JP2021160233A - Outdoor sucker-adhesive decorative sheet - Google Patents

Abstract

To provide a sucker adhesive decorative sheet which is excellent in reworkability and exhibits excellent weather resistance in long-term outdoor use.MEANS FOR SOLVING THE PROBLEM: The sucker adhesive decorative sheet comprises a protective layer, a design layer, a substrate layer and a sucker adhesive layer in this order, where the protective layer contains ultraviolet absorbers, where the content of the ultraviolet absorbers is 1 pt.mass or more and 10 pts.mass or less inclusive based on 100 pts.mass of a resin forming the protective layer, and where the content of the ultraviolet absorbers having melting points at or above 90°C is 45 mass% or more based on the total amount of the ultraviolet absorbers.SELECTED DRAWING: Figure 1

Description

The present invention relates to an outdoor suction cup adhesive decorative sheet.

Since the decorative sheet needs to be in close contact with the adherend without peeling off for a long period of time, the adhesive used for the decorative sheet is formed on the entire surface of the decorative sheet in contact with the adherend and has strong adhesiveness. It was necessary to have power. However, once it is pasted, it is difficult to reuse it by peeling it off and re-pasting it. For example, if wrinkles occur during pasting, it cannot be corrected and the decorative sheet has to be peeled off and discarded. .. Further, when the adherend is reused, it is necessary to remove the adhesive (so-called "glue residue") remaining on the surface of the adherend when the decorative sheet is peeled off. For this reason, it was difficult to prepare a decorative material using a decorative sheet and to attach the decorative sheet because special equipment was required and a skilled skill (person) was required. .. Therefore, in order to make the decorative sheet easier to use, it is required to improve the reworkability so that the decorative sheet can be peeled off and reattached as it is when the attachment fails while maintaining the necessary long-term adhesion. Was there.

Further, not only the decorative sheet but also various uses, the adhesive sheet is required to have high reworkability.

Therefore, as a method for improving the reworkability of a decorative sheet or the like, a form in which suction cup adhesive is used instead of the adhesive has been proposed. For example, Patent Document 1 proposes an advertising poster using a micro suction cup (sucker adhesive) instead of an adhesive.

Japanese Unexamined Patent Publication No. 2001-356724 Japanese Unexamined Patent Publication No. 2003-076308

The advertising poster of Patent Document 1 was able to improve the reworkability by using a micro suction cup. However, the advertising poster of Patent Document 1 is not suitable for long-term outdoor use because the pattern tends to fade due to the influence of wind, rain, ultraviolet rays from sunlight, etc., and the adhesive strength of the micro suction cup tends to decrease. Met.

As a method of displaying a design outdoors, Patent Document 2 proposes an advertising poster sheet in which a pattern is directly printed on the side of a micro suction cup sheet. By printing the pattern directly on the micro suction cup sheet side, for example, the poster can be placed from the inside of the shop window or the like with the pattern facing the outside, so that the influence of wind and rain can be avoided. However, in the style of Patent Document 2, not only the pattern but also the micro suction cup faces the outdoor side, so that the problem that the pattern tends to fade or the adhesive strength decreases with time cannot be solved, and it is suitable for long-term use. It was inadequate. Further, the advertising poster sheet of Patent Document 2 can give a design only to a transparent adherend represented by glass such as a show window, and lacks versatility in outdoor use. Met.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a suction cup adhesive decorative sheet having excellent reworkability and excellent weather resistance when used outdoors for a long period of time. do.

In order to solve the above problems, the present invention provides the following [1] to [3].
[1] The protective layer, the design layer, the base material layer, and the suction cup adhesive layer are provided in this order, the protective layer contains an ultraviolet absorber, and the content of the ultraviolet absorber with respect to 100 parts by mass of the resin forming the protective layer. Is 1 part by mass or more and 10 parts by mass or less, and the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber.
[2] The suction cup adhesive decorative sheet according to [1], which has a concave shape on at least the surface of the suction cup adhesive layer opposite to the surface on the base material layer side.
[3] The suction cup adhesive decorative sheet according to [1] or [2], wherein the amount of the suction cup adhesive layer applied after formation is 13 g / m ² or more and 100 g / m ^{2 or less.}

According to the present invention, it is possible to provide a suction cup adhesive decorative sheet having excellent reworkability and excellent weather resistance when used outdoors for a long period of time.

It is sectional drawing which shows one Embodiment of the sucker adhesive decorative sheet of this invention. It is a photographic image which shows the appearance of the melting point measurement of the ultraviolet absorber used in an Example and a comparative example.

<Sucker adhesive decorative sheet>
The suction cup adhesive decorative sheet of the present invention has a protective layer, a design layer, a base material layer and a suction cup adhesive layer in this order, and the protective layer contains an ultraviolet absorber, and the said to 100 parts by mass of the resin forming the protective layer. The content of the ultraviolet absorber is 1 part by mass or more and 10 parts by mass or less, and the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber.
By having the protective layer of the suction cup adhesive decorative sheet of the present invention having an ultraviolet absorber having a melting point of 90 ° C. or higher at the above content, the suction cup adhesive decorative sheet can be used in a harsh environment, especially under harsh temperature conditions. However, the bleed out of the ultraviolet absorber is suppressed, and excellent weather resistance can be obtained.

