomer, vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters such as methyl acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate; butyl malate and the like Maleates such as diethyl malate; fumaric esters such as dibutyl fumarate and diethyl fumarate; vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; vinyl cyanides 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; Halogenated vinyls; phthalate allyl such as diallyl phthalate, and the like. You may use these monomers individually or in combination of 2 or more types.

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

  500-4000 are preferable, as for the average degree of polymerization of vinyl chloride-type resin, 700-3900 are more preferable, and 1000-3800 are still more preferable. When the average degree of polymerization is in the above range, excellent mechanical strength can be obtained, and excellent moldability can be obtained. The average degree of polymerization is an average degree of polymerization measured in accordance with JIS K6721.

  In the case of using a vinyl chloride resin as the resin base sheet, it is preferable to add a plasticizer in order to improve the processability. The plasticizer is not particularly limited as long as it is compatible with the vinyl chloride resin, and examples thereof include dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), and diisodecyl phthalate Phthalic acid plasticizers such as DIDP), diundecyl phthalate (DUP); adipic acid plasticizers such as dibutyl adipate; phosphoric acid plasticizers such as tributyl phosphate, tricresyl phosphate, triphenyl phosphate; Trimellitic acid plasticizers such as tributyl acid and trioctyl trimellitic acid; various known polyester plasticizers such as adipic acid polyester; citric acid esters such as acetyl tributyl citrate and acetyl trioctyl citrate; and the like . You may use these plasticizers individually or in combination of 2 or more types.

  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 necessary processing suitability can be maintained. On the other hand, a plasticizer is preferable because it does not bleed out as it is 50 mass parts or less. From the above viewpoints, 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.

A thermoplastic resin having a relatively low moisture permeability and a good processability, such as vinyl chloride resin, olefin resin such as polypropylene, polyethylene and polymethylpentene, and polycarbonate as resin of resin base sheet used in the present invention Can also be preferably used.
The moisture permeability of the resin substrate sheet is preferably 80 g / m ² · 24 hours or less, and more preferably 40 g / m ² · 24 hours or less.

  The thickness of the resin base sheet is preferably 80 to 180 μm. When it is 80 μm or more, it is usually used in various concavo-convex patterns such as wood grain ditch, cloth texture, grain, satin, hairline, cleavage plane of granite board surface, skin grain and the like used for this kind of decorative material Within the range, it is advantageous in that the plate depth is deep even in the case of embossing, and the effect on the back surface is small, and if it is 180 μm or less, it is advantageous in terms of bending workability such as lapping. From the above viewpoints, the thickness of the vinyl chloride resin base sheet is more preferably in the range of 90 to 160 μm, and still more 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 protects the resin base sheet and also plays a role of protecting the pattern layer 12 described later.
The surface protective layer used for the decorative sheet of the present invention is preferably one having high transparency from the viewpoint of designability, and is high in weather resistance and durability, and high in adhesion to the resin base sheet and the pattern layer. Then, an acrylic resin film is used.
Examples of the acrylic resin constituting the acrylic resin film include polymethyl methacrylate, methyl methacrylate-butyl methacrylate copolymer, butyl methacrylate-methyl methacrylate copolymer and the like. Further, it is also preferable to use an acrylic resin matrix in which particles made of a crosslinked rubber core and a graft polymer shell are dispersed in an acrylic resin matrix in which the processability and weatherability are improved by improving the brittleness and cracking of the acrylic resin. Hereinafter, the acrylic resin of such a form is also referred to as "acrylic resin-based core-shell polymer".

The acrylic resin film used for the surface protective layer of the decorative sheet of the present invention has a moisture permeability of 180 g / m ² · 24 hours or less measured according to JIS Z 0208: 1976 cup method. When the moisture permeability is 180 g / m ² · 24 hours or less, the generation of blistering of the decorative sheet can be suppressed. The moisture permeability of the acrylic resin film is preferably 150 g / m ² · 24 hours or less, and more preferably 120 g / m ² · 24 hours or less.
There is no lower limit to the moisture permeability of the acrylic resin film of the surface protective layer from the viewpoint that the generation of blistering bubbles due to an increase in the amount of residual water in the surface protective layer can be suppressed. The moisture permeability is preferably 70 g / m ² · 24 hours or more, and more preferably 90 g / m ² · 24 hours or more, from the viewpoint that it is easy to escape and also contributes to suppression of the generation of blisters.

