JP6900733B2 - Exterior decorative sheet - Google Patents

Description

The present invention relates to a decorative sheet provided with a polyvinyl chloride resin base material, a decorative portion, and a blocking layer, and the plasticizer does not easily migrate from the inside of the resin base material to the outside when used for an exterior. The decorative sheet of the present invention is mainly used for exterior building materials such as window frames, doors, handrails, roofs, and fences.

A decorative sheet having a decorative layer is attached to an exterior building material such as a window frame or a door to visually decorate the exterior building material. As an example of this exterior decorative sheet, one in which a decorative layer is provided on one surface of a polyvinyl chloride resin base material is known.
A plasticizer is usually used for the resin base material for the purpose of imparting flexibility to the polyvinyl chloride-based resin base material. However, as a result of the passage of time, use in a high temperature environment, etc., the plasticizer in the polyvinyl chloride resin base material migrates (bleeds out) to the outside of the resin base material or to other members, and as a result, the resin base material is reduced. It is known that the elastic modulus of The decrease in flexibility of the polyvinyl chloride resin base material causes the entire exterior decorative sheet to float or peel off from the peripheral members, and the exterior decorative sheet becomes fragile, causing cracks or cracks when an external force is applied. Further, the plasticizer that has migrated to the surface of the base material acts as a mold release agent, and as a result, various layers formed by adhering and laminating adjacent to the base material, such as a decorative layer, a transparent resin layer, and a top coat. The adhesive force with the layer, the adhesive layer, etc. is reduced, and it becomes easy to peel off from the other laminated layers. Therefore, retaining the plasticizer in the polyvinyl chloride resin base material in an amount of a certain amount or more contributes to the long-term durability of the exterior decorative sheet.

Conventionally, various techniques have been developed to prevent the transfer of the plasticizer from the polyvinyl chloride resin base material.
Patent Document 1 describes a technique in which a polyvinyl chloride film contains a non-migratory plasticizer in a decorative sheet for exterior of a metal sash formed by laminating a transparent acrylic resin film on a polyvinyl chloride film provided with a pattern printing layer. It is disclosed. The document describes that the use of a non-migratory plasticizer can prevent delamination of the transparent acrylic resin film and the polyvinyl chloride film over time.

Patent Document 2 describes in a weather-resistant decorative sheet in which a thermoplastic resin layer and a protective layer containing an ultraviolet absorber are laminated, an adipic acid-based polyester plasticizer and a phthalic acid-based polyester are used as plasticizers for the thermoplastic resin layer. A technique using a mixture with a plasticizer is disclosed. The document describes that by using a mixture of these two types of plasticizer, the plasticizer does not migrate to the protective layer, and as a result, the effect of the ultraviolet absorber is not lost.

Patent Document 3 contains 90 to 99.9% by weight of an ethylene-vinyl ester copolymer saponified product having an ethylene content of 20 to 65 mol% and a vinyl ester component having a saconification degree of 90 mol% or more, and antibacterial metal ions. A decorative board made of a laminate having a composition layer composed of 10 to 0.1% by weight of an inorganic oxoate having a plasticizer on at least one surface of a polyvinyl chloride resin layer containing a plasticizer is disclosed. The document describes that the decorative board has a function of blocking a plasticizer for a polyvinyl chloride resin.

On the other hand, although the transfer of the plasticizer is not mentioned, a technique for preventing the transfer of the pigment from the decorative layer to the base material in the laminated structure of the exterior decorative sheet is also known. Patent Document 4 discloses an exterior decorative sheet in which an isolation layer such as an acrylic resin, a pattern printing layer, and a weather-resistant plastic film are laminated in this order on a polyvinyl chloride base film. This technique aims to prevent the outflow of pigment from the pattern printing layer to the base film by means of the isolation layer.

Special Fair 7-67788 Gazette Japanese Unexamined Patent Publication No. 7-24970 Japanese Unexamined Patent Publication No. 2000-103014 Jikken 4-46924 Gazette

However, in the technique of Patent Document 1-2, since the type of plasticizer is limited to a special one, the raw material cost also rises, and the types of polyvinyl chloride resin base materials that can be used naturally and various types that can be expressed. The range of physical properties is also limited. Further, in the technique of Patent Document 3-4, since an isolation layer using an organic compound as a base material is used, it is not possible to prevent the migration of the plasticizer when a plasticizer having an affinity for the organic compound is used. As described above, in the prior art, the effect of blocking the migration of the plasticizer is insufficient, the price is high, and the materials that can be used and the physical characteristics that can be expressed are limited.
The present invention has been achieved in view of the above-mentioned actual conditions regarding the migration of a plasticizer, and is provided with a polyvinyl chloride-based resin base material, a decorative portion, and a blocking layer, and is plasticized from the resin base material when used for an exterior. An object of the present invention is to provide a decorative sheet to which the agent is difficult to transfer.

The exterior decorative sheet of the present invention includes a polyvinyl chloride-based resin base material containing a plasticizer, a decorative layer arranged on at least one side of the polyvinyl chloride-based resin base material, and the poly. An exterior decorative sheet comprising at least one decorative portion selected from the group consisting of decorative surfaces obtained by directly decorating all or part of the surface of a vinyl chloride resin base material, wherein the polyvinyl chloride resin base is used. A blocking layer is further provided on the side of at least one of the surfaces of the material, and the entire blocking layer is a film formed by self-assembling scaly inorganic particles . The bottom surface is aligned in a direction parallel or substantially parallel to the surface of the polyvinyl chloride resin base material on the side provided with the blocking layer, and adjacent scaly inorganic particles are directly bonded to each other. The average thickness of the blocking layer is in the range of 1.0 to 100 μm .

In the present invention, before Symbol scale-like inorganic particles are scaly silica particles, a film formed by the self-organization, be a film scaly silica particles adjacent formed by bonding to each other by Si-O bond Good.

The present invention may include the blocking layer in contact with the decorative portion.
In the present invention, the blocking layer may be provided on the side opposite to the decorative portion with the polyvinyl chloride resin base material interposed therebetween.
In the present invention, at least the decorative layer may be provided as the decorative portion, and the blocking layer may be provided between the polyvinyl chloride resin base material and the decorative layer.
In the present invention, blocking layers may be provided on both sides of the polyvinyl chloride resin base material.

In the present invention, it is preferable to further provide a transparent resin layer on one surface side of the laminate including the polyvinyl chloride resin base material, the decorative portion, and the blocking layer from the viewpoint of protection of the laminate.

According to the present invention, since a blocking layer, which is a film containing flat inorganic particles, is provided on at least one side of the polyvinyl chloride resin base material, plasticization from the polyvinyl chloride resin base material is provided. It is possible to prevent the transfer of the agent, and as a result, it is possible to suppress the floating, peeling and cracking of all or a part of the exterior decorative sheet, and it is possible to improve the durability.