Regarding the fact that the bleed-out of the UV absorber is likely to occur under harsh temperature conditions, the mechanism of the bleed-out is not clear, but the UV absorber liquefies due to the temperature rise of the suction cup adhesive decorative sheet and leaks from the protective layer. It is speculated that it may occur by issuing it. When the UV absorber liquefies, it becomes easier to bleed out from the protective layer, and as the occurrence of bleed-out progresses, the amount of UV absorber held by the suction cup adhesive decorative sheet itself decreases, and the weather resistance deteriorates. it is conceivable that. Furthermore, even if the liquefied UV absorber remains in the protective layer, if the temperature condition at which the suction cup adhesive decorative sheet is used falls below the melting point of the UV absorber, it will liquefy once and the neighboring UV absorbers will aggregate. Since it hardens in this state, it exists in a lump form in the protective layer, and the good dispersed state of the ultraviolet absorber in the protective layer is lost, resulting in a decrease in weather resistance.

The temperature conditions that the suction cup adhesive decorative sheet is exposed to during use repeatedly rise and fall throughout the day, and as a result, the ultraviolet absorber liquefies, bleeds out, partially aggregates, and this solidifies. As a result, the cycle of being present in a lump is repeated, and as a result of bleeding out, the ultraviolet absorber that comes out from the inside of the protective layer of the suction cup adhesive decorative sheet to the outermost surface of the protective layer of the suction cup adhesive decorative sheet is rain. It is considered that the suction cup adhesive decorative sheet is washed away and gradually disappears from the surface of the suction cup adhesive decorative sheet, and the weather resistance is lowered by the amount of the disappeared ultraviolet absorber, and the deterioration of the suction cup adhesive decorative sheet is further promoted. .. The suction cup adhesive decorative sheet of the present invention further suppresses the bleed-out of the ultraviolet absorber and exhibits excellent weather resistance even in such a usage environment.

FIG. 1 is a cross-sectional view showing a typical embodiment of the suction cup adhesive decorative sheet 1 of the present invention. The vertical direction in FIG. 1 corresponds to the thickness direction of the suction cup adhesive decorative sheet 1 of the present invention.

The suction cup adhesive decorative sheet 1 of FIG. 1 has a protective layer 10, a design layer 20, a base material layer 30, and a suction cup adhesive layer 40 in this order. The suction cup adhesive layer 40 has concave shapes 41 on both sides in the thickness direction thereof.
The concave shape 41 may be formed evenly on both sides of the suction cup adhesive layer 40 as shown in FIG. 1, and although it is not shown, it is formed only on the surface of the suction cup adhesive layer 40 opposite to the base material layer 30 side. It may be formed.
Although not shown, the suction cup adhesive decorative sheet 1 of FIG. 1 has a peeling base material layer on the surface of the suction cup adhesive layer 40 opposite to the surface in contact with the base material layer 30. May be good. Further, although not shown, a primer layer may be provided between the layers in order to improve the adhesion between the layers constituting the suction cup adhesive decorative sheet 1. Further, although not shown, the suction cup adhesive decorative sheet 1 of FIG. 1 may further have another functional layer.

<Base layer>
As the base material layer, those usually used as decorative materials can be adopted without limitation, for example, films, sheets and boards made of resin, paper, non-woven fabric or woven fabric, wood, metal, non-metal inorganic material and the like. Can be mentioned.
Usually, a flat base material layer having a predetermined thickness is referred to as a film, a sheet, and a plate in ascending order of thickness. However, in the present invention, it is not particularly necessary to distinguish the difference in thickness. In the book, these names are treated as if there is no essential difference even if they are replaced with each other as appropriate. Further, the difference in the names (difference in thickness) does not cause a difference in the interpretation of the claims of the present invention.
Among the base material layers, it is preferable to use resin or paper from the viewpoint of handleability, and it is more preferable to use resin from the viewpoint of ensuring mechanical strength, molding processability, water resistance and the like.

When the base material layer is a resin, for example, polypropylene, polyethylene, polyolefin-based thermoplastic elastomer, polyolefin resin such as ionomer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalate. Acid-isophthalic acid copolymer, polyester resin such as polyester thermoplastic elastomer, polycarbonate resin, polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer and other acrylic Examples thereof include thermoplastic resins such as resins, acrylonitrile-butadiene-styrene resins (ABS resins), and vinyl chloride resins.
In the specification of the present application, for example, the notations such as "(meth) acrylate" and "(meth) acryloyl group" are "acrylate or methacrylate (or methacrylate)" and "acryloyl group or metaacryloyl group (or metacryloyl group), respectively. It is an abbreviation that means "group)".
Among these, it is preferable to use an olefin resin, a polyester resin, and a vinyl chloride resin from the viewpoints of weather resistance, water resistance, printing suitability, processing suitability, and the like.

When the base material layer is paper, for example, kraft paper, titanium paper, linter paper, parchment paper, glassine paper, parchment paper, resin impregnated paper, thin leaf paper, Japanese paper and the like can be mentioned.
When the base material layer is a woven fabric or a non-woven fabric, it is composed of inorganic fibers such as glass fibers, alumina fibers, silica fibers and carbon fibers, and organic fibers of various synthetic resins such as polyester resin, acrylic resin, polyethylene resin and polypropylene resin. Examples include woven fabrics or non-woven fabrics, and composites thereof.