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

The decorative sheet 10 of the present invention can have the pattern layer 12 between the resin base sheet 11 and the surface protective layer 13. The picture layer is for providing the decorative sheet with a design. The picture layer is formed, for example, by printing various patterns using an ink and a printing machine. As a pattern, a stone pattern imitating the surface of a rock such as a wood grain pattern, a marble pattern (for example, travertine marble pattern), a cloth pattern imitating a grain pattern or a cloth-like pattern, a skin pattern (shibo) pattern, a tiled pattern, There are brickwork patterns, letters, figures, etc. These patterns are formed by various printing methods such as ordinary gravure printing, offset printing, silk screen printing, flexographic printing, ink jet printing and the like.
In addition, a colored layer (solid layer) formed in a single color may be provided over the entire surface, or may be combined with the above picture layer.
The thickness of these pattern layers is usually in the range of 1 to 5 μm.

A decorative material 20 formed by sticking the decorative sheet 10 of the present invention to the adherend substrate 15 via the adhesive layer 14 on the resin base 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 bond the resin substrate sheet to the adherend substrate, but from the viewpoint of adhesiveness, a solvent-based adhesive is preferable, and specific These include phenolic resins, vinyl acetate resins, vinyl chloride resins, cellulose resins such as nitrocellulose, thermoplastic resin, two-component curable urethane resin, moisture curable urethane resin, epoxy resin, solvent vinyl acetate resin And emulsions of acrylic resin and the like.
In addition, a material in which the residual solvent does not easily remain is preferable, and may be a one-component curing type or a two-component curing type.

As the adherend substrate 15, those having various shapes such as flat plates, curved plates, pillars of various cross-sectional shapes used for handrails and window frames, and the like are used according to applications.
When the adherend substrate is made of resin, as the resin constituting the adherend substrate, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate-isophthalate copolymer, polyarylate, etc .; ethylene-vinyl alcohol Copolymer; Polymethylene resin; Polycarbonate resin; Polyimide resin; Polystyrene resin; Polyamide resin; ABS (acrylonitrile-butadiene-styrene copolymer) resin; AS (acrylonitrile-styrene copolymer); Cellulose resin; Polyamide resin etc. Are preferred, and hard ones are preferred. The adherend substrate may be a single layer composed of these resins, or a laminate of two or more layers composed of two or more different resin layers selected from among these resins.
When the adherend substrate is made of metal, iron or iron alloy, aluminum or aluminum alloy, copper, brass, titanium or the like is used as the metal to be used. When the adherend is wood, examples of wood used include veneers of various wood species such as cedar, mulberry, pine, pine, rawan and teak, plywood, particle board, fiber plate, laminated wood and the like. When the adhesion base material is a ceramic-based inorganic material, cement-based materials, calcium silicate, chinaware, glass, various ceramics, etc. may be mentioned.

The decorative sheet and the decorative material of the present invention are produced, for example, by the following method.
For example, in the case of the decorative sheet shown in FIG. 1, first, the pattern layer 12 is formed on the resin base sheet 11 by a printing method or the like. Subsequently, the decorative layer shown in FIG. 1 can be manufactured by thermally laminating the surface protection layer 13 on the pattern layer side of the resin substrate sheet and performing embossing.
Moreover, if it is a cosmetic material shown in FIG. 2, it is a method of apply | coating a solvent type adhesive agent to the back surface of the decorative sheet 10, forming the adhesive bond layer 14, and sticking the adhesion base material 15 after that.

The decorative sheet of the present invention is useful as a sheet for heat bonding such as lapping. Here, the thermal bonding process includes an embodiment in which bonding is performed while heating, an embodiment in which heating is performed after bonding at normal temperature, and an embodiment in which bonding and processing are simultaneously performed while heating.
Further, in the lapping process, it is preferable that the decorative sheet has a surplus portion, and the seams of the end portions of the decorative sheet overlap and be stuck at the surplus portion.