It is a perspective schematic view of the laminated body in which barrier layers are formed on both sides of a polyvinyl chloride resin base material. FIG. 3 is a schematic perspective view showing a part of the surface of the blocking layer 2 in FIG. 1 extracted. It is a cross-sectional schematic diagram of the laminated body in which the blocking layer is formed on one side of the polyvinyl chloride resin base material, and the bottom surface of the flat inorganic particles in the blocking layer is on one surface of the polyvinyl chloride resin base material. It shows how they are aligned in parallel directions. It is a cross-sectional schematic diagram of the laminated body in which the blocking layer is formed on one side of the polyvinyl chloride resin base material, and the bottom surface of the flat inorganic particles in the blocking layer is on one surface of the polyvinyl chloride resin base material. It shows that they are aligned in substantially parallel directions. It is a cross-sectional schematic diagram of a laminated body in which a blocking layer is formed on one side of a decorative treated polyvinyl chloride resin base material, and the bottom surface of the flat inorganic particles in the blocking layer is made of a polyvinyl chloride resin base material. It shows that they are aligned in a direction parallel to one surface. It is a cross-sectional schematic diagram of a laminated body in which a blocking layer is formed on one side of a decorative treated polyvinyl chloride resin base material, and the bottom surface of the flat inorganic particles in the blocking layer is made of a polyvinyl chloride resin base material. It shows that they are aligned in a direction substantially parallel to one surface. It is a cross-sectional schematic diagram of a laminate in which a blocking layer is formed on one side of a decorative treated polyvinyl chloride resin base material, and the arrangement of flat inorganic particles located in the recesses of the resin base material is irregular. Shows how it looks. It is sectional drawing which comprises the polyvinyl chloride resin base material, the decorative layer, and the barrier layer. It is sectional drawing of the other laminated body provided with a polyvinyl chloride resin base material, a decorative layer, and a blocking layer. FIG. 5 is a schematic cross-sectional view of a laminated body including a polyvinyl chloride resin base material provided with a decorative surface and a blocking layer. FIG. 5 is a schematic cross-sectional view of a laminated body including a polyvinyl chloride resin base material having a decorative surface, a decorative layer, and a blocking layer. It is sectional drawing of the embodiment of the decorative sheet for exterior of this invention. (A) The surface of the olefin sheet that was not used in the evaluation laminate, (b) the contact surface of the olefin sheet A with the barrier layer, and (c) the contact surface of the olefin sheet B with the polyvinyl chloride resin substrate. It is a graph which showed each FT-IR spectrum side by side. It is a graph which showed each FT-IR spectrum of one surface and the other surface of a polyvinyl chloride resin base material side by side.

Next, the embodiment of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the purpose.
In the present invention, the (meth) acrylate represents each of acrylate and methacrylate.
In the present invention, the cured product of a resin means a solidified product that has undergone or has not undergone a chemical reaction.

The exterior decorative sheet of the present invention includes a polyvinyl chloride-based resin base material containing a plasticizer, a decorative layer arranged on at least one side of the polyvinyl chloride-based resin base material, and the poly. An exterior decorative sheet comprising at least one decorative portion selected from the group consisting of decorative surfaces obtained by directly decorating all or part of the surface of a vinyl chloride resin base material, wherein the polyvinyl chloride resin base is used. A blocking layer is further provided on the side of at least one of the surfaces of the material, and the blocking layer is a film containing flat inorganic particles as an essential component and may further contain a binder resin, and is contained in the blocking layer. The bottom surface of the flat inorganic particles is aligned in a direction parallel to or substantially parallel to the surface of the polyvinyl chloride resin base material provided with the blocking layer, and the flat inorganic particles are adjacent to each other. It is characterized in that it is bonded to each other directly or via a binder resin.

1. 1. Polychlorinated resin base material The polyvinyl chloride-based resin base material is provided to maintain the shape of the decorative sheet for exterior use.
In the present invention, the "polyvinyl chloride resin" means a resin having 50 mol% or more of vinyl chloride monomer units. Examples of the polyvinyl chloride resin include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl alcohol copolymer, vinyl chloride-vinyl butyral copolymer, and chloride. Examples thereof include a vinyl-ethylene copolymer and a vinyl chloride-ethylene-vinyl acetate copolymer.

The polyvinyl chloride resin base material contains a plasticizer. The plasticizer is used for the purpose of imparting flexibility to the resin base material and controlling its hardness.
Examples of the plasticizer used include phthalates such as dioctylphthalate, trimellitic acids such as trioctyl trimellitic acid, adipic acid esters, polyester adipic acid, polyester phthalates, phosphoric acid esters, and quen. Examples thereof include acid esters, benzoic acid esters, terephthalates, epoxidized vegetable oils, and chlorinated paraffins.
The content of the plasticizer is not particularly limited. For example, when the mass of the polyvinyl chloride resin base material is 100 parts by mass, it may be 5 to 60 parts by mass, or 15 to 35 parts by mass. Is preferable.

The polyvinyl chloride resin base material may contain a colorant. The colorant colors at least one surface of the polyvinyl chloride resin substrate to a desired hue. Coloring agents include inorganic pigments such as titanium white, zinc flower, petals, vermilion, ultramarine blue, cobalt blue, yellow lead, titanium yellow, and carbon black, isoindolinone, Hansa yellow A, quinacridone, permanent red 4R, and phthalocyanine blue. , Azomethine azo compounds, organic pigments such as perylene compounds, dyes, metal pigments made of metal foil powders such as aluminum and brass, titanium dioxide-coated mica, pearl pigments made of foil powders such as basic lead carbonate, etc. Conventionally known coloring pigments are used. The coloring may be either transparent coloring or opaque (concealment) coloring, but in general, opaque coloring is preferable in order to conceal the adherend.
The content of the colorant is not particularly limited. For example, when the mass of the polyvinyl chloride resin base material is 100 parts by mass, it may be 1 to 40 parts by mass, or 5 to 20 parts by mass. Is preferable.

Further, if necessary, a heat stabilizer, a flame retardant, a radical scavenger, an ultraviolet absorber and the like are added. The heat stabilizer is known as a phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine-based, etc., and is used to further improve the preventive property of deterioration such as thermal discoloration during heat processing. .. As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy. Examples of the radical scavenger include bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl). A hindered amine radical scavenger such as Sevakate is used. Examples of the ultraviolet absorber include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine and 2- (2-hydroxy-4-hexyloxyphenyl). ) -4,6-Diphenyl-s-triazine and other triazines, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dithr) Butylphenyl) -5-chlorobenzotriazole and other benzotriazoles, benzophenones, benzoates and the like are used.
The content of these additives may be, for example, 1 to 50 parts by mass, preferably 10 to 25 parts by mass, when the mass of the polyvinyl chloride resin base material is 100 parts by mass.

A polyvinyl chloride resin base material can be obtained by forming a film of a mixture of a polyvinyl chloride resin, a plasticizer, and an additive such as a colorant if necessary by a usual method such as a calendar manufacturing method. ..
The average thickness of the obtained polyvinyl chloride resin base material can be appropriately set according to the material so that its strength and heat resistance are appropriate, and is generally about 1 μm to 1,000 μm, preferably about 1 μm to 1,000 μm. It is 10 μm to 500 μm.

The method for measuring the average thickness of each layer (polyvinyl chloride resin base material, blocking layer, and if necessary, decorative layer, transparent resin layer, top coat layer, etc.) constituting the exterior decorative sheet according to the present invention is It is as follows. First, the cross section of the exterior decorative sheet is observed with an optical microscope, an electron microscope, or the like. The thickness of the layer to be measured is measured at about 3 to 10 places, and the average of the calculated thickness is defined as the average thickness of the layer.
However, when the polyvinyl chloride resin base material has a decorative surface, the thickness of the portion where the decorative surface is concave and the thickness of the portion where the decorative surface is convex are different. Therefore, for the polyvinyl chloride-based resin base material provided with the decorative surface, the thickness of the portion having the convex shape of the decorative surface is measured by the above method, and the average thickness is calculated.

2. Decorative part The decorative part is a general term for a decorative layer and a decorative surface, which will be described later, and is a part to which a color or a pattern is applied to visually decorate an object (adhesive body) on which a decorative sheet is installed. The color, pattern, etc. given to the exterior decorative sheet by the decorative portion are not particularly limited as the design, material, and forming method are appropriately selected depending on the use of the exterior decorative sheet.

(1) Decorative layer The decorative layer is arranged on the side of at least one surface of the polyvinyl chloride resin base material.
Examples of the pattern formed on the surface of the polyvinyl chloride resin base material by the decorative layer include a three-dimensional pattern and a two-dimensional pattern.
Examples of the three-dimensional pattern include a simple uneven pattern, a wood grain board conduit groove, a stone board surface unevenness (granite cleavage surface, etc.), a cloth surface texture, a satin finish, a sand grain, a hairline, and a perforated groove. A colorant may be filled in the concave portion of the three-dimensional pattern. Filling may be performed by a conventionally known wiping method or the like. The above-mentioned materials can be used as the colorant.
Examples of the flat pattern include a pattern that imitates the surface appearance of a natural object such as wood grain, stone grain, and cloth, an abstract pattern such as a polka dot pattern, a striped pattern, and a geometric pattern, and a pattern that includes letters or numbers. ..
Examples of the color imparted to the surface of the polyvinyl chloride resin base material by the decorative layer include a single color solid surface and a combination of a plurality of colors. The decorative layer may be a combination of a plurality of colors to reproduce a photograph or a painting, or may itself be a painting.