When the base material layer is wood, wood of various tree species such as cedar, cypress, pine, oak, lauan, teak, and rubber tree can be mentioned. When wood is used as the base material layer, it may be in the form of a film or sheet called a veneer, or in the form of a single plate, plywood, laminated lumber, particle board, fiber plate or the like.
When the base material layer is a metal, examples thereof include iron, aluminum, copper, tin, titanium, and metals made of alloys containing at least one of these metals (for example, carbon steel, stainless steel, duralmin, brass, bronze, etc.). ..
When the base material layer is a non-metallic inorganic material, examples thereof include cement, gypsum, calcium silicate, ceramics, glass, and various ceramics.

The base material layer may be colored or may not be colored (may be transparent), and when it is colored, the mode of coloring is not particularly limited and may be transparently colored. , Opaque coloring (concealment coloring) may be used, and these may be arbitrarily selected.

When the base material layer is colored, the colorants include, for example, inorganic pigments such as titanium white, antimony white, iron black, yellow lead, titanium yellow, valve handle, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. Organic pigments or dyes such as isoindolinone yellow, phthalocyanine blue, nickel-azo complex, azomethine azo black pigment, perylene black pigment; metal pigment consisting of scaly foil pieces such as aluminum and brass; titanium dioxide-coated mica, base Examples thereof include colorants such as pearl luster (pearl) pigments composed of scaly foil pieces such as lead carbonate. For example, when the surface hue of the adherend to which the suction cup adhesive decorative sheet is attached varies, it is white when it is desired to conceal the surface hue and improve the stability of the color tone of the design layer provided as desired. Inorganic pigments such as pigments may be used.

The thickness of the base material layer is not particularly limited, but when the base material layer is a resin, it is preferably 20 to 3200 μm, more preferably 40 to 200 μm, further preferably 40 to 160 μm, and even more preferably 40 to 100 μm. When the substrate layer is paper, the basis weight, usually preferably ^{20~150g / m 2, 30~100g / m} 2 is more preferable.

The shape of the base material layer is not limited to a flat plate shape, and may be a special shape such as a curved plate, a polyhedron, a cone, a pyramid, a truncated cone, or a three-dimensional shape such as a pyramid.
In order to improve the adhesion of the base material layer to other layers of the decorative sheet and the adherend, one or both sides of the base material layer may be physically surface-treated by an oxidation method, an unevenness method, or a chemical surface. Surface treatment such as treatment may be performed, or a primer layer may be formed.

<Protective layer>
The protective layer in the present invention is, for example, a layer formed to impart weather resistance to a suction cup adhesive decorative sheet. The protective layer needs to be arranged on the outermost surface of the suction cup adhesive decorative sheet from the viewpoint of imparting weather resistance to the suction cup adhesive decorative sheet and particularly protecting the design layer and the suction cup adhesive decorative layer.

The protective layer in the present invention is required to contain an ultraviolet absorber in a content of 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin forming the protective layer. If the content of the ultraviolet absorber is less than 1 part by mass, the performance as an ultraviolet absorber cannot be sufficiently obtained, and the suction cup adhesive decorative sheet cannot be imparted with weather resistance. Further, if the content of the ultraviolet absorber exceeds 10 parts by mass, bleed-out is likely to occur and the strength of the protective layer may be lowered, so that the suction cup adhesive decorative sheet is provided with long-term weather resistance. Can't. The lower limit of the content of the ultraviolet absorber contained in the protective layer is more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, based on 100 parts by mass of the resin forming the protective layer. Further, as the upper limit value, 6 parts by mass or less is more preferable, 5 parts by mass or less is further preferable, and 4 parts by mass or less is further preferable with respect to 100 parts by mass of the resin forming the protective layer.

The ultraviolet absorber contained in the protective layer of the present invention contains 45% by mass or more of the ultraviolet absorber having a melting point of 90 ° C. or higher as shown below with respect to the total amount of the ultraviolet absorber contained in the protective layer. It takes that. If the content of the UV absorber having a melting point of 90 ° C. or higher is less than 45% by mass, the UV absorber is more likely to bleed out from the protective layer when used in an environment with large temperature changes such as outdoors. It is not possible to impart long-term weather resistance to the sheet.
The ratio of the ultraviolet absorber at 90 ° C. or higher to the total amount of the ultraviolet absorber contained in the protective layer is more preferably 55% by mass or more, more preferably 65% by mass or more, further preferably 75% by mass or more, and 80% by mass. Even more preferably, it is particularly preferably 100% by mass.

As the ultraviolet absorber used for the protective layer, any ultraviolet absorber having a melting point of 90 ° C. or higher can be used without particular limitation, and any organic or inorganic ultraviolet absorber can be used. As the ultraviolet absorber, it is preferable to use an organic ultraviolet absorber from the viewpoint of the transparency of the protective layer, the dispersibility in the transparent protective layer, and the processability of the decorative sheet.

For example, examples of the organic-based ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers, and among them, hydroxyphenyltriazine-based ultraviolet absorbers. Is preferable.

Examples of the inorganic ultraviolet absorber include titanium dioxide, ferric oxide, zinc oxide, cerium oxide, zirconium oxide and the like having an average particle size of 380 nm or less, preferably 100 nm or less, and more preferably 50 nm or less.

As the ultraviolet absorber used for the protective layer, the ultraviolet absorbers exemplified in the present specification can be used alone or in combination of two or more.

The hydroxyphenyltriazine-based ultraviolet absorber is an ultraviolet absorber having a hydroxyphenyltriazine structure. The hydroxyphenyltriazine structure has a molecular structural property that it bleeds out from the protective layer and is difficult to come off from the viewpoint of steric hindrance, and bleeding out due to liquefaction occurs because it has a melting point of 90 ° C. or higher. It is difficult and the dispersed state in the protective layer remains good, so that excellent weather resistance can be obtained.
In the present invention, by using a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of 90 ° C. or higher, it is possible to suppress the occurrence of bleed-out due to liquefaction that may occur during the use of the suction cup adhesive decorative sheet, and maintain excellent weather resistance. Can be done.

The melting point of the ultraviolet absorber used for the protective layer is preferably 95 ° C. or higher, more preferably 100 ° C. or higher, and more preferably 105 ° C. or higher from the viewpoint of further suppressing the occurrence of bleed-out due to liquefaction and improving the weather resistance. More preferred. The upper limit is not particularly limited, but is preferably 200 ° C. or lower, more preferably 160 ° C. or lower, and even more preferably 130 ° C. or lower, from the viewpoint of solubility in the coating liquid for forming a protective layer.
In the present specification, the melting point of the ultraviolet absorber is "the temperature at which liquefaction begins". Specifically, the ultraviolet absorber is placed in a glass container and allowed to stand in an oven for 1 hour. The temperature at which liquefaction started when the temperature was set to a predetermined temperature was defined as the melting point.

More specifically, as the hydroxyphenyltriazine-based ultraviolet absorber, those represented by the following general formula (1) are preferably mentioned.

In the general formula (1), R ¹¹ is a divalent organic group or a single bond, and R ¹² is a monovalent organic group, an ester group represented by ^{−C (= O) OR 15, −OC (=).} O) The ^{acyloxy group represented by R 16} or the organoloxy group represented by −O R ¹⁷ , and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently hydrogen atoms or monovalents, respectively. It is an organic group, X is an oxygen atom or a single bond, and n ₁₁ and n ₁₂ are independently integers of 1 to 5. Further, ^{when there are a plurality of R 13} and R ¹⁴ , they may be the same or different.

The divalent organic group R ^11, an alkylene group, an aliphatic hydrocarbon group, an alkenylene group is preferably exemplified, from the viewpoint of weather resistance, an alkylene group is more preferable. The number of carbon atoms of these aliphatic hydrocarbon groups is preferably 1 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 4 or less. The alkylene group and the alkaneylene group may be linear, branched or cyclic, but linear or branched is preferable.

As the ^{monovalent organic group of R 12} , an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like are preferably mentioned, and an alkyl group is more preferable. The number of carbon atoms of the alkyl group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less. The alkyl group or alkenyl group may be linear, branched or cyclic, but linear or branched is preferable, and branched is more preferable.

Examples of the monovalent organic group of R ¹³ and R ¹⁴ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aromatic hydrocarbon group such as an aryl group and an arylalkyl group can be used. Preferably, an aryl group is more preferred.

The alkyl group of the monovalent organic group of R ¹³ and R ¹⁴ preferably has 20 or less carbon atoms, more preferably 12 or less, further preferably 4 or less, and particularly preferably 2 or less. That ^{is, as the monovalent alkyl group of R 13} and R ^14, a methyl group and an ethyl group are particularly preferable. Further, in consideration of availability, a methyl group is preferable.

The ^{number of carbon atoms of the aryl groups of R 13} and R ¹⁴ is preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and further preferably 10 or less. The number of carbon atoms of the arylalkyl group is preferably 7 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and further preferably 10 or less.

Examples of the monovalent organic group of R ¹⁵ , R ¹⁶ and R ¹⁷ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aliphatic hydrocarbon such as an alkyl group and an alkenyl group. Groups are preferred, alkyl groups are more preferred. When R ¹⁵ , R ¹⁶ and R ¹⁷ are an alkyl group or an alkenyl group, the number of carbon atoms is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, still more preferable. Is 12 or less.

The groups of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ described above have substituents such as halogen atoms, hydroxyl groups, amino groups, and alkyl groups having 1 to 4 carbon atoms. May be.

Further, n ₁₁ and n ₁₂ are independently integers of 1 to 5, preferably integers of 1 to 3, and more preferably integers of 1 to 2. When n ₁₁ and n ₁₂ are integers of 2 or more, the plurality of R ¹³ and R ¹⁴ may be the same or different, and are preferably the same from the viewpoint of availability.

Typical hydroxyphenyltriazine-based ultraviolet absorbers having a melting point of 90 ° C. or higher are represented by the following chemical formula (2), that is, in the above general formula (1), R ¹¹ is an ethylene group and R. It is preferably exemplified that ¹² is an acyloxy group represented by −OC (= O) R ^{16 (R 16} is a 3-heptyl group), and R ¹³ and R ^{14 are hydrogen atoms.} This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercially available product (manufactured by ADEKA Corporation, trade name "ADEKA STUB LA-46", melting point: 106 ° C.).

Typical hydroxyphenyltriazine-based ultraviolet absorbers having a melting point of 90 ° C. or higher are represented by the following chemical formula (3), that is, in the above general formula (1), R ¹¹ is a single bond and R. It is preferably exemplified that ¹² is an isooctyl group, R ¹³ and R ¹⁴ are phenyl groups, and n ₁₁ and n _{12 are 1.} This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercially available product (manufactured by BASF, trade name "Tinuvin 1600", melting point: 120 ° C.).

The reason why it is easy to impart long-term weather resistance to the suction cup adhesive decorative sheet by using the hydroxyphenyltriazine compound represented by the above chemical formula (3) is that it decomposes when used outdoors, such as an ester bond in its structure. This is thought to be because the molecule does not contain a structure that is likely to be the starting point for changes in the molecular structure. Since the molecule does not have a structure such as an ester bond, decomposition and mutation of the molecular structure are unlikely to occur, bleed-out can be easily suppressed, and long-term weather resistance can be easily imparted. Further, due to the above characteristics, even if the content of the hydroxyphenyltriazine compound represented by the above chemical formula (3) in the protective layer is small, it is possible to impart good weather resistance to the suction cup adhesive decorative sheet.

Typical hydroxyphenyltriazine-based ultraviolet absorbers having a melting point of 90 ° C. or higher are represented by the following chemical formula (4), that is, in the above general formula (1), R ¹¹ is a single bond and R. It is also preferably exemplified that ¹² is a hexyl group and R ¹³ and R ^{14 are hydrogen atoms.} This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercially available product (manufactured by BASF, trade name "Tinuvin 1577", melting point: 148 ° C.).

In the present invention, as the ultraviolet absorber that can be used for the protective layer, in addition to the above-mentioned ultraviolet absorber having a melting point of 90 ° C. or higher, other ultraviolet absorbers, that is, an ultraviolet absorber having a melting point of less than 90 ° C. can also be used. Is. In this case, a conventionally widely used ultraviolet absorber can be used without particular limitation, and a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a hydroxyphenyltriazine-based ultraviolet absorber, and the like can be used. It can be appropriately selected and used from the ultraviolet absorbers. In this case, as the other ultraviolet absorber, a hydroxyphenyltriazine-based ultraviolet absorber is preferable. That is, when an ultraviolet absorber other than an ultraviolet absorber having a melting point of 90 ° C. or higher is used in combination, it is preferable to use a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of less than 90 ° C. as the other ultraviolet absorber. It is preferable to use a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of 90 ° C. or higher and a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of less than 90 ° C. in combination. When a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of less than 90 ° C. is used, the melting point of the ultraviolet absorber is preferably 55 ° C. or higher, more preferably 65 ° C. or higher.

In general, ultraviolet rays that deteriorate various suction cup adhesive decorative sheet constituent materials (base material, protective layer, suction cup adhesive layer, design layer, etc.) only with a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of 90 ° C. or higher, which is actually put into practical use. In many cases, it cannot fully absorb the entire wavelength range of. Therefore, it is preferable to use an ultraviolet absorber having a complementary ultraviolet absorption wavelength range with a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of 90 ° C. or higher, but such an ultraviolet absorber having a complementary ultraviolet absorption wavelength range is preferable. As a result, a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of less than 90 ° C. is a suitable candidate when various performances such as ultraviolet absorption ability, low bleed-out property, price, and colorless transparency are combined. Examples of the hydroxyphenyltriazine-based ultraviolet absorber having a melting point of less than 90 ° C. as described above include the hydroxyphenyltriazine compound represented by the following chemical formula (5). This ultraviolet absorber can effectively absorb the ultraviolet wavelength range that contributes to the deterioration of the propylene-based copolymer containing polypropylene and propylene as the main components of the monomer, and can effectively absorb the base material, the protective layer, and the like. Good weather resistance can be imparted to the sucker adhesive decorative sheet containing polypropylene or a propylene-based copolymer in the sucker adhesive layer, the design layer and the like. This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercially available product (manufactured by BASF, trade name "Tinuvin 479", melting point: 70 ° C.).

The content of the hydroxyphenyltriazine-based UV absorber having a melting point of less than 90 ° C. as described above is preferably less than 55% by mass, more preferably 45% by mass or less, based on the total amount of the UV absorber contained in the protective layer. , 35% by mass or less is more preferable. When the content of the hydroxyphenyltriazine-based UV absorber having a melting point of less than 90 ° C. is less than 55% by mass, the UV absorber bleeds out from the protective layer when used in an environment with a large temperature change such as outdoors. Since it is easy to suppress, it is possible to easily impart long-term weather resistance to the suction cup adhesive decorative sheet.
On the other hand, from the viewpoint of expecting the various performances of the hydroxyphenyltriazine-based UV absorber having a melting point of 90 ° C. or higher, for example, the effect of complementing the UV-absorbing wavelength range, the content of the hydroxyphenyltriazine-based UV absorber having a melting point of less than 90 ° C. The lower limit of is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, based on the total amount of the ultraviolet absorber contained in the protective layer.

From the viewpoint of improving scratch resistance, the protective layer preferably contains a cured product of a curable resin composition as a resin component. The ratio of the cured product of the curable resin composition to the total resin components constituting the protective layer is preferably 70% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. It is more preferable to have 100% by mass, and it is particularly preferable to have 100% by mass.

Examples of the curable resin composition include a thermosetting resin composition containing a thermosetting resin, an ionizing radiation curable resin composition containing an ionizing radiation curable resin, and a mixture thereof. Among these, it is preferable to use a thermosetting resin composition from the viewpoint of processability.
The curable resin composition preferably does not contain cyclohexyl (meth) acrylate as a monomer component. In other words, the protective layer preferably does not contain a cured product of cyclohexyl (meth) acrylate. When the curable resin composition contains cyclohexyl (meth) acrylate as a monomer component, the protective layer may become hard and the processability of the suction cup adhesive decorative sheet may decrease, resulting in inconvenience in using the suction cup adhesive decorative sheet. It is possible that there is.

The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. These can be used alone or in combination of two or more. Further, the thermosetting resin composition may be obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resins. Among these, an acrylic resin is preferable, and an acrylic resin to which an isocyanate curing agent is added is more preferable.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter, also referred to as “ionizing radiation curable compound”). The ionizing radiation curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group.
Further, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, an ultraviolet ray (UV) or an electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also included.
Specifically, the ionizing radiation curable compound can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is in the molecule. Examples thereof include (meth) acrylate monomers having two or more ionizing radiation curable functional groups and having at least a (meth) acryloyl group as the functional groups.
From the viewpoint of improving processing characteristics, scratch resistance and weather resistance, the number of functional groups of the polyfunctional (meth) acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, and further preferably 2 or more and 4 or less. More preferably 2 or more and 3 or less. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

Examples of the polymerizable oligomer include a (meth) acrylate oligomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. For example, radical polymerization type oligomers such as urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, and acrylic (meth) acrylate oligomers. Can be mentioned.
Further, as the polymerizable oligomer, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond in the main chain. In molecules such as aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resins having many reactive groups in small molecules, novolac type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers and the like having cationically polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination of two or more. From the viewpoint of improving processing properties, scratch resistance and weather resistance, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate. One or more selected from oligomers and acrylic (meth) acrylate oligomers is preferable, one or more selected from urethane (meth) acrylate oligomers and polycarbonate (meth) acrylate oligomers is more preferable, and urethane (meth) acrylate oligomers are even more preferable. ..

The number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less, more preferably 6 or less, still more preferably 4 or less, from the viewpoint of improving processing characteristics, scratch resistance and weather resistance. 3 or less is even more preferable.
The weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, and more preferably 3,000 or more and 7,000 or less, from the viewpoint of improving processing characteristics, scratch resistance and weather resistance. , 3,500 or more and 6,000 or less are more preferable. As used herein, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

A monofunctional (meth) acrylate can be used in combination with the ionizing radiation curable resin composition for the purpose of reducing the viscosity of the ionizing radiation curable resin composition. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

When the ionizing radiation curable compound is an ultraviolet curable compound, it is preferable to include an additive such as a photopolymerization initiator or a photopolymerization accelerator.
Examples of the photopolymerization initiator include acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethyl ketal, benzoylbenzoate, α-acyloxym ester, and thioxanthones in the case of radical polymerization type oligomers and monomers. , Can be used alone or in combination of two or more. In the case of an oligomer or monomer having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaserone compound, a benzoin sulfonic acid ester, or the like may be mixed alone or in combination of two or more. Can be used. The amount of these photopolymerization initiators added is about 0.1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable compound.
Further, the photopolymerization accelerator can reduce the polymerization inhibition by air at the time of curing and accelerate the curing rate. For example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like can be used. Can be used alone or in combination of two or more.

The thickness of the protective layer is preferably 1.5 μm or more and 30 μm or less, more preferably 2 μm or more and 20 μm or less, and further preferably 3 μm or more and 15 μm or less from the viewpoint of the balance between processing characteristics, scratch resistance and weather resistance.

<Design layer>
In the present invention, the design layer is, for example, a layer formed to impart designability to a suction cup adhesive decorative sheet. The design layer is required to be formed between the base material layer and the protective layer from the viewpoint of displaying a design such as an advertisement or a pattern and from the viewpoint of enhancing the weather resistance of the design layer.

A pattern can be formed as a design layer. As a pattern, for example, a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric pattern,
Characters, symbols, line drawings, various abstract patterns, monochromatic solid patterns, monochromatic gradations can be mentioned, and these may be combined.

The design layer is a known method such as a printing method such as an offset printing method, a flexographic printing method, a gravure printing method, a screen printing method, a spray printing method and an inkjet printing method, and a transfer method for transferring a printed pattern. Can be formed by

The design layer in the present invention is particularly preferably a layer formed by an inkjet printing method from the viewpoint of obtaining a suction cup adhesive decorative sheet having high designability and enabling multicolor and high-definition printing. However, the multicolor and high-definition printing for obtaining a suction cup adhesive decorative sheet having high designability is not limited to the inkjet printing method but may be, for example, a gravure printing method only from that viewpoint. However, in the gravure printing method, it is necessary to prepare a plate cylinder for each type and ink color, and when switching types, it is necessary to replace the plate cylinder in the printing machine, and the thickness of each ink color is adjusted. It is not suitable for small-lot, high-mix production, as it is necessary. Also, in the offset printing method, it is necessary to prepare an original plate called a PS plate for each color (Y (yellow), M (magenta), C (cyan), K (black)), and a printing machine is used when switching types. As with the gravure printing method, it is not suitable for small-lot, high-mix production, as the PS plate needs to be replaced.

On the other hand, by forming the design layer of the present invention by an inkjet printing method, it is not necessary to produce a plate cylinder (or PS plate), and when the product type is switched, the plate cylinder (or PS plate) is formed in the printing machine. No replacement work is required. Furthermore, in color tone adjustment, there is no need for heavy-duty work such as meat adjustment work in the gravure printing method or re-production of the PS plate in the offset printing method, and only adjustment of the image data to be transmitted to the inkjet printing machine is required. It is possible to match the color tones of the faded design layer. That is, the inkjet printing method is a printing method suitable for the production of a large number of small quantities because the workload at the time of switching the product types and the preparation thereof is low. Therefore, the suction cup adhesive decorative sheet of the present invention is suitable for small-quantity production in which a wide variety of products are produced little by little, or in small-quantity production in which only the damaged part is replaced with a suction cup adhesive decorative sheet whose color is matched to the color tone of the surrounding design layer. Can be applied to.

In the case of the inkjet printing method, the design layer is preferably a layer formed by the inkjet printing method using an ultraviolet curable ink. By using the ultraviolet curable ink, the ink after ejection can be instantly cured by the ultraviolet light source mounted on the print head portion, so that the ink can be easily thickened and a wider range of color tones can be expressed easily. Further, since it is not necessary to apply heat during curing (drying), the base layer is less damaged by heat, and the curing (drying) time can be easily shortened. In addition, solvent-based inks generally have high gloss, but UV-curable inks can be adjusted from low gloss to high gloss similar to solvent-based inks according to preference, and suction cup adhesive makeup. It becomes easy to give a high design to the sheet.

As the ultraviolet curable ink used for forming the design layer, a photopolymerization type is generally used, and mainly photopolymerizable oligomers, photopolymerization monomers, photopolymerization initiators, colorants composed of organic or inorganic pigments, etc. are used. Composition. In such an ultraviolet curable ink, radicals are generated from the photopolymerization initiator by ultraviolet irradiation to attack and activate reactive monomers and oligomers. After that, the activated reactive monomers and oligomers react with each other to be polymerized, which facilitates fixation to the above-mentioned base material layer, the above-mentioned primer layer, and the like.

The ultraviolet curable ink preferably contains an ionizing radiation curable resin composition, and particularly preferably contains an ultraviolet curable resin composition. As the ionizing radiation curable resin composition contained in the ultraviolet curable ink, the ionizing radiation curable resin composition exemplified in the above-mentioned protective layer can be used, and among them, the ultraviolet curable urethane acrylate oligomer is used. Is particularly preferred.
When an ultraviolet curable urethane acrylate oligomer is used as the ionizing radiation curable resin composition, the acrylate components constituting the ultraviolet curable urethane acrylate oligomer include, for example, 1,6-hexanediol diacrylate and tetrahydrofur acrylate. Acrylates such as frills and isobonyl acrylate can be preferably mentioned. Further, as the isocyanate component constituting the ultraviolet curable urethane acrylate oligomer, for example, an isocyanate such as hydrogenated diphenylmethane diisocyanate can be preferably mentioned.

Pigments contained in UV curable ink include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petals, cadmium red, ultramarine blue, cobalt blue and other inorganic pigments, and quinacridone red. , Isoindolinone yellow and phthalocyanine blue, organic pigments such as azo compounds such as nickel-azo complex. Among these, it is preferable that an organic pigment is contained from the viewpoint of being suitable for an inkjet printing method and enabling multicolor and high-definition printing.

In general, organic pigments tend to be inferior in weather resistance, so that the design layer containing the organic pigment has low weather resistance and cannot withstand long-term outdoor use.
However, in the suction cup adhesive decorative sheet of the present invention, as described above, the protective layer contains 1 part by mass or more and 10 parts by mass or less of the ultraviolet absorber with respect to 100 parts by mass of the resin forming the protective layer, and contains the ultraviolet absorber. Since the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more based on the total amount of the above, it is possible to improve the weather resistance even when the design layer contains an organic pigment, and it is possible to improve the weather resistance for a long period of time outdoors. It becomes possible to withstand the use of.

The thickness of the design layer may be appropriately selected according to the desired pattern, but from the viewpoint of hiding the ground color of the base material layer and improving the design, it is preferably 0.5 μm or more and 30 μm or less, and 1 μm or more and 20 μm. The following is more preferable, and 2 μm or more and 10 μm or less is further preferable.

<Sucker adhesive layer>
The suction cup adhesive layer in the present invention has adhesiveness for attaching the suction cup adhesive decorative sheet to the adherend.
Here, the adhesiveness of the suction cup adhesive layer is a property developed by the adhesive force and the adhesive force. Since the suction cup adhesive layer develops adhesiveness due to the adhesive force and the adhesive force, it has further removability to the adherend. Since the suction cup adhesive layer has adhesiveness and re-peelability, the suction cup adhesive decorative sheet of the present invention has so-called reworkability, that is, even if it is once attached to an adherend, it can be peeled off and reattached.
The suction cup adhesive layer needs to be formed on the surface of the base material layer opposite to the design layer in order to impart adhesiveness and removability to the suction cup adhesive decorative sheet.

As the suction cup adhesive layer, a general-purpose one can be used. As such a layer, for example, a layer in which a suction cup is formed on an adhesive resin or the like disclosed in Japanese Patent No. 6553792 can be used. Examples of the suction cup formed on the suction cup adhesive layer include a concave shape formed on the surface of the suction cup adhesive layer. The suction cup adhesive layer has a concave shape at least on the surface of the suction cup adhesive layer opposite to the surface of the suction cup adhesive layer on the base material layer side (the surface in contact with the adherend) from the viewpoint of imparting an adsorption force to the suction cup adhesive layer. Is preferable.

The suction cup adhesive layer of the present invention preferably contains a resin having the adhesiveness exemplified below. By including the adhesive resin, the suction cup adhesive layer tends to exhibit adhesive force to the adherend.

Further, the suction cup adhesive layer of the present invention has a large number of hole-shaped concave shapes opened on the surface, so that the concave shape acts as a fine suction cup as follows. As such a concave shape, a hemispherical concave portion opened on the surface of the suction cup adhesive layer is typical and suitable as a means for solving the problem of the present invention, but other types of concave portions may be adopted. can.
When the suction cup adhesive decorative sheet is attached to an adherend or the like, the suction cup adhesive layer is elastically deformed by the applied pressure. After that, when the pressure is released, when the suction cup adhesive layer tries to return from the deformed state, the closed space in the concave shape becomes a negative pressure, so that the suction cup adhesive layer exhibits a so-called suction cup-like action. Let me.
By such a mechanism, the suction cup adhesive layer tends to exhibit an attractive force with respect to an adherend or the like.

Since the suction cup adhesive layer of the present invention has adhesiveness to the adherend due to the adhesive force and the adsorption force as described above, it can be attached to various adherends.
Although the suction force of the concave shape alone is weak, the suction cup adhesive layer of the present invention can form a large number of concave shapes on its surface, so that it is easy to secure the necessary suction force as a whole. Sufficient adhesiveness can be ensured. Further, when the suction cup adhesive layer is produced, the amount of the concave shape can be adjusted by adjusting the density or the like as a parameter, so that the adhesiveness of the suction cup adhesive layer can be adjusted.

Due to the above-mentioned characteristics, the adhesive force of the suction cup adhesive layer of the present invention is strong in the vertical direction but weak in the horizontal direction. Therefore, when a person peels off the suction cup adhesive decorative sheet, a force is applied in the horizontal direction, so that the suction cup adhesive decorative sheet can be easily peeled off from the adherend. On the other hand, since the force in the horizontal direction is hardly applied except by an artificial action, the suction cup adhesive decorative sheet can be attached to the adherend for a long period of time.

Further, the suction cup adhesive layer preferably has a concave shape on both sides thereof. Further, it is more preferable that the suction cup adhesive layer has a concave shape evenly on both sides thereof. By having a concave shape evenly on both sides of the suction cup adhesive layer, the physical properties of the suction cup adhesive layer can be made uniform, so that the difference in adhesive strength between both sides of the suction cup adhesive layer can be reduced, and the difference in adhesive strength can be reduced. It becomes easy to make the adhesiveness uniform on the entire surface of the suction cup adhesive layer. Therefore, it becomes easy to develop sufficient adhesive force to the base material layer, the peeling base material layer and the adherend, and further, it becomes easy to develop the re-peeling property to the adherend more satisfactorily. Due to these effects, the reworkability of the suction cup adhesive decorative sheet can be further improved.

Here, regarding the state in which the suction cup adhesive layer has a concave shape evenly on both sides thereof, it is preferable to satisfy the following conditions in more detail.
The average value of the diameters of the concave openings existing on the surface of the suction cup adhesive layer on the substrate layer side is ^Dave ₁ , and the surface opposite to the surface on the substrate layer side (the side in contact with the adherend). when the D ^{ave _2,} of each opening concave present on the surface), it is preferable to satisfy the following condition (1).
| D ^ave _1- D ^ave ₂ | / D ^ave ₂ ≤ 0.5 (1)
Further, the condition (1) is ^{more preferably | D ave} _1- D ^ave ₂ | / D ^ave ₂ ≤ 0.25, and further preferably | D ^ave _1- D ^ave ₂ | / D ^ave ₂ ≤ 0.15. preferable.

By satisfying the condition (1) for the concave shape of the suction cup adhesive layer, the physical properties of the suction cup adhesive layer can be made more uniform, so that the difference in adhesive strength between both sides of the suction cup adhesive layer can be made smaller. It also makes it easier to make the adhesiveness more uniform on the entire surface of the suction cup adhesive layer. Therefore, it becomes easy to develop sufficient adhesive force to the base material layer, the peeling base material layer and the adherend, and further, it becomes easy to develop the re-peeling property to the adherend more satisfactorily. Due to these effects, the reworkability of the suction cup adhesive decorative sheet can be further improved.

Since it is practically impossible to obtain the average of all the openings for the average value of the diameters of the openings, here, in the observation range of 1500 μm × 1100 μm, the openings having the largest diameters are ordered in order. The diameter was measured, and the average value was taken as the average value of the diameters of each opening.

Examples of the method for forming the suction cup adhesive layer include a method of forming a composition containing bubbles (hereinafter, may be referred to as a “bubble-containing composition”) by a coating method using, for example, a comma coater or the like. ..

As a method for obtaining the bubble-containing composition, for example, by stirring the undiluted solution for forming a suction cup adhesive layer such as an emulsion containing an adhesive resin while mixing nitrogen gas, air bubbles are contained in the undiluted solution for forming a suction cup adhesive layer. Can be mentioned as a method of obtaining by including. At this time, since the density of the bubble-containing composition can be adjusted by adