JP2017113980A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make positioning and rearrangement of a decorative sheet arranged on a target to be adhered.SOLUTION: A decorative sheet 1 has a substrate layer 2 and an adhesive layer 3 laminated on a surface 2a of the substrate layer 2 and having an adhesive agent. The adhesive layer 3 has a plurality of projections 10 arranged on a main surface 3a in opposite side to the surface 2a of the substrate layer 2. The projections 10 have an apex 12a with an acuminate shape on a tip 12. Shear storage elastic modulus of the adhesive layer 3 at 20°C is 2.0×10or more.SELECTED DRAWING: Figure 4

Description

  One aspect of the present invention relates to a decorative sheet used as an interior / exterior decorative material.

  A stretchable polymer film (for example, refer to Patent Document 1) for decorative use in which a pressure-sensitive adhesive having a fine structure is bonded to the surface is known.

Japanese Patent No. 3550096

  When this type of film is used as a decorative material for interior and exterior and is attached to a base material that has been subjected to primer treatment or the like, high adhesive strength can be expected and it is difficult to peel off. As a result, once it is pasted, subsequent position adjustment (Slidability) and rearrangement (Repositionability) become difficult, and skill level is required for construction, and further improvement and improvement are necessary for improving workability.

One embodiment of the present invention is a decorative sheet for interior and exterior, and includes a base material layer and a pressure-sensitive adhesive layer that is laminated on the surface of the base material layer and has a pressure-sensitive adhesive. It has a plurality of protrusions provided on the main surface opposite to the surface of the material layer, the protrusion has a pointed apex at the tip, and the shear storage modulus of the adhesive at 20 ° C. is 2 0.0 × 10 ⁵ or more.

When this decorative sheet is arranged on an adherend target object such as a base material to which a primer is applied, the pressure-sensitive adhesive layer comes into contact with the adherend target object via a plurality of top portions. That is, the pressure-sensitive adhesive layer is substantially in a state where a plurality of protrusions are in point contact or line contact with the object to be bonded, and compared with the state in which the surface is in contact with the adhesive layer and the object to be bonded. The contact area is reduced. In particular, in this decorative sheet, since the shear storage elastic modulus at 20 ° C. of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is 2.0 × 10 ⁵ or more, unless an external pressing force is applied to the pressure-sensitive adhesive layer. The plurality of protrusions are not easily crushed and have high shape stability. As a result, it is easy to slide the decoration sheet along the object to be adhered in a state where the decoration sheet is simply arranged on the object to be adhered, for example, in a temporary placement state, and it is easy to peel the decoration sheet from the object to be adhered. . That is, position adjustment and rearrangement can be easily performed as long as the decorative sheet is simply placed on the adherend.

  According to one aspect of the present invention, the position adjustment and rearrangement of the decorative sheet disposed on the adherend object are facilitated.

It is sectional drawing which shows one Embodiment of the decoration sheet which concerns on this invention. It is a cross-sectional perspective view which shows the protrusion of the adhesive layer in the decoration sheet shown in FIG. (A) is an expanded sectional view which shows the protrusion shown in FIG. (B) is an expanded sectional view showing a projection concerning a modification. (A) is sectional drawing which shows the state which temporarily set | placed the decoration sheet shown in FIG. 1 along a base material. (B) is sectional drawing which shows the state which gave the pressing force with respect to the base material about the decoration sheet shown to (a). It is a graph which shows the shear storage elastic modulus of an adhesive. It is a cross-sectional perspective view which shows the protrusion of the adhesive layer in other embodiment of the decoration sheet which concerns on this invention. (A) is a cross-sectional perspective view which shows the protrusion of the adhesive layer which concerns on the comparative example 2. FIG. (B) is an expanded sectional view which shows the protrusion shown to (a).

  Embodiments of the present invention will be described below with reference to the accompanying drawings. In the following description, the same or equivalent elements will be denoted by the same reference numerals, and redundant description will be omitted.

  The term “decorative sheet” in the present specification broadly includes sheet-like decorative materials used for architectural purposes. “Interior / exterior” means not only cosmetic materials that can be applied to indoor floors, walls, ceilings, etc., but also those that can be applied to eaves, which are considered to be outdoors. included. The “pressure-sensitive adhesive layer” is an adhesive layer having a pressure-sensitive adhesive that bonds the decorative sheet to the base material. The “projection” is a part of the pressure-sensitive adhesive layer that projects toward the side opposite to the surface of the base material layer. “Pointed shape” means a shape with a sharp tip, excluding a shape with a flat tip, but is not limited to a cone with a single point, but a sharp tip with a ridge shape Continuous shapes are also included. Microscopically, a shape having a curved tip is also included.

  FIG. 1 is a cross-sectional view showing an embodiment of a decorative sheet according to the present invention. As shown in FIG. 1, the decorative sheet 1 includes a base material layer 2 and a pressure-sensitive adhesive layer 3 laminated on the surface 2 a of the base material layer 2. The decorative sheet 1 may include a liner 4 on the main surface 3a of the pressure-sensitive adhesive layer 3 opposite to the base material layer 2. The liner 4 is, for example, release paper or the like, and protects the adhesive layer 3 when not used.

  In the decorative sheet 1, for example, the liner 4 is peeled off from the main surface 3 a of the pressure-sensitive adhesive layer 3 so that the main surface 3 a is exposed and disposed along the base material 6. The base material 6 is an article (target object) to which the decorative sheet 1 is bonded. When the decorative sheet 1 is used as an interior / exterior decorative material, the base material 6 is, for example, a plaster board. A primer 7 for improving the adhesive force between the pressure-sensitive adhesive layer 3 and the base material 6 may be applied to the base material 6. In the following description, not only the base material 6 to which the primer 7 is not applied but also the base material 6 to which the primer 7 is applied may be simply referred to as “base material 6”.

  The base material layer 2 is a layer that includes the base material of the decorative sheet 1 and a film member that serves as a base to be decorated or colored for the purpose of decorating the base material 6 as necessary. The base material layer 2 itself may be colored by containing a pigment, or may be transparent. Moreover, the base material layer 2 may include a printing layer on which a printing pattern for decoration is formed. The printed pattern can be formed on the film member using a toner or an ink colorant. The printed pattern can be formed by using a printing technique such as gravure printing, electrostatic printing, screen printing, inkjet printing, offset printing, or the like.

  The polymer (resin) contained in the base material of the base material layer 2 is at least selected from the group consisting of polyvinyl chloride (PVC), polyurethane, polyethylene, polypropylene, vinyl chloride-vinyl acetate, acrylic, cellulose, and fluororesin. One type is mentioned. The film member may be a single layer or a laminate of a plurality of layers. The polymer used in the base material layer 2 is preferably polyvinyl chloride. In this case, diethylhexyl phthalate (DOP) plasticizer, trimellitic acid plasticizer, polyester plasticizer and the like may be included as a plasticizer. The addition amount of the plasticizer is 5% by weight or more and 40% by weight or less, preferably 25% by weight, based on the resin. If the amount of the plasticizer is too large, the mechanical strength of the base material layer 2 is lowered and sufficient scratch resistance and wear resistance cannot be obtained. On the other hand, if the amount of the plasticizer is too small, the flexibility of the base material layer 2 is obtained. The follow-up to the third-order curved surface is deteriorated and the workability is deteriorated as a result. Furthermore, as stabilizers, stabilizers such as Ba stabilizers, Zn stabilizers and antioxidants are 0.5% by weight to 8% by weight, preferably 1% by weight to 3% by weight, based on the resin. The processing aids such as ethylene / vinyl acetate copolymer (EVA) and polymethyl methacrylate (PMMA) are contained in an amount of 1 to 10% by weight, preferably 3 to 5% by weight based on the resin. % Or less.

  The base material layer 2 may have a bright layer. The bright layer is made of aluminum, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead, zinc, etc. formed on the base material layer 2 by vacuum deposition, sputtering, ion plating, plating, etc. A metal thin film containing a metal such as germanium, an alloy or a compound thereof may be included.

  The base material layer 2 has a surface 2a on which the pressure-sensitive adhesive layer 3 is laminated and a surface opposite to the surface 2a. Hereinafter, the opposite surface is referred to as a back surface 2b for convenience. The base material layer 2 may have a back surface protective layer on the back surface 2b. The back protective layer is made of a resin film such as polyester such as polyethylene terephthalate (PET), polyvinyl chloride, polyimide, polyurethane, acrylic resin, epoxy resin, or fluororesin, directly on the back surface 2b of the base material layer 2 or via a bonding layer. Can be formed by laminating them, or by applying the resin composition to the back surface 2b of the base material layer 2 and drying it. The back protective layer can be given a glossy finish or a matte finish depending on the intended application.

  The base material layer 2 may have an uneven shape on the back surface 2b by embossing. The concavo-convex pattern or pattern may be regular or irregular, and is not particularly limited. For example, a line, wood grain, sand grain, stone grain, cloth grain, satin, leather, mat, hairline, spin , Letters, symbols, geometric figures and the like.

  The base material layer 2 may contain additives such as plasticizers, fillers, reinforcing agents such as glass fibers, pigments such as zinc oxide and titanium oxide, antioxidants, ultraviolet absorbers, and heat stabilizers.

  The thickness of the base material layer 2 is, for example, 0.4 mm or less, more preferably 0.35 mm or less, and still more preferably 0.3 mm or less. On the other hand, since the thickness of the base material layer 2 may be difficult to handle if it is too thin, it is preferably 0.05 mm or more, for example.

  The pressure-sensitive adhesive layer 3 is an adhesive layer having a pressure-sensitive adhesive that adheres the decorative sheet 1 to the base material 6. As shown in FIGS. 2 and 3A, the pressure-sensitive adhesive layer 3 has a plurality of protrusions 10. The protrusion 10 is provided on the main surface 3 a on the side opposite to the surface 2 a of the base material layer 2 in the pressure-sensitive adhesive layer 3. The protrusion 10 is a part of the pressure-sensitive adhesive layer 3 protruding toward the side opposite to the surface 2 a of the base material layer 2. In the protrusion 10, the cross-sectional area along the base material layer 2 gradually decreases as it goes to the tip side.

  Although the shape of the protrusion 10 is not limited, for example, in addition to a triangular pyramid, a quadrangular pyramid, other polygonal pyramids, a cone or the like can be used. In one embodiment, the shape of the protrusion 10 is a regular quadrangular pyramid shape (pyramid shape). The plurality of protrusions 10 are adjacent to each other, and are continuously arranged via the connection portions 11 (each base of a regular quadrangular pyramid). The length A (see FIG. 3) of each base of the regular quadrangular pyramid is, for example, 10 μm or more and 400 μm or less, for example, 20 μm or more and 300 μm or less, or 20 μm or more and 200 μm or less.

The protrusion 10 has a pointed apex 12a at the tip 12 in a state where at least the pressure-sensitive adhesive layer 3 and the base material 6 are not in contact with each other. Top 12a forms a corner in the shape that is pointed to the opposite side of the base layer 2 and top portion 12a as the vertex in the cross section including a vertical top part 12a to the base layer 2. In one embodiment, the apex 12a is a apex that includes the apex of a regular quadrangular pyramid. The angle α (see FIG. 3) of the apex of the regular quadrangular pyramid is 30 ° or more and 160 ° or less as an example, for example, 60 ° or more and 130 ° or less. Note that the height B (see FIG. 3) from the top 12a of the regular quadrangular pyramid to the virtual bottom surface of the regular quadrangular pyramid is 8 μm or more and 110 μm or less, for example, 10 μm or more and 35 μm or less.

The density of the protrusions 10 is, for example, 15 pieces / mm ² or more and 3000 pieces / mm ² or less. The density of the protrusions 10 is preferably 20 pieces / mm ² or more and 200 pieces / mm ² or less. The density of the protrusions 10 means the number of protrusions 10 per unit area on the main surface 3a of the pressure-sensitive adhesive layer 3. By setting the density of the protrusions 10 within the above range, the contact area between the pressure-sensitive adhesive layer 3 and the base material 6 becomes appropriate, and the adhesive force between the pressure-sensitive adhesive layer 3 and the base material 6 becomes appropriate.

  The shape or the like of the plurality of protrusions 10 is determined by the shape or the like of the unevenness formed on the liner 4. For example, the liner 4 is formed with unevenness having a shape corresponding to the protrusion 10. The plurality of protrusions 10 are formed by applying a pressure-sensitive adhesive solution on the liner 4 on which irregularities are formed, and drying the pressure-sensitive adhesive solution. The thickness of the pressure-sensitive adhesive layer 3 is 10 μm or more and 100 μm or less, for example, 30 μm or more and 50 μm or less from the viewpoint of balancing workability and adhesive force.

  As another form, the shape of the protrusion 10 may be a shape having a plurality of stepped side surfaces, that is, a shape in which a cone or a polygonal pyramid is further provided on the top surface of the truncated cone or the polygonal frustum. It is. For example, a two-stage square pyramid may be used. As shown in FIG. 3B, the two-stage quadrangular pyramid has a shape in which a small quadrangular pyramid is further provided on the top surface of the quadrangular pyramid. In this case, the tip 12 may be the tip of a small quadrangular pyramid, and the apex 12a may be the apex of the small quadrangular pyramid. The plurality of protrusions 10 may be provided so as to be arranged at a predetermined distance from each other along the main surface 3a. The protrusions 10 may be continuously arranged with each other via a connection portion 11 (a spaced portion between two-stage square pyramids) connected to another protrusion 10 adjacent to the protrusion 10.

As an example, the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 3 is a cured product of a pressure-sensitive adhesive composition containing an acrylic pressure-sensitive adhesive polymer and an acrylic non-sticky polymer. Further, the pressure-sensitive adhesive may contain fine particles (filler) that are dispersed and present in the pressure-sensitive adhesive composition. As an example of the filler, titanium dioxide (TiO ₂ ) can be used. The filler is not limited to this example. In one embodiment, when titanium dioxide is used as a filler, the average particle size of titanium dioxide is 0.10 μm to 0.50 μm, or 0.15 μm to 0.30 μm. In addition, a particle size here means the particle size of primary particles, not aggregated particles (secondary particles). By making the average particle diameter of the filler within this range, the filler can be more uniformly dispersed in the pressure-sensitive adhesive. The average particle size of the titanium dioxide is the volume cumulative particle diameter D ₅₀ which can be determined using a laser diffraction / scattering particle size distribution measurement. Moreover, the compounding quantity of titanium dioxide is 15 mass parts or more and 150 mass parts or less with respect to 100 weight part of adhesive compositions except a filler, for example, or 20 mass parts or more and 100 mass parts or less. By adjusting the filler amount within the above range, the shear storage elastic modulus of the adhesive can be adjusted while maintaining the adhesiveness of the adhesive, and as a secondary effect, the base material layer 2 is transparent. In this case, titanium dioxide also functions as a white pigment to whiten the pressure-sensitive adhesive layer 3 and add a concealing effect to the decorative sheet 1.

  Specifically, the acrylic adhesive polymer includes at least one acrylic adhesive polymer selected from the group consisting of adhesive acrylic homopolymers and copolymers. For example, the acrylic adhesive polymer is selected from the group consisting of methyl acrylate, butyl acrylate, isoamyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, and ethacrylonitrile. Including homopolymers of monomers or copolymers of two or more of these monomers.

  The acrylic non-adhesive polymer specifically includes a homopolymer of a monomer selected from the group consisting of methyl methacrylate, butyl methacrylate, and (dimethylamino) ethyl methacrylate, or a copolymer of two or more of these monomers. . The acrylic non-adhesive polymer may be a basic acrylic polymer.

  In one embodiment, the acrylic adhesive polymer has a weight average molecular weight of 100,000 or more and 800,000 or less. For example, the weight average molecular weight of the acrylic adhesive polymer is about 620,000. The weight average molecular weight of the acrylic non-adhesive polymer is 30,000 or more and 100,000 or less. For example, the weight average molecular weight of the acrylic non-adhesive polymer is about 68,000. The weight average molecular weight of the acrylic adhesive polymer and the weight average molecular weight of the acrylic non-adhesive polymer are determined using standard polystyrene by a GPC (gel permeation chromatography) method.

  The acrylic pressure-sensitive adhesive polymer and the acrylic non-sticky polymer are obtained by polymerizing the monomer or the mixture of the monomers using a normal radical polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization and the like. be able to. As polymerization initiators, organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 2-methylbutyronitrile), dimethyl-2,2-azobis (2-methylpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-methylpropionic acid) ) Azo polymerization initiators such as dimethyl and azobis (2,4-dimethylvaleronitrile) (AVN) can be used.

  The acrylic adhesive polymer and the acrylic non-adhesive polymer may be crosslinked with a crosslinking agent. Examples of the crosslinking agent include isocyanate compounds, melamine compounds, poly (meth) acrylate compounds, epoxy compounds, amide compounds, and bisamide compounds, for example, dibasic acid bis such as 1,1′-isophthaloyl-bis (2-methylaziridine). Aziridine derivatives and the like can be used. As the crosslinking agent, it is preferable to use an isocyanate compound, particularly hexamethylene diisocyanate. Although the addition amount of a crosslinking agent is based also on the kind of crosslinking agent, it is about 0.1 mass part or more normally about 10 mass with respect to 100 mass parts which is the sum total of an acrylic adhesive polymer and an acrylic non-adhesive polymer. Or less. As the crosslinking agent, a bisamide compound (for example, 1,1′-isophthaloyl-bis (2-methylaziridine)) can be preferably used.

The glass transition temperature of the acrylic adhesive polymer is preferably 10 ° C. or lower. The glass transition temperature of the acrylic non-adhesive polymer is preferably 60 ° C. or higher. The glass transition point can be determined from the FOX equation (the following equation), assuming that each polymer is copolymerized from n types of monomers.

However,
Tg ₁ : Glass transition temperature of homopolymer of component 1 Tg ₂ : Glass transition temperature of homopolymer of component 2
Tg _n : Glass transition temperature of homopolymer of component n X ₁ : Mass fraction of monomer of component 1 added during polymerization X ₂ : Mass fraction of monomer of component 2 added during polymerization
X _n : mass fraction of monomer of component n added during polymerization X ₁ + X ₂ +... + X _n = 1

The shear storage elastic modulus of the pressure-sensitive adhesive is 2.0 × 10 ⁵ or more under test conditions of a frequency of 1.0 Hz and an atmospheric temperature of 20 ° C. (hereinafter also simply referred to as “at 20 ° C.”). It can be 0 × 10 ⁵ or more, and further can be 4.0 × 10 ⁵ or more. The shear storage modulus of the pressure-sensitive adhesive at 20 ° C. is advantageously 1.0 × 10 ⁷ or less, or 1.0 × 10 ⁶ or less. The shear storage elastic modulus is a real part of the complex elastic modulus when sinusoidal shear strain is applied to the viscoelastic body, and is an index representing the hardness of the viscoelastic body. Specifically, the shear storage elastic modulus can be measured as follows.

  The shear storage modulus can be measured using, for example, a dynamic viscoelasticity measuring device ARES (manufactured by TA Instruments Japan Co., Ltd.). In this measurement method, first, a test specimen is formed by punching out so as to have a thickness of about 3 mm and a diameter of about 7.9 mm. The shear storage elastic modulus G ′ is measured while applying a force to the test body so as to twist the test body in a predetermined shear mode. The shear mode here is a mode in which a force is applied so as to twist the specimen in a circumferential direction with the thickness direction of the specimen as an axis. The direction in which the force is applied alternates between a clockwise and counterclockwise circumferential direction at a frequency of 1.0 Hz. The atmospheric temperature may be, for example, in the range of −60 ° C. or higher and 200 ° C. or lower, and the rate of temperature increase may be 5.0 ° C./second. The shear storage modulus G ′ thus measured is shown in FIG.

  FIG. 5 is a graph showing the shear storage modulus of the pressure-sensitive adhesive. In FIG. 5, the plot of the pressure-sensitive adhesive X is a plot corresponding to the physical properties (temperature characteristics of shear storage elastic modulus) of the pressure-sensitive adhesive including the acrylic pressure-sensitive adhesive polymer, the acrylic non-pressure-sensitive polymer, and the filler. The plot of the pressure-sensitive adhesive Y is a plot corresponding to the physical properties of the pressure-sensitive adhesive including the acrylic pressure-sensitive adhesive polymer and the acrylic non-sticky polymer but not including the filler. The plot of the pressure-sensitive adhesive Z is a plot corresponding to the physical properties of the pressure-sensitive adhesive including the acrylic pressure-sensitive adhesive polymer but not including the acrylic non-sticky polymer and the filler.

As shown in FIG. 5, the shear storage modulus G ′ (viscoelasticity) of the adhesive Z is 2.0 × 10 ⁵ or less at an ambient temperature of 20 ° C. The pressure-sensitive adhesive Z is relatively higher in wettability with respect to an object to be bonded such as the base material 6 (the property of spreading on and sticking to the surface of the object to be bonded) than the pressure-sensitive adhesive X or pressure-sensitive adhesive Y. If such a pressure-sensitive adhesive Z is used as the pressure-sensitive adhesive layer 3 having a plurality of protrusions 10, for example, the pressure-sensitive adhesive layer 3 is temporarily placed on the base material 6 without applying an external pressing force. Even if it exists, it will become easy to be in the state where a plurality of projections 10 will be crushed easily, and a plurality of projections 10 will be in surface contact with foundation material 6. That is, the shape stability of the protrusion 10 is relatively low.

On the other hand, the plot of the adhesive X and the adhesive Y is distributed upward with respect to the plot of the adhesive Z. Specifically, the shear storage elastic modulus G ′ of the adhesive X and the adhesive Y is 2.0 × 10 ⁵ or more at 20 ° C. The pressure-sensitive adhesive X and pressure-sensitive adhesive Y are relatively lower in wettability than the pressure-sensitive adhesive Z with respect to an object to be bonded such as the base material 6. When such a pressure-sensitive adhesive X or pressure-sensitive adhesive Y is used as the pressure-sensitive adhesive layer 3 having a plurality of protrusions 10, for example, in a state where the pressure-sensitive adhesive layer 3 is temporarily placed on the base material 6, an external pressing force is used. Unless a plurality of protrusions 10 are provided, the plurality of protrusions 10 are not easily crushed, and it is easy to maintain a state in which the plurality of protrusions 10 are in point contact with the base material 6. That is, the shape stability of the protrusion 10 is relatively high. Further, the shear storage elastic modulus G ′ of the adhesive X and the adhesive Y is 1.0 × 10 ⁷ or less, or 1.0 × 10 ⁶ or less at 20 ° C. Therefore, the adhesive X and the adhesive Y have properties as an adhesive from the viewpoint of viscoelasticity (Dahlquist criterion, source / adhesive handbook (Japan Adhesive Tape Industry Association)). When such an adhesive X or adhesive Y is used as the adhesive layer 3 having a plurality of protrusions 10, for example, by receiving a pressing force, this time the protrusions 10 are crushed and are in surface contact, Appropriate adhesive force can be imparted to the pressure-sensitive adhesive layer 3.

  The shear storage modulus G ′ (viscoelasticity) of the pressure-sensitive adhesive can be adjusted by the mixing ratio of the acrylic pressure-sensitive adhesive polymer and the acrylic non-sticky polymer, or the amount of filler added such as titanium dioxide. It is also possible to select an acrylic adhesive polymer having a glass transition temperature at which a desired shear storage modulus G ′ is obtained, or to adjust the mixing ratio of a plurality of acrylic adhesive polymers having different glass transition temperatures.

  In one embodiment, the pressure-sensitive adhesive adjusts the shear storage elastic modulus G ′ of the pressure-sensitive adhesive by mixing an acrylic pressure-sensitive adhesive polymer having a low glass transition temperature and an acrylic non-sticky polymer having a high glass transition temperature. Can do. For example, a mixture of an acrylic adhesive polymer having a glass transition temperature of 10 ° C. or lower, −20 ° C. or lower, or −40 ° C. or lower and an acrylic non-adhesive polymer having a glass transition temperature of 60 ° C. or higher can be used.

  Examples of the liner 4 include those prepared from paper (for example, kraft paper) or a polymer material (for example, polyolefin such as polyethylene or polypropylene, polyester such as ethylene vinyl acetate, polyurethane, and polyethylene terephthalate). The liner 4 may be coated with a layer of a release agent such as a silicone-containing material or a fluorocarbon-containing material as necessary. The thickness of the liner 4 is generally about 5 μm or more, about 15 μm or more, or about 25 μm or more, about 300 μm or less, about 200 μm or less, or about 150 μm or less.

  The decorative sheet 1 is preferably used by sticking it on the wall surface, ceiling surface, floor surface, partition, or the like of a general house, apartment house, building or other building.

Next, the operation and effect of the decorative sheet 1 will be described. As shown in FIG. 4A, in a state where the decorative sheet 1 is simply disposed on the base material 6, for example, in a temporarily placed state, the adhesive layer 3 is applied to the base material 6 via the plurality of top portions 12a. It comes into contact. That is, the pressure-sensitive adhesive layer 3 in the temporarily placed state is merely a state in which the plurality of protrusions 10 are in point contact with the base material 6, and the pressure-sensitive adhesive layer 3 and the base material 6 are compared with the surface contact state. The contact area with is small. In particular, in this decorative sheet 1, the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 3 has a shear storage elastic modulus at 20 ° C. of 2.0 × 10 ⁵ or more, and gives an external pressing force to the pressure-sensitive adhesive layer 3. Unless this is done, the plurality of protrusions 10 are not easily crushed and have high shape stability. As a result, for example, the temporarily placed decorative sheet 1 is easy to slide along the base material 6, and the decorative sheet 1 is easy to peel off from the base material 6. That is, if the decorative sheet 1 is simply placed on the base material 6, position adjustment and rearrangement can be easily performed.

  In addition, since the protrusions 10 of the pressure-sensitive adhesive layer 3 are conical and the plurality of protrusions 10 are substantially in point contact with the base material 6, the decorative sheet 1 is placed in the position adjustment. It is easy to slide isotropically along the base material 6.

When the position of the decorative sheet 1 is adjusted or rearranged and the position of the decorative sheet 1 with respect to the base material 6 is determined, the decorative sheet 1 is sufficiently pressed toward the base material 6 as shown in FIG. . By this pressing, the pressure-sensitive adhesive layer 3 receives a pressing force. Here, in the case of the decorative sheet 1, the shear storage elastic modulus G ′ at 20 ° C. of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 3 is 1.0 × 10 ⁷ or less, or 1.0 × 10 ⁶ or less. Therefore, when the decorative sheet 1 receives an external pressing force, the protrusion 10 is now crushed and brought into surface contact, and an appropriate adhesive force can be applied to the adhesive layer 3. That is, when the predetermined position where the decorative sheet 1 is pasted is determined, the decorative sheet 1 can be appropriately bonded by applying a pressing force to the decorative sheet 1 this time.

  Although one embodiment of the present invention has been described above, the present invention is not limited to the above embodiment. For example, the shape of the protrusion 10 may be a mountain shape extending linearly along a predetermined direction (see FIG. 6). In the case of this form, the protrusion 10 has a top portion 12a having a shape in which a sharp tip is continuous in a ridge shape. In this form, in the temporarily placed state, the plurality of protrusions 10 of the pressure-sensitive adhesive layer 3 are in line contact with the base material 6 via the top 12a, and are more adhesive than in the surface contact state. The contact area between the agent layer 3 and the base material 6 is reduced. Further, the plurality of protrusions 10 may be provided so as to be adjacent to each other along the main surface 3a. Further, the protrusions 10 may be arranged continuously with each other via connection portions 11 (valleys at both ends of the mountain shape) connected to other adjacent protrusions 10. In this case, for example, in the temporarily placed state, it is easy to slide the decorative sheet 1A along at least the extending direction of the mountain shape.

As described above, as an example of the embodiment, one aspect of the present invention is a decorative sheet for interior and exterior use, and is a pressure-sensitive adhesive that is laminated on the surface of a base material layer and the base material layer and has a pressure-sensitive adhesive. And a layer. The pressure-sensitive adhesive layer has a plurality of protrusions provided on the main surface opposite to the surface of the base material layer, the protrusion has a pointed top at the tip, and the adhesive is sheared at 20 ° C. The storage elastic modulus is 2.0 × 10 ⁵ or more.

In such a side surface, when this decorative sheet is arranged on an adherend target object such as a base material coated with a primer, the pressure-sensitive adhesive layer is in contact with the adherend target object via a plurality of top portions. . That is, the pressure-sensitive adhesive layer is substantially in a state where a plurality of protrusions are in point contact or line contact with the object to be bonded, and compared with the state in which the surface is in contact with the adhesive layer and the object to be bonded. The contact area is reduced. In particular, in this decorative sheet, since the shear storage elastic modulus at 20 ° C. of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is 2.0 × 10 ⁵ or more, unless an external pressing force is applied to the pressure-sensitive adhesive layer. The plurality of protrusions are not easily crushed and have high shape stability. As a result, it is easy to slide the decoration sheet along the object to be adhered in a state where the decoration sheet is simply arranged on the object to be adhered, for example, in a temporary placement state, and it is easy to peel the decoration sheet from the object to be adhered. . That is, position adjustment and rearrangement can be easily performed as long as the decorative sheet is simply placed on the adherend.

In the decorative sheet according to another aspect, the shear storage elastic modulus of the pressure-sensitive adhesive at 20 ° C. may be 1.0 × 10 ⁷ or less, or 1.0 × 10 ⁶ or less. Since the shear storage elastic modulus at 20 ° C. of the pressure-sensitive adhesive is 1.0 × 10 ⁷ or less, or 1.0 × 10 ⁶ or less, when receiving a pressing force, the protrusions are crushed and are in surface contact. Appropriate adhesive strength can be imparted to the adhesive layer. In other words, when the position adjustment or rearrangement is performed with the decoration sheet placed on the object to be bonded, and the predetermined position is determined, the decoration sheet can be appropriately bonded by applying a pressing force. .

  In the decorative sheet according to another aspect, the pressure-sensitive adhesive contains an acrylic pressure-sensitive adhesive polymer having a glass transition temperature of 10 ° C. or lower and an acrylic non-sticky polymer having a glass transition temperature of 60 ° C. or higher. It may be a cured product. Thereby, the shear storage elastic modulus of an adhesive can be adjusted appropriately.

  In the decorative sheet according to another aspect, the pressure-sensitive adhesive may contain a filler. Thereby, the shear storage elastic modulus of an adhesive can be adjusted more appropriately.

Further, in the decorative sheet according to another aspect, the filler may be made of TiO _2.

  In the decorative sheet according to another aspect, the shape of the protrusion may be a cone shape. This makes it easy to adjust the position of the decorative sheet by sliding isotropically along the adherend target object such as a base material.

In the decorative sheet according to another aspect, the number of protrusions per unit area on the main surface of the pressure-sensitive adhesive layer may be 15 / mm ² or more and 3000 / mm ² or less. Thereby, for example, the adhesive force between the adherend target object such as the base material coated with the primer and the adhesive layer can be appropriately set.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to an Example.

[Create liner sample]
Liners L1 to L6 having specifications as shown in Table 1 were prepared. Here, the shape of the protrusion formed by the liner L1 was a truncated cone shape as shown in FIGS. 7 (a) and 7 (b). The tip portion did not have a top portion, and had a circular top surface of about 23 μm. The shape of the protrusion formed by the liner L2 was a two-stage square pyramid as shown in FIG. 3B, and had a top at the tip. The liner L3 was planar and did not form protrusions on the pressure-sensitive adhesive layer 3.

  The shape of the protrusion formed by the liner L4, the liner L5, and the liner L6 was a regular quadrangular pyramid as shown in FIG. 2, and had a top at the tip. The density of the formed protrusions was different depending on the liner L4, the liner L5, and the liner L6.

[Create decoration sheet sample]
First, DuPont Taipure ^TM titanium oxide as a filler, acrylic non-adhesive polymer (basic acrylic polymer) shown in Table 2, and methyl isobutyl ketone (solvent) in a weight ratio of 27.5: 55.0: 17 .50 was mixed to prepare a premix solution. To a liquid in which 9% by weight of the premix solution and 26% by weight of the acrylic adhesive polymer shown in Table 2 were mixed, 0.2% of a bisamide compound (“RD1054” manufactured by 3M Corporation) shown in Table 2 was used as a crosslinking agent. The first pressure-sensitive adhesive solution was prepared by mixing by weight%.

  Subsequently, the prepared first pressure-sensitive adhesive solution was applied to the L-2 liner by knife coating to form a pressure-sensitive adhesive layer. The formed pressure-sensitive adhesive layer was heated at 90 ° C. for 3 minutes to dry and crosslink the pressure-sensitive adhesive layer. The application amount of the first pressure-sensitive adhesive solution was such that the thickness of the pressure-sensitive adhesive layer after drying was 40 μm.

  Subsequently, a 150 μm-thick PVC film (manufactured by 3M Japan Ltd.) was prepared as a base material layer. The composition of the PVC film is polyvinyl chloride, a plasticizer (diisononyl phthalate), and an organic stabilizer (acrylic resin, zinc stearate), and the respective mass ratios are 66.5: 19.5: 14. 0. This base material layer and the above-mentioned pressure-sensitive adhesive layer were dry laminated to obtain a decorative sheet of Example 1.

  The decorative sheet of Example 2 was prepared in the same manner as the decorative sheet of Example 1 except that the liner to which the first adhesive solution was applied was changed to an L-5 liner.

  The decorative sheet of Example 3 was prepared in the same manner as the decorative sheet of Example 1 except that the liner to which the first adhesive solution was applied was changed to an L-6 liner.

  The decorative sheet of Example 4 is the same as the decorative sheet of Example 1, except that the first adhesive solution was changed to the second adhesive solution and the second adhesive solution was applied to the L-2 liner. Created in the same way. The 2nd adhesive solution was created like the 1st adhesive solution except the point which does not use a filler.

  The decorative sheet of Example 5 was prepared in the same manner as the decorative sheet of Example 1 except that the liner to which the first adhesive solution was applied was changed to an L-4 liner.

  The decorative sheet of Comparative Example 1 was prepared in the same manner as the decorative sheet of Example 1 except that the liner to which the first adhesive solution was applied was changed to an L-3 liner.

  The decorative sheet of Comparative Example 2 was prepared in the same manner as the decorative sheet of Example 1 except that the liner to which the first adhesive solution was applied was changed to an L-1 liner.

  In the decorative sheet of Comparative Example 3, the first adhesive solution was changed to a third adhesive solution prepared without using any acrylic non-adhesive polymer and filler, and a liner on which the third adhesive solution was applied. It was produced in the same manner as the decorative sheet of Example 1 except that was changed to an L-1 liner. The third pressure-sensitive adhesive solution was prepared by mixing 1.52% by weight of a bisamide compound (“RD1054” manufactured by 3M Corporation) as a cross-linking agent with respect to 100% by weight of the pressure-sensitive adhesive polymer shown in Table 2.

  The decorative sheet of Comparative Example 4 was the same except that the first pressure-sensitive adhesive solution was changed to the third pressure-sensitive adhesive solution, and the liner to which the third pressure-sensitive adhesive solution was applied was changed to an L-1 liner to form a truncated cone with beads. This was prepared in the same manner as the decorative sheet of Example 1.

  The decorative sheet of Comparative Example 5 is the decorative sheet of Example 1 except that the first pressure-sensitive adhesive solution is changed to the third pressure-sensitive adhesive solution and the liner to which the third pressure-sensitive adhesive solution is applied is changed to the L-3 liner. Created in the same way as the sheet.

  The decorative sheet of Comparative Example 6 was prepared in the same manner as the decorative sheet of Example 1 except that the first adhesive solution was changed to the third adhesive solution.

[Measurement of force required for position adjustment]
The decorative sheets of Examples 1 to 5 and Comparative Examples 1 to 6 were each cut to a length of 100 mm × 25 mm and used as test specimens. A SUS304 plate (70 mm × 150 mm × 0.5 mm thickness) was prepared as a base material to which the test body was attached. Subsequently, the liner was peeled from the decorative sheet, and the test specimen was placed so that the pressure-sensitive adhesive layer was in contact with the SUS304 plate, and was allowed to stand still. A 52.3 g weight was placed on the base material layer side of the test body. Ten seconds after the weight was placed, the test body was pulled by a push-pull gauge (Shinpo FGP-50) along the SUS304 plate (180 ° direction) to move the test body by 50 mm. At that time, the force required for position adjustment was recorded based on the indicated value of the push-pull gauge. The ambient temperature was 27 ° C. The results are shown in Table 3.

  The significance of placing a 52.3 g weight on the base material layer side of the test specimen is to create a state in which the weight (self-weight) of the decorative sheet itself is applied to the adhesive layer, that is, a state in which the decorative sheet is temporarily placed. It is.

[Slidability on primed surface test]
The decorative sheets of Examples 1 to 5 and Comparative Examples 1 to 6 were each cut to a length of 100 mm × 25 mm and used as test specimens. As a base material on which the test specimen was pasted, a 9.5 mm thick plaster board (manufactured by Yoshino Gypsum Co., Ltd.) was coated with 3M Japan WP-2000 primer and dried for 1 hour. Subsequently, the liner was peeled from the decorative sheet, and the test specimen was placed so that the pressure-sensitive adhesive layer was in contact with the primer-treated surface, and was allowed to stand still. An attempt was made to move (slide) the decorative sheet in a direction along the base material while the pressure-sensitive adhesive layer of the decorative sheet and the primer-treated surface were in contact with each other. If the decoration sheet can be moved smoothly in the direction along the base material, it is judged as “◯”. If the decoration sheet cannot be moved in the direction along the base material, or the decoration sheet is moved in the direction along the base material. If it was able to be caught, it was judged as “x”. The results are shown in Table 3.

[Repositionability test]
The decorative sheets of Examples 1 to 5 and Comparative Examples 1 to 6 were each cut to a length of 100 mm × 25 mm and used as test specimens. As a base material on which the test specimen was pasted, a DP-900N3 primer manufactured by 3M Japan was applied to a 9.5 mm thick plaster board (manufactured by Yoshino Gypsum Co., Ltd.) and dried for 1 hour. Subsequently, the liner was peeled from the decorative sheet, and the test specimen was placed so that the pressure-sensitive adhesive layer was in contact with the primer-treated surface, and was allowed to stand still. A 200 g weight was placed on the base material layer side of the test body. Ten seconds after the weight was placed, the specimen was pulled in the normal direction of the base material (90 ° direction). At that time, when the test specimen could be peeled off from the base material without causing adhesive residue or destruction of the base material layer, it was determined as “◯”, and when it was not, it was determined as “x”. The results are shown in Table 3.

Each pressure-sensitive adhesive layer of Examples 1 to 5 has a protrusion having a vertex (first condition), and the shear storage elastic modulus at 20 ° C. of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is 2.0. × 10 ⁵ or more (second condition). On the other hand, Comparative Examples 1 and 2 satisfied the second condition but did not satisfy the first condition. Further, Comparative Examples 3, 4, and 5 did not satisfy both the first condition and the second condition. In Comparative Example 6, the first condition was satisfied, but the second condition was not satisfied. In Examples 1 to 5, as shown in Table 3, both the position adjustment determination result and the rearrangement determination result were “◯”. On the other hand, in Comparative Example 1 and Comparative Examples 3 to 6, the position adjustment determination result and the rearrangement determination result are both “x”, and in Comparative Example 2, the rearrangement determination result is “x”. It was. That is, by satisfying the first condition and the second condition, it was possible to obtain a result that position adjustment was possible and rearrangement was possible.

  Moreover, when Example 3 and Example 4 are compared, the shear storage elastic modulus in 20 degreeC of the adhesive which forms the adhesive layer of Example 4 compared with Example 3 is high. When the force required for position adjustment is compared between Example 3 and Example 4, Example 4 is lower than Example 3. That is, when the ease of position adjustment is quantitatively evaluated from the correlation between the shear storage modulus of the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer and the force required for position adjustment, the higher the shear storage modulus, the higher the protrusion The shape stability is high, and as a result, it is possible to obtain an estimation result that is advantageous in terms of easy position adjustment and rearrangement with the decorative sheet temporarily placed.

Moreover, when Example 2 was compared with Example 3 about the density of the protrusion, the density of Example 2 was 174 pieces / mm < ² > and the density of Example 3 was 25 pieces / mm < ² >. And both the force required for position adjustment of Example 2 and Example 3 is 1 kg or less. On the other hand, the density of Example 5 was 2500 pieces / mm < ² >, and the force required for position adjustment exceeded 1 kg. That is, when the ease of position adjustment is quantitatively evaluated from the correlation between the density of the protrusions and the force required for position adjustment, if the density of the protrusions is 200 pieces / mm ² or less, the decorative sheet is temporarily placed. It is possible to obtain an estimation result that is advantageous in terms of ease of position adjustment and rearrangement in the above state.

  DESCRIPTION OF SYMBOLS 1,1A ... Decoration sheet, 2 ... Base material layer, 2a ... Surface, 3 ... Adhesive layer, 3a ... Main surface, 10 ... Projection, 12 ... Tip, 12a ... Top part.

Claims (7)

A decorative sheet for interior and exterior,
A base material layer;
And being laminated on the surface of the base material layer, and having an adhesive layer having an adhesive,
The pressure-sensitive adhesive layer has a plurality of protrusions provided on the main surface opposite to the surface of the base material layer,
The protrusion has a pointed apex at the tip,
The adhesive sheet has a shear storage elastic modulus at 20 ° C. of 2.0 × 10 ⁵ or more. The decorative sheet according to claim 1, wherein the adhesive has a shear storage elastic modulus at 20 ° C. of 1.0 × 10 ⁷ or less.   The said adhesive is a hardened | cured material of the adhesion composition containing the acrylic adhesive polymer whose glass transition temperature is 10 degrees C or less, and the acrylic non-adhesive polymer whose glass transition temperature is 60 degrees C or more. Or the decorative sheet of 2.   The decorative sheet according to claim 3, wherein the adhesive contains a filler. The decorative sheet according to claim 4, wherein the filler is made of TiO ₂ .   The decorative sheet according to any one of claims 1 to 5, wherein a shape of the protrusion is a cone shape. The number of the said protrusions per unit area in the said main surface of the said adhesive layer is 15 pieces / mm < ² > or more and 3000 pieces / mm < ² > or less as described in any one of Claims 1-6. Decorative sheet.