Examples of the material for forming the decorative layer include a metal thin film, an ink in which the above-mentioned colorant is dispersed in a binder, and the like.
Examples of the metal thin film include thin films of metals such as aluminum, chromium, gold, silver, and copper. These metal thin films are formed by a method such as vacuum deposition or sputtering.
Examples of the binder used for the ink include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins, acrylic resins, polyvinyl acetates, vinyl chloride-vinyl acetate copolymers, and cellulose-based resins. These binders may be used alone or in combination of two or more. As an example of a binder in which two or more kinds of resins are mixed, for example, an acrylic resin such as polyvinyl methacrylate and a vinyl chloride-vinyl acetate copolymer are used as the mass of the acrylic resin / vinyl chloride-vinyl acetate copolymer. Examples thereof include binders formed by appropriately mixing in the range of mass = 80/20 to 20/80. A material obtained by adding the above-mentioned colorant to such a binder is used as an ink for a decorative layer.
When printing decorative layer ink directly on a polyvinyl chloride resin base material, it is recommended to use a mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer or urethane resin as a binder in terms of adhesiveness. preferable.

The decorative layer may be provided on the entire surface of the surface of the polyvinyl chloride resin base material, or may be provided on a part of the surface. The decorative layer may have a pattern portion and a color portion mixed. The decorative layer may be a mixture of a portion formed by the above ink and a portion of a metal thin film.
The decorative layer may be provided only on one side of the polyvinyl chloride resin base material, or may be provided on both sides.

The average thickness of the decorative layer can be appropriately set according to the content of the decoration and the type of color pattern, and is generally about 0.1 μm to 20 μm, preferably 0.5 μm to 10 μm.

(2) Decorative surface The decorative surface means a surface on which all or part of the surface of the polyvinyl chloride resin base material is directly decorated. Here, "decorative treatment" means decorating all or part of the surface of the resin base material by processing all or part of the polyvinyl chloride resin base material. Specific examples of the decorative treatment include cutting all or part of the surface of the polyvinyl chloride resin base material, embossing the polyvinyl chloride resin base material, and the like. The term "embossing" as used herein means that all or part of the polyvinyl chloride resin base material is heated and softened, pressed and shaped with an embossed plate, and cooled and fixed to form.
The pattern imparted to the polyvinyl chloride resin base material by the decorative treatment is the same as in the case of the decorative layer described above.

3. 3. Blocking layer The blocking layer is a film containing flat inorganic particles as an essential component. As will be described later, the blocking layer may further contain a binder resin.
FIG. 1 is a schematic perspective view of a laminate 10 in which barrier layers 2 are formed on both sides of a polyvinyl chloride resin base material 1. Note that FIG. 1 is a schematic diagram for explaining the configuration of the blocking layer, and the present invention is not necessarily limited to the form shown in FIG. As shown in FIG. 1, the flat inorganic particles 12 have various shapes and are folded and exist in the blocking layer 2.

FIG. 2 is a schematic perspective view showing a part of the surface of the blocking layer 2 in FIG. 1 extracted. In the present invention, the surface having the largest area among the surfaces of the flat inorganic particles is defined as the bottom surface. As shown in FIG. 2, in the blocking layer 2, a plurality of flat inorganic particles 12 are folded mainly via the bottom surfaces 12a.

For flat inorganic particles, the diameter of the bottom surface is
(1) If a circumscribed circle on the bottom surface can be drawn, the diameter of the circumscribed circle is used as the diameter of the bottom surface.
(2) If the circumscribed circle on the bottom cannot be drawn, the longest diagonal length is used as the diameter of the bottom.
(3) If the bottom surface is a circle or an ellipse, the major axis (or diameter) shall be the diameter of the bottom surface.
When defined as, the value obtained by dividing the diameter of the bottom surface by the length (thickness) in the direction substantially perpendicular to the bottom surface is preferably 5 to 50, more preferably 10 to 40. .. In the case of such a flat shape, the particles are likely to be arranged parallel to or substantially parallel to one surface of the polyvinyl chloride resin base material.
The shape of the bottom surface of the flat inorganic particles is not particularly limited, and examples thereof include a circular shape, an elliptical shape, and a polygonal shape.

The flat inorganic particles have an average diameter of 0.01 μm to 10.00 μm on the bottom surface and an average length (average thickness) of 0.01 to 1.00 μm in a direction substantially perpendicular to the bottom surface. It is preferable to have. Within this range, the particles are likely to be arranged in parallel or substantially parallel to one surface of the polyvinyl chloride resin base material, and the film forming property is improved.
Here, the average diameter (in the case of a circle, it is the diameter) is measured by a laser scattering method, a diffraction type particle size distribution meter, etc., and the average thickness of the particles is measured by a scanning electron microscope of 100 particles. Each is calculated from the average value.

3A and 3B are schematic cross-sectional views of a laminated body in which a blocking layer 2 is formed on one side of a polyvinyl chloride resin base material 1. In these figures, for the sake of explanation, the cross section of the flat inorganic particles is shown by a rectangle 12.
FIG. 3A shows how the bottom surface 12a of the flat inorganic particles 12 in the blocking layer 2 is aligned in a direction parallel to the surface 1a on the side of the polyvinyl chloride resin base material 1 provided with the blocking layer 2. Shown. Moreover, the flat inorganic particles 12 are made of a polyvinyl chloride resin base material so that they can be easily understood from FIGS. 1 and 2 (although they are perspective views) in a plan view looking down from above in the drawing. The surface 1a of 1 is covered with no gap, that is, the entire surface is covered so that the underlying surface 1a is not exposed.
By stacking the flat inorganic particles 12 in parallel with the polyvinyl chloride resin base material 1 in this way, it is possible to prevent the transfer of the plasticizer from the inside of the polyvinyl chloride resin base material 1.
On the other hand, FIG. 3B shows how the bottom surface 12a of the flat inorganic particles 12 in the blocking layer 2 is aligned with the surface 1a of the polyvinyl chloride resin base material 1 at an inclination of an angle α. Further, as in the form of FIG. 3A, the flat inorganic particles 12 cover the entire surface 1a of the polyvinyl chloride resin base material 1 without gaps in a plan view. If this angle α is too large, the plasticizer inside the polyvinyl chloride resin base material 1 slips between the flat inorganic particles 12 and moves to the outside, which is not preferable. When the angle α is sufficiently small and the bottom surface 12a is substantially parallel to the surface 1a, specifically, when the angle α is in the range of 0 to 30 °, preferably in the range of 0 to 10 °. Since the amount of the plasticizer that slips through the flat inorganic particles 12 and migrates to the outside is suppressed, the effect of the present invention is fully exhibited.
The angle α does not have to be equal for all the flat inorganic particles, and the angle distribution may have a range. Further, as long as the aligned structure of the flat inorganic particles can be maintained, the state shown in FIG. 3A and the state shown in FIG. 3B may be mixed.

4A to 4C are schematic cross-sectional views of a laminated body in which a blocking layer 2 is formed on one side of a decorated polyvinyl chloride resin base material 1. The rectangle 12 in these figures shows a cross section of the flat inorganic particles as in FIGS. 3A and 3B. In principle, the surface 1a of the polyvinyl chloride-based resin base material 1 that serves as a reference for the orientation of the flat inorganic particles is based on the convex portion of the resin base material 1. This is because the bottom 1b of the recess in the decorative treatment is not always flat as shown in FIGS. 4A to 4C.
FIG. 4A shows how the bottom surface 12a of the flat inorganic particles 12 in the blocking layer 2 is aligned in a direction parallel to the surface 1a of the polyvinyl chloride resin base material 1. As shown in FIG. 4A, the orientation of the flat inorganic particles 12 does not change even in the recesses on the surface of the polyvinyl chloride resin base material 1, and the particles are aligned parallel to the surface 1a. By aligning the flat inorganic particles 12 in this way, it is possible to prevent the migration of the plasticizer as in the case of FIG. 3A.
On the other hand, FIG. 4B shows how the bottom surface 12a of the flat inorganic particles 12 in the blocking layer 2 is aligned with the surface 1a of the polyvinyl chloride resin base material 1 at an inclination of an angle α. This angle α is the same as in FIG. 3B described above. Further, as shown in FIG. 4B, when the recess on the surface of the polyvinyl chloride resin base material 1 is flat, the bottom surface 12a of the flat inorganic particles 12 has an angle β with respect to the bottom 1b of the recess. It may be aligned by inclination. The numerical range of the angle β is the same as the angle α. Further, the angle β and the angle α may be equal or different.
FIG. 4C is the same as FIG. 4B except that the arrangement of the flat inorganic particles located inside the recesses of the polyvinyl chloride resin base material is irregular. In this way, even if the arrangement of the flat inorganic particles is irregular inside the recess, the flat inorganic particles are directional in the thick portion of the blocking layer (2A portion in FIG. 4C) covering the recess. If it is arranged in, the migration of the plasticizer can be prevented as in the case of FIGS. 4A and 4B.
As long as the aligned structure of the flat inorganic particles can be maintained, the state shown in FIG. 4A, the state shown in FIG. 4B, and the state shown in FIG. 4C may be mixed.

The ratio of the size of the flat inorganic particles to the size of the recesses on the surface of the polyvinyl chloride resin base material formed by the decorative treatment is not limited to the embodiment shown in FIGS. 4A to 4C. When the diameter and thickness of the flat inorganic particles are too large with respect to the width of the recess, the flat inorganic particles do not necessarily have to be arranged inside the recess. Further, the number density of the flat inorganic particles arranged inside the recess (the number per unit volume) may be different from the number density of the flat inorganic particles in the other blocking layers.

Adjacent flat inorganic particles bond to each other either directly or via a binder resin. Examples of cases where the flat inorganic particles are directly bonded to each other include a covalent bond as described later, a coordination bond, an ionic bond, a metal bond, a hydrogen bond, and the like. Further, when the flat inorganic particles are bonded to each other via the binder resin, the binder resin acts as a matrix and plays a role of holding the flat inorganic particles together.

The flat inorganic particles are preferably selected from known ceramic particles and mixtures thereof. Examples include particles of silica, alumina, mica, titania, zirconia, magnesia, molybdenum oxide, tungsten oxide, zinc oxide, tin oxide, barium titanate, aluminum titanate, silicon carbide, silicon nitride and the like. Among these, the flat inorganic particles are more preferably silica particles, alumina particles and mica particles having excellent mechanical strength and chemical stability. Further, dissimilar metal elements may be added to the flat inorganic particles for the purpose of improving mechanical strength and the like.

From the viewpoint of preventing the plasticizer from migrating to the outside, the flat inorganic particles are preferably scaly inorganic particles, and at least a part of the blocking layer is preferably a film formed by self-assembling the scaly inorganic particles.
Here, "self-organization" means that independent individual scaly inorganic particles function as a blocking layer due to their own physical properties without requiring any physical action or chemical influence from the outside. It means that it is united as an aggregate having. As described above, the film made of scaly inorganic particles has a high barrier property because there is no possibility that the plasticizer permeates and permeates the film unlike a general resin film. Further, since the film made of scaly inorganic particles is mechanically harder than the resin film, the strength of the exterior decorative sheet itself can be increased.
From the viewpoint of improving the barrier property, the entire blocking layer may be the self-assembled monolayer.

The scaly inorganic particles are scaly silica particles, and the self-assembled film may be a film in which adjacent scaly silica particles are bonded to each other by Si—O bonds.
Scaly silica particles usually have silanol groups (Si-OH) on their surface. Si-O bonds are formed by causing a dehydration condensation reaction between silanol groups between adjacent scaly silica particles. Since the Si—O bond is a covalent bond and can be said to be a bond generally stronger than other chemical bonds (for example, coordination bond, ionic bond, etc.), a strong self-assembling film is formed.
By using the scaly silica particles, a continuous self-assembled film can be formed under moist conditions. For example, a self-assembled monolayer is formed on the surface of a vinyl chloride resin base material by applying a water slurry containing scaly silica and drying to remove water. This coating method is superior to the film forming method by a vapor deposition method such as CVD in that a self-assembled monolayer can be easily obtained in a short time without requiring a complicated device.

Examples of the scaly silica particles include Sun Lovely LFS HN-150 (trade name) and Sun Lovely LFS HN-050 (trade name, manufactured by AGC Si-Tech Co., Ltd.).

The flat inorganic particles may be plate-like alumina particles or foil-like mica particles, or these may be used in combination. Plate-like alumina particles and foil-like mica particles have low self-assembling ability by themselves, and therefore require a binder to be formed as a film.
When plate-shaped alumina particles and / or foil-shaped mica particles are used, the total mass of the plate-shaped alumina particles and foil-shaped mica particles in the blocking layer is 50 to 99% by mass when the mass of the blocking layer is 100%. It is preferable to have. When the total mass of the plate-shaped alumina particles and the foil-shaped mica particles is less than 50% by mass, the amount of the binder is too large, so that the plasticizer may permeate and easily permeate. On the other hand, when the total mass of the plate-shaped alumina particles and the foil-shaped mica particles exceeds 99% by mass, the amount of the binder is too small, and the formability of the film may be deteriorated.
Examples of the plate-shaped alumina particles include Seraph 00160 (product name), Seraph 02050 (product name, manufactured by Kinsei Matek Co., Ltd.), Sera Sur BMF-B (product name, manufactured by Kawai Lime Industry Co., Ltd.), and the like. Be done.
Examples of foil-like mica particles include mica powder wet pulverized grade A-11 (trade name), mica powder hybrid pulverized fine particle grade (trade name, manufactured by Matsuo Sangyo Co., Ltd.), and non-swelling mica PDM-5B (trade name). , Toby Industry Co., Ltd.) and the like.

The binder resin may be a cured product of a curable resin. The binder resin may be a matrix composed of a cured product of the curable resin in the barrier layer.
The binder resin is not particularly limited, and is, for example, an ionizing radiation curable resin such as (meth) acrylate-based, epoxy-based, polyester-based, and thermosetting resin such as (meth) acrylate-based, urethane-based, epoxy-based, and polysiloxane-based. Examples thereof include various materials such as resins, (meth) acrylate-based, polyester-based, polycarbonate-based, polyethylene-based, and polypropylene-based thermoplastic resins, and various cured forms of molding resins. In addition, ionizing radiation means electromagnetic waves or charged particles having energy capable of polymerizing and curing molecules, and for example, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, and gamma rays. , X-ray, electron beam and the like.
Among these, an ionizing radiation curable resin and a thermosetting resin are preferably used from the viewpoint that a heat-resistant binder resin is more preferable for exterior use.
From the viewpoint of improving the adhesion between the vinyl chloride resin base material and the blocking layer, the binder resin is preferably a resin having high adhesion to the vinyl chloride resin base material. Further, from the viewpoint that the blocking layer plays a role of preventing the migration of the plasticizer, the binder resin in the blocking layer is preferably a resin having poor compatibility with the plasticizer.

The binder resin may be used together with scaly silica. When the flexibility of the blocking layer is poor with only the scaly silica particles, a binder resin can be added to reduce the content ratio of the scaly silica particles in the blocking layer to impart flexibility to the blocking layer. However, when the binder resin is used in combination, the barrier property against the plasticizer may be lower than when only the scaly silica particles are used.

When the scaly silica particles and the binder resin are used in combination, the mass of the scaly silica particles in the blocking layer is preferably 50% by mass or more and less than 100% by mass when the mass of the blocking layer is 100%. When the mass of the scaly silica particles is less than 50% by mass, the amount of the binder is too large, so that the plasticizer may permeate and easily permeate. On the other hand, since the scaly silica particles can be used alone, there is no upper limit to the content of the scaly silica particles unless flexibility is particularly considered.

From the viewpoint of preventing the migration of the plasticizer, the average thickness of the blocking layer is preferably in the range of 0.1 to 200 μm, more preferably in the range of 0.5 to 150 μm, and more preferably in the range of 0.5 to 150 μm. It is in the range of 1.0 to 100 μm.
If the average thickness of the barrier layer exceeds 200 μm, the exterior decorative sheet or its intermediate may be bent or broken during the manufacture of the exterior decorative sheet or during the handling of the finished exterior decorative sheet. As a result, the aligned structure of the flat inorganic particles in the barrier layer is likely to be impaired, and the barrier effect may be insufficient. On the other hand, when the average thickness of the blocking layer is less than 0.1 μm, a sufficient amount of flat inorganic particles are not contained in the blocking layer, so that a sufficient barrier effect may not be obtained.

It can be said that it is a necessary property for a decorative sheet that the blocking layer has adhesion to the other layer to the extent that it does not float or peel off from the other adjacent layer. When the average thickness of the blocking layer is within the range of 0.1 to 200 μm, the adhesion between the blocking layer and other adjacent layers can be ensured. In particular, when the average thickness of the blocking layer exceeds 200 μm, the barrier layer may be peeled off from other adjacent layers due to bending or folding of the exterior decorative sheet or its intermediate.
When the average thickness of the blocking layer is within the range of 0.1 to 200 μm, it can be said that the blocking layer and the other adjacent layers are adhered to each other. Here, "adhesion" means that the blocking layer and the other layer are bonded to each other to the extent that the blocking layer existing on the surface of the other layer is not removed even if it is rubbed or wiped by hand. It means that it is.

When the blocking layer is provided directly on the decorative surface of the polyvinyl chloride resin base material, it corresponds to the thickness of the blocking layer corresponding to the portion where the decorative surface is concave and the portion where the decorative surface is convex. The thickness of the barrier layer is different. Therefore, in such a case, the thickness of the blocking layer corresponding to the portion where the decorative surface is convex is measured, and the average thickness is calculated. The length indicated by the double-headed arrow 2A in FIGS. 4A to 4C described above corresponds to the thickness of the blocking layer corresponding to the portion where the decorative surface has a convex shape.

The adhesion between the blocking layer and another adjacent layer is evaluated by a peeling test, a bending test, a winding test, or the like.
An example of the test method of the peeling test is as follows. First, in the exterior decorative sheet or its intermediate (hereinafter, these may be referred to as "exterior decorative sheet or the like"), when all or a part of the blocking layer appears on the surface, the blocking layer Stick the adhesive tape on and peel it off. After that, visually check whether the blocking layer of the portion to which the adhesive tape is attached is cracked, floated, or peeled off. When the blocking layer does not appear on the surface of the exterior decorative sheet or the like, the following bending test or wrapping test may be performed.
An example of the test method of the bending test is as follows. First, fold the exterior decorative sheet or the like in half. After that, the exterior decorative sheet or the like is returned to the original state, and visually confirm whether the barrier layer is cracked, floated, or peeled off.
An example of the test method of the winding test is as follows. First, wrap an exterior decorative sheet or the like around a round bar having a diameter of 2 mm and squeeze it several times. After that, in the exterior decorative sheet or the like, visually check whether the barrier layer is cracked, floated, or peeled off.
In the bending test and the wrapping test, when the blocking layer is inside the exterior decorative sheet or the like, the cracking of the blocking layer is determined from the cross section of the exterior decorative sheet or the like.

The above test may be performed based on a known test method. For example, the peeling test may be performed in accordance with JIS 8504: 1999 15.1 (tape test method) or the corresponding ISO 2819 (peeling test). The bending test may be performed in accordance with JIS 8504: 1999 18 (bending test method) or the corresponding ISO 2819 (bending test). The wrapping test may be performed in accordance with JIS 8504: 1999 19 (wrapping test method) or the corresponding ISO 2819 (wrapping test).

4. Transparent Resin Layer The exterior decorative sheet of the present invention preferably further includes a transparent resin layer on one side of the laminate having the above-mentioned polyvinyl chloride resin base material, decorative portion, and blocking layer.
In particular, when a decorative layer is provided, when the decorative layer is exposed to the atmosphere, the decorative layer may be deteriorated, peeled off, or fallen due to water (rain), air (particularly oxygen), ultraviolet rays, and heat. Further, the same problem may occur when the polyvinyl chloride resin base material containing the colorant is exposed to the atmosphere. Therefore, in order to prevent deterioration of the decorative layer and fading of the polyvinyl chloride resin base material and to protect the entire laminate, it is preferable to cover the surface of the laminate with a transparent resin layer.

The material used for the transparent resin layer is not particularly limited as long as it can prevent the above-mentioned physical damage and chemical deterioration of the laminate, and examples thereof include acrylic resins and olefin resins. Examples of acrylic resins include polyacrylic acid esters (methyl polyacrylic acid, ethyl polyacrylic acid, propyl polyacrylic acid, butyl polyacrylic acid, etc.) and polymethacrylic acid esters (methyl polymethacrylate, ethyl polymethacrylate, poly). Examples thereof include propyl methacrylate, polybutyl methacrylate, etc.), and copolymers thereof. Examples of the olefin resin include polypropylene, polyethylene, polybutene, and an ethylene-propylene copolymer.

In order to reinforce the function required as the surface layer of the decorative sheet, the transparent resin layer contains various additives, reinforcing agents, fillers, for example, ultraviolet absorbers, light stabilizers, heat-resistant stabilizers, and antioxidants, if desired. Agents, antistatic agents, flame retardants, etc. are added.

Weatherproofing agents such as ultraviolet absorbers and light stabilizers are for imparting good weather resistance (light resistance) to the resin, and the amount of the added amount is usually 0.1 to 5 for both the ultraviolet absorber and the light stabilizer. It is about mass%. In general, it is preferable to use an ultraviolet absorber and a light stabilizer in combination. Examples of the ultraviolet absorber include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine and 2- (2-hydroxy-4-hexyloxyphenyl). ) -4,6-Diphenyl-s-triazine and other triazines, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dithr) In addition to benzotriazole-based benzotriazole-based agents such as butylphenyl) -5-chlorobenzotriazole, organic-based ultraviolet absorbers such as benzophenone-based and salicylate ester-based agents, fine-grained zinc oxide, cerium oxide, and titanium oxide having a particle size of 0.2 μm or less. Inorganic UV absorbers such as the above can also be used. Examples of the light stabilizer include bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. Hindered amine radical scavengers can be used.

A transparent resin film is obtained by forming a film of a mixture of these materials by a usual method such as a calendar manufacturing method. This transparent resin film is used for forming the transparent resin layer. The thickness of the transparent resin film is about 50 to 100 μm, preferably about 80 μm.
The method for forming the transparent resin layer is not particularly limited. For example, a method of sticking a transparent resin film on one side of a laminate provided with a polyvinyl chloride resin base material and a blocking layer using an adhesive or the like can be mentioned. Further, a method in which a decorative layer is coated and formed on one side of a transparent resin film is attached to one side of a laminate provided with a polyvinyl chloride resin base material and a blocking layer.

5. Top coat layer A top coat layer may be further provided on top of the transparent resin layer. The top coat layer is a layer formed of a thermosetting resin, an ionizing radiation curable resin, or the like. After applying these resins from above the transparent resin layer, the resins are cured by applying heat or irradiating ionizing radiation to form a top coat layer. Examples of the thermosetting resin and the ionizing radiation curable resin are as described above.

6. Layer structure The exterior decorative sheet of the present invention is not particularly limited as long as it includes a polyvinyl chloride resin base material, a decorative portion, and a blocking layer.
Hereinafter, embodiments of the laminate including the polyvinyl chloride-based resin base material, the decorative portion, and the blocking layer will be described with reference to FIGS. 5 to 8. The layer structure of the laminated body is not limited to the embodiments shown in FIGS. 5 to 8. Further, the embodiments shown in FIGS. 5 to 8 include both the case where the polyvinyl chloride resin base material contains and the case where the colorant is not contained.

FIG. 5 is a schematic cross-sectional view of a laminate provided with a polyvinyl chloride resin base material, a decorative layer, and a blocking layer.
The blocking layer 2 may be provided between the polyvinyl chloride resin base material 1 and the decorative layer 3 (FIG. 5 (A)). On the contrary, the blocking layer 2 may be provided on the side opposite to the decorative layer 3 with the polyvinyl chloride resin base material 1 interposed therebetween (FIG. 5 (B)).
When the blocking layers 2 are provided on both sides of the polyvinyl chloride resin base material 1, the decorative layer 3 may be further provided on the outside of one of the blocking layers 2 (FIG. 5 (C)). ), The decorative layer 3 may be provided on the outside of both of the blocking layers 2 (FIG. 5 (D)). Further, the blocking layer 2 may be provided on one surface of the polyvinyl chloride resin base material 1, and the decorative layers 3 may be provided on both sides of the laminate.
When the decorative layer 3 is provided on a part of the side of one surface of the polyvinyl chloride resin base material 1, the blocking layer 2 may be provided on that surface (FIG. 5 (E)). .. The blocking layer 2 may be provided on the surface of the polyvinyl chloride resin base material 1 facing the side of the surface on which the decorative layer 3 is provided.
When the decorative layer 3 is provided on a part of one side of the polyvinyl chloride resin base material 1 and the decorative layer 3 is provided on the entire surface of the other surface, the blocking layers 2 are provided on both sides of the decorative layer 3. It may be (FIG. 5 (F)). Further, the blocking layer 2 may be provided on either one of these two surfaces.
When the decorative layer 3 is provided on a part of both sides of the polyvinyl chloride resin base material 1, the blocking layer 2 may be provided on both sides of the decorative layer 3 (FIG. 5 (G)). .. Further, the blocking layer 2 may be provided on either one of these two surfaces.

As described above, the blocking layer may be provided between the polyvinyl chloride resin base material and the decorative layer (FIGS. 5 (A) and (C) to (G)), and the polyvinyl chloride resin. It may be provided on the side opposite to the decorative layer with the base material interposed therebetween (FIG. 5 (B)). The blocking layer may be provided in contact with the decorative layer (FIGS. 5 (A) and (C) to (G)). The blocking layer may be provided on both sides of the polyvinyl chloride resin base material (FIGS. 5 (C), (D), (F) and (G)).
In FIGS. 5 (A) and 5 (C) to (G), since the blocking layer is arranged inside the decorative layer, it is preferable in that the pattern and color of the decorative layer easily appear on the surface of the exterior decorative sheet. ..

FIG. 6 is a schematic cross-sectional view of another laminate provided with a polyvinyl chloride resin base material, a decorative layer, and a blocking layer.
The blocking layer 2 may be provided on the side opposite to the polyvinyl chloride resin base material 1 with the decorative layer 3 interposed therebetween (FIG. 6 (A)).
When the decorative layer 3 and the blocking layer 2 are provided in this order on one surface of the polyvinyl chloride resin base material 1, the blocking layer 2 may be provided on the other surface (FIG. 6 (B)). The blocking layer 2 and the decorative layer 3 may be provided on the other surface in this order (FIG. 6C), or the decorative layer 3 and the decorative layer 2 may be provided on the other surface in this order (in this order). FIG. 6 (D).
When the decorative layer 3 is provided on a part of one surface of the polyvinyl chloride resin base material 1, a blocking layer 2 may be further provided on the surface (FIG. 6 (E)). When the decorative layer 3 is provided on a part of one surface of the polyvinyl chloride resin base material 1 and the decorative layer 3 is provided on the entire surface of the other surface, even if the blocking layers 2 are provided on both sides of the decorative layer 3. Good (Fig. 6 (F)).
When the decorative layer 3 is provided on a part of both surfaces of the polyvinyl chloride resin base material 1, the blocking layer 2 may be provided on both surfaces thereof (FIG. 6 (G)). Further, the blocking layer 2 may be provided on either one of these two surfaces.

As described above, the blocking layer may be provided between the polyvinyl chloride-based resin base material and the decorative layer (FIG. 6 (C)), or the polyvinyl chloride-based resin base material may be sandwiched between the decorative layer. May be provided on opposite sides (FIGS. 6 (A), (B) and (D)-(G)). The blocking layer may be provided in contact with the decorative layer (FIGS. 6A to 6G). The blocking layer may be provided on both sides of the polyvinyl chloride resin base material (FIGS. 6 (B) to (D), (F) and (G)).

FIG. 7 is a schematic cross-sectional view of a polyvinyl chloride resin base material having a decorative surface and a laminate having a barrier layer. In FIGS. 7 and 8, the uneven portion of the polyvinyl chloride resin base material 1 means a decorative treatment formed on the surface of the base material 1. This decorated portion becomes a decorative surface.

The blocking layer 2 may be provided on the side of the decorative surface of the polyvinyl chloride resin base material 1 (FIG. 7 (A)). On the contrary, the blocking layer 2 may be provided on the surface opposite to the decorative surface (FIG. 7 (B)).
When all of both sides of the polyvinyl chloride resin base material 1 are decorative surfaces, a blocking layer 2 may be provided on one of the surfaces (FIG. 7 (C)), or the blocking layer 2 may be provided on both sides. May be provided (FIG. 7 (D)).
When a part of one surface of the polyvinyl chloride resin base material 1 is a decorative surface, the blocking layer 2 may be provided on that surface (FIG. 7 (E)). The blocking layer 2 may be provided on a surface facing the decorative surface.
When a part of one surface and the entire other surface of the polyvinyl chloride resin base material 1 are decorative surfaces, the blocking layers 2 may be provided on both sides of the polyvinyl chloride resin base material 1 (). FIG. 7 (F). Further, the blocking layer 2 may be provided on either one of the polyvinyl chloride resin base materials 1.
When a part of both surfaces of the polyvinyl chloride resin base material 1 is a decorative surface, barrier layers 2 may be provided on both sides of the polyvinyl chloride resin base material 1 (FIG. 7 (G)). ). Further, the blocking layer 2 may be provided on either one of the polyvinyl chloride resin base materials 1.

As described above, the blocking layer may be provided on the side opposite to the decorative surface with the polyvinyl chloride resin base material interposed therebetween (FIG. 7 (B)). The blocking layer may be provided in contact with the decorative surface (FIGS. 7 (A) and (C) to (G)). The blocking layer may be provided on both sides of the polyvinyl chloride resin base material (FIGS. 7 (D), (F) and (G)).

FIG. 8 is a schematic cross-sectional view of a laminate including a polyvinyl chloride resin base material having a decorative surface, a decorative layer, and a blocking layer.
In FIG. 8A, one surface of the polyvinyl chloride resin base material 1 is a decorative surface, a decorative layer 3 is provided on the other surface, and a blocking layer 2 is further provided on both sides. Indicates a laminated body.
In FIG. 8B, a part of one surface of the polyvinyl chloride resin base material 1 is a decorative surface, and the blocking layer 2 is provided on both sides of the resin base material 1, and the decorative layer is further provided on both sides of the resin base material 1. The laminate in which 3 is provided is shown. On one surface of the polyvinyl chloride resin base material 1, a decorative layer 3 is provided on a portion other than the decorative surface.
In the laminates shown in FIGS. 8C to 8E, all or a part of both sides of the polyvinyl chloride resin base material 1 is a decorative surface, and a blocking layer 2 is provided on the outside of both sides thereof. There is. Of these, in the laminate shown in FIG. 8C, the decorative layer 3 is provided on a portion other than the decorative surface on one surface of the polyvinyl chloride resin base material 1. Further, in the laminate shown in FIG. 8D, decorative layers 3 are provided on the portions of both surfaces of the polyvinyl chloride resin base material 1 other than the decorative surfaces. Further, in the laminate shown in FIG. 8 (E), a decorative layer 3 is provided on a part of the polyvinyl chloride resin base material 1 other than the decorative surface on both surfaces.

A transparent resin layer and, if necessary, a top coat layer are further provided in this order on at least one surface side of the laminate shown in FIGS. 5 to 8 to complete the exterior decorative sheet of the present invention. FIGS. 5 to 8 show an embodiment in which the area of the blocking layer is equal to the area of the polyvinyl chloride resin base material, but the area of the blocking layer may be smaller than the area of the polyvinyl chloride resin base material. Good. That is, the blocking layer may be provided only on a part of the polyvinyl chloride resin base material.
FIG. 9 is a schematic cross-sectional view of an embodiment of the exterior decorative sheet of the present invention. The laminated body 10 in FIG. 9 corresponds to the laminated body 10 of FIG. 5 (C). In the laminated body 10, the transparent resin layer 4 and the top coat layer 5 are further provided in this order on the side facing the decorative layer 3, to obtain the exterior decorative sheet 100.
The present invention is not limited to the structure shown in FIG.

The layer structure of the exterior decorative sheet can be appropriately selected according to the object (adhesive body) on which the decorative sheet is installed. For example, when the adherend is an inorganic substance such as a metal, the plasticizer is mainly transferred to the front side exposed to the atmosphere (the surface opposite to the adherend), so that the blocking layer is on the front side. Should be provided. On the other hand, when the adherend is an organic substance, the plasticizer easily migrates to the adherend, so that the blocking layer is preferably provided between the polyvinyl chloride resin base material and the adherend. However, even if the adherend is an inorganic substance, when the exterior decorative sheet and the adherend are joined by an adhesive, the plasticizer moves toward the adhesive and covers the exterior decorative sheet. A blocking layer is also required on the side of the joint surface because it may adversely affect the adhesiveness to the body.
As described above, the necessity of the blocking layer is determined by whether or not the material in contact with the exterior decorative sheet is a material through which the plasticizer easily permeates. Therefore, it is inherently preferable to provide blocking layers on both sides of the polyvinyl chloride resin base material. However, if the blocking layer is provided for two surfaces, there may be a problem of cost and a problem of adhesion inside the laminated structure of the exterior decorative sheet. Therefore, an exterior decorative sheet having a blocking layer on both sides is used for an adherend to which the plasticizer is easily transferred, and an exterior decorative sheet having a blocking layer on one side is used for an adherend to which the plasticizer is difficult to transfer. The exterior decorative sheet having a different layer structure may be used properly.

The average thickness of the exterior decorative sheet is not particularly limited, and is generally about 10 μm to 1,000 μm, preferably 50 μm to 300 μm.

7. Use of Decorative Sheet The decorative sheet of the present invention is not particularly limited as long as it is for exterior use, and is used for surface makeup of various adherends. The adherend includes flat plates of various materials for exteriors, plate materials such as curved plates, three-dimensional articles, and articles of various shapes such as sheets (or films). For example, as a material used as a plate material or a three-dimensional shape article, a wood plate material such as a wood single plate, a wood plywood, a particle board, a wood fiber plate such as MDF (medium density fiber plate), or a glass, ceramics, etc. There are non-cement ceramic materials such as ceramics and plaster, and ceramic materials such as non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates. Metal materials such as aluminum, acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber, etc. There are resin materials, and the materials used exclusively as sheets include papers such as high-quality paper and Japanese paper, and non-woven fabrics or woven fabrics made of fibers such as carbon, asbestos, glass, and synthetic resin.

Examples of the method of laminating the decorative sheet on these various adherends include a method of laminating the decorative sheet by pressing it on a plate-shaped base material with an adhesive between them with a pressure roller, and a method of laminating the decorative sheet on both male and female molds of injection molding. After arranging in between, the molten resin is injection-filled in the mold, and a decorative sheet is adhered and laminated on the surface of the resin molded product at the same time, so-called injection molding simultaneous laminating method, on the surface of three-dimensional articles such as molded products. A so-called vacuum press laminating method, in which a decorative sheet is placed facing or placed between them via an adhesive, and the decorative sheet is laminated on the surface of the three-dimensional article by a pressure difference due to vacuum suction from the three-dimensional article side, a columnar, many. While supplying the decorative sheet in the long axis direction of the columnar base material such as a square pillar via an adhesive layer, the decorative sheet is sequentially added to a plurality of side surfaces constituting the columnar base material by a plurality of rollers having different orientations. There is a so-called wrapping processing method in which pressure bonding is performed and lamination is performed.

As a further processing method for a decorative sheet made by laminating decorative sheets, first, the decorative sheet is laminated on a plate-shaped base material via an adhesive layer to form a decorative board, which is opposite to the decorative sheet. On the side surface, a groove having a V-shaped or U-shaped cross section that reaches the interface between the decorative sheet and the plate-shaped base material is cut, and then an adhesive layer is applied in the groove, and then the groove is formed. There is a so-called V-cut or U-cut processing method for forming a folded box or columnar body.

When the adherend is a plate material, the laminate of decorative sheets is used as a decorative plate, and when the adherend is a sheet, the laminate itself may also be used as a decorative sheet. Articles made by laminating decorative sheets include, for example, exteriors of buildings such as outer walls, fences, and roofs, surface makeup of fittings such as window frames, door frames, doors, and handrails, automobiles, trains, and aircraft. It is used as an interior of a vehicle such as a ship, or as a decorative window glass.

1. 1. Manufacture of Laminated Body [Example 1]
In order to evaluate the degree of bleed-out of the plasticizer, a laminate in which a blocking layer was laminated on one surface of a polyvinyl chloride resin base material was produced.

First, a vinyl chloride-based resin base material having a thickness of 120 μm was prepared by forming a film by a calendar manufacturing method using a vinyl chloride compound Vinica (trade name, manufactured by Mitsubishi Chemical Corporation) containing a plasticizer.

The ink for the barrier layer was prepared by the following method. First, as an aqueous slurry containing flat inorganic particles, a silica aqueous dispersion (Sun Lovely LFS HN-050 (trade name), manufactured by AGC Si-Tech Co., Ltd., solid content 15%) was prepared. This silica aqueous dispersion was diluted 2-fold with ethanol to obtain an ink for a blocking layer.

The ink for the barrier layer was applied to one surface of the polyvinyl chloride resin base material using an applicator, and dried in the air at room temperature overnight. A blocking layer containing scaly silica particles derived from an aqueous silica dispersion was formed on one surface of a polyvinyl chloride resin base material.
The cross section of the obtained laminate was observed with an electron microscope, the thickness of the blocking layer was measured at about 10 points, and the average was calculated. As a result, the average thickness of the blocking layer was 1.0 μm.

[Example 2-Example 10]
Similar to Example 1, a laminate in which a blocking layer was laminated on one surface of a polyvinyl chloride resin base material was produced except that the coating amount of the blocking layer ink was changed (Example 2-Example). 10). The average thickness of the blocking layer in Example 2-Example 10 is shown in Table 1 below.

[Comparative Example 1]
For comparison, the polyvinyl chloride-based resin base material itself on which the barrier layer was not formed was subjected to the following analysis and test.

2. FT-IR analysis The laminates of Examples 1 to 10 were sandwiched between two olefin sheets and brought into close contact with each other. Further, by sandwiching the obtained laminate between two glass plates, an evaluation having a six-layer structure (glass plate / olefin sheet A / blocking layer / polyvinyl chloride resin base material / olefin sheet B / glass plate) is obtained. A laminate for use was prepared.
Similarly, the polyvinyl chloride resin base material of Comparative Example 1 is also sandwiched between two olefin sheets and two glass plates, and has a five-layer structure (glass plate / olefin sheet / polyvinyl chloride resin base material / An evaluation laminate having an olefin sheet / glass plate) was prepared.

Each evaluation laminate was allowed to stand in a drying oven at 80 ° C. Two days later, the evaluation laminate was removed from the drying oven and cooled to room temperature. Two glass plates and two olefin sheets were peeled off from both sides of the evaluation laminate.
(A) Surface of olefin sheet not used for evaluation laminate, (b) Contact surface of olefin sheet A with barrier layer, (c) Contact surface of olefin sheet B with polyvinyl chloride resin base material , FT-IR analysis was performed. The results of Example 7 are shown in FIG.
FT-IR analysis was also performed on both sides of the polyvinyl chloride resin base material that was not used in the evaluation laminate. The result is shown in FIG.

The transfer amount of the plasticizer in each evaluation laminate was determined by the following method. First, in the FT-IR spectrum of the olefin sheet, one reference peak was determined at a wavelength different from ^{1730 cm -1.} Next, in the FT-IR spectrum of the olefin sheet used for the evaluation laminate of Comparative Example 1, the peak area A _{0 of} ^{the infrared absorption peak (around 1730 cm -1} ) derived from the plasticizer and the peak area of the reference peak were described. B ₀ was calculated respectively.
On the other hand, in the FT-IR spectrum of the olefin sheet A used for the evaluation laminate of Examples 1 to 10, the peak area A _x (x = ^{) of the infrared absorption peak (around 1730 cm -1) derived from the plasticizer.} 1 to 10) and the peak area B _x (x = 1 to 10) of the reference peak were calculated, respectively. Here, the number x corresponds to the embodiment number.
The plasticizer transfer amount P (%) was calculated by the following formula 1. The amount of plasticizer transferred to the evaluation laminate of Comparative Example 1 was 100%.
Equation 1: P = [(A _x / B _x ) / (A ₀ / B ₀ )] × 100
(In the above formula 1, P indicates the amount of plasticizer transfer (%), and A _x , B _x , A ₀ , and B ₀ indicate the respective peak areas described above.)

3. 3. Adhesion Evaluation With respect to the laminate of Example 1 to Example 10, the adhesion of the barrier layer to the polyvinyl chloride resin base material was evaluated by the following test.
Each laminate was wound around a round bar having a diameter of 2 mm so that the blocking layer was located on the outside, and after squeezing several times, it was visually confirmed whether the blocking layer was cracked, floated, or peeled off (rolling). Attached test). Subsequently, after folding in half so that the barrier layer was located on the outside, it was visually confirmed whether the barrier layer was damaged in the same manner (bending test).
Adhesion was evaluated based on the following criteria.
A: No cracking, floating or peeling of the barrier layer was observed in either the winding test or the bending test.
B: By either the winding test or the bending test, a symptom of cracking, floating, or peeling was observed in a part of the blocking layer.
C: Most of the barrier layer collapsed in both the winding test and the bending test.
F: The entire barrier layer was completely cracked and crushed by both the winding test and the bending test.

4. Discussion FIG. 11 is a graph showing the FT-IR spectra of one surface and the other surface of the polyvinyl chloride resin base material side by side. ^{The peak (around 1730 cm -1} ) indicated by the arrow in FIG. 11 indicates infrared absorption derived from the plasticizer. From FIG. 11, ^{the intensities of the peaks near 1730 cm -1} are the same in all aspects as compared with the intensities of the other peaks. Therefore, it can be said that the amount of the plasticizer exuding from the polyvinyl chloride resin base material is almost the same in any aspect of the base material.

FIG. 10 shows (a) the surface of the olefin sheet not used in the evaluation laminate, (b) the contact surface with the blocking layer in the olefin sheet A, and (c) the polyvinyl chloride resin base material in the olefin sheet B. It is a graph which showed each FT-IR spectrum of the contact surface side by side. FIG. 10 is the result of Example 7. The above (a) to (c) correspond to the spectra (a) to (c) in FIG. ^{In FIG. 10, the vicinity of 1730 cm -1} where the infrared absorption peak derived from the plasticizer appears is shown by enclosing it in a broken line frame.
First, from the spectrum (a) of FIG. 10, it was confirmed that the plasticizer did not exude from the unused olefin sheet. ^{Next, the peak intensity near 1730 cm -1} in the spectrum (b) of FIG. 10 is clearly weaker than the peak intensity near ^{1730 cm -1} in the spectrum (c) of FIG. ^{This is also clear when comparing the peak intensity ratio near 1730 cm -1 with} respect to the intensity of other peaks (for example, ^{the peak near 2920 cm -1} ) between the spectra (b) and (c). From this result, it can be seen that the amount of the plasticizer exuded to the olefin sheet A is smaller than the amount of the plasticizer exuded to the olefin sheet B.
From the above, it was demonstrated that the blocking layer can suppress the amount of bleed-out of the plasticizer from the polyvinyl chloride resin base material to the outside.

From Table 1 above, comparing each plasticizer transfer amount P of Example 1 and Comparative Example 1, it can be seen that the plasticizer can be blocked by as much as 7% by providing a blocking layer having an average thickness of 1.0 μm. Further, comparing the average thickness of the blocking layers of Examples 1 to 10 with the plasticizer transfer amount P, it can be seen that the plasticizer transfer amount P decreases as the average thickness of the blocking layer increases. Therefore, it was demonstrated that the thicker the barrier layer on the surface of the polyvinyl chloride resin base material, the more difficult it is for the plasticizer to migrate.
Although the correlation is not always clear, from the results in Table 1 above, for example, the amount of plasticizer transferred is halved in order to double the durability as compared with the conventional decorative sheet without a blocking layer. If it is necessary to set it to 1, it is presumed that the average thickness of the blocking layer needs to be 10 μm or more.

On the other hand, from Table 1 above, when the average thickness of the blocking layer was sufficiently thin (Examples 1 to 7), no cracking of the blocking layer was observed, so that the surface of the polyvinyl chloride resin base material was not observed. On the other hand, it can be said that the blocking layer exhibits excellent adhesion. Further, even when the average thickness of the blocking layer is relatively thick (Examples 8 to 10), only a part of the blocking layer is cracked or the like, so that it can be used as an exterior decorative sheet. It is considered that the required level of adhesion is satisfied.

1 Polyvinyl chloride resin base material 1a Side surface of the polyvinyl chloride resin base material provided with the blocking layer 1b Bottom of the recess of the decorated polyvinyl chloride resin base material 2 Blocking layer 2A Thickness of the blocking layer 3 Decorative layer 4 Transparent resin layer 5 Top coat layer 10 Laminate with at least a polyvinyl chloride resin base material and a blocking layer 12 Flat inorganic particles 12a Bottom surface of flat inorganic particles 100 Exterior decorative sheet α, β Flat inorganic particles The angle between the bottom surface of the

Claims (7)

A polyvinyl chloride-based resin base material containing a plasticizer, a decorative layer arranged on the side of at least one of the surfaces of the polyvinyl chloride-based resin base material, and the surface of the polyvinyl chloride-based resin base material. An exterior decorative sheet comprising at least one decorative portion selected from the group consisting of decorative surfaces, all or part of which is directly decorated.
A blocking layer is further provided on the side of at least one surface of the polyvinyl chloride resin base material.
The entire blocking layer is a film formed by self-assembling scaly inorganic particles, and in the blocking layer, the bottom surface of the scaly inorganic particles is the side of the polyvinyl chloride resin base material provided with the blocking layer. The scaly inorganic particles aligned in parallel or substantially parallel to the plane of the surface and adjacent to each other are directly bonded to each other, and the average thickness of the blocking layer is in the range of 1.0 to 100 μm. An exterior decorative sheet that is characterized by this. The scaly inorganic particles are scaly silica particles, and the scaly inorganic particles are
The exterior decorative sheet according to claim 1 , wherein the self-assembled film is a film in which adjacent scaly silica particles are bonded to each other by a Si—O bond. The exterior decorative sheet according to claim 1 or 2 , further comprising the blocking layer in contact with the decorative portion. The exterior decorative sheet according to any one of claims 1 to 3 , wherein the blocking layer is provided on the side opposite to the decorative portion with the polyvinyl chloride resin base material interposed therebetween. At least the decorative layer is provided as the decorative portion, and the decorative layer is provided.
The exterior decorative sheet according to any one of claims 1 to 4 , further comprising the blocking layer between the polyvinyl chloride resin base material and the decorative layer. The exterior decorative sheet according to any one of claims 1 to 5 , further comprising blocking layers on both sides of the polyvinyl chloride resin base material. The exterior decorative sheet according to any one of claims 1 to 6 , further comprising a transparent resin layer on one surface side of the laminate having the polyvinyl chloride resin base material, the decorative portion and the blocking layer.

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