  As a specific application of the decorative sheet of the present invention, the decorative sheet is useful as a surface decorative material of an exterior building material, an interior building material, and furniture which is heated and post-processed. More specifically, it is extremely useful as a surface covering material for furniture such as windows, doors, gates, exteriors such as handrails and fences, interior materials such as wall materials, floorings, and ceiling materials, furniture such as bags, desks, and cabinets. is there.

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

Example 1
A resin composition containing 30 parts by mass of a polyester-based plasticizer (adipic acid-based polyester) as a plasticizer was extruded with respect to 100 parts by mass of a polyvinyl chloride resin to obtain a vinyl chloride-based resin base sheet (thickness 120 μm, moisture permeability: 40 g / m ² · 24 hours).
Next, a wood grain pattern pattern layer is printed on the surface of the resin base sheet, and the acrylic resin core-shell polymer 1 is thermally laminated thereon to form a surface protective layer (thickness: 50 μm) made of a transparent acrylic resin film. , I got a cosmetic sheet. The moisture permeability of the used acrylic resin film and the degree of hot water blistering of the obtained decorative sheet were 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). On the adhesive layer, a hard vinyl chloride resin plate was adhered as an adherend substrate to obtain a cosmetic material.

Example 2
A decorative sheet and a cosmetic material were obtained in the same manner as in Example 1 except that a surface protective layer (thickness: 50 μm) was formed using an acrylic resin core-shell polymer 2 as an acrylic resin constituting an acrylic resin film. The moisture permeability of the acrylic resin film and the degree of hot water expansion of the decorative sheet were measured by the above method, and the results are shown in Table 1.

Example 3
A decorative sheet and a cosmetic material were obtained in the same manner as in Example 1 except that a surface protective layer (thickness: 50 μm) was formed using an acrylic resin core-shell polymer 3 as an acrylic resin constituting an acrylic resin film. The moisture permeability of the acrylic resin film and the degree of hot water expansion of the decorative sheet were measured by the above method, and the results are shown in Table 1.

Comparative Example 1
A decorative sheet and a cosmetic material were obtained in the same manner as in Example 1 except that a surface protective layer (thickness: 50 μm) was formed using an acrylic resin core-shell polymer 4 as an acrylic resin constituting an acrylic resin film. The moisture permeability of the acrylic resin film and the degree of hot water expansion of the decorative sheet were measured by the above method, and the results are shown in Table 1.

As shown in Table 1, the decorative sheets of Examples 1 to 3 using an acrylic resin film having a moisture permeability of 180 g / m ² · 24 hours or less have a good appearance with less generation of hot water blisters. The On the other hand, the decorative sheet of Comparative Example 1 using an acrylic resin film having a moisture permeability of more than 180 g / m ² · 24 hours had many hot water blisters and the appearance was poor.

  The decorative sheet and the decorative material of the present invention are excellent in processing suitability, are excellent in thermoforming property, embossing property and the like, and are also excellent in transparency, weather resistance and heat resistance. Therefore, it is extremely useful as an exterior construction material such as a window frame, a door, a gate, a handrail, and a fence.

DESCRIPTION OF REFERENCE NUMERALS 10 decorative sheet 11 resin base sheet 12 pattern layer 13 surface protective layer 14 adhesive layer 15 coated base material 20 exterior cosmetic material

Claims (6)

A decorative sheet having a resin base sheet and a surface protection layer made of a transparent acrylic resin film on the surface of the resin base sheet, wherein the moisture permeability of the acrylic resin film measured according to JIS Z0208: 1976 cup method is Cosmetic sheet for exterior material which is 180 g / m ² · 24 hours or less.   The decorative sheet for exterior material according to claim 1, wherein the acrylic resin film of the surface protective layer is obtained by dispersing particles composed of a crosslinked rubber core and a graft polymer shell in an acrylic resin matrix.   The decorative sheet for exterior material according to claim 1 or 2, wherein the resin base sheet is a plasticizer-containing vinyl chloride resin base sheet.   The thickness of the said resin base material sheet is 80-180 micrometers, The thickness of the said acrylic resin film is 20-100 micrometers, The decorative sheet for exterior materials of any one of Claims 1-3.   An exterior decorative material formed by sticking the exterior material decorative sheet according to any one of claims 1 to 4 and an adherend base material via an adhesive layer.   The window frame which is a cosmetic for exteriors of Claim 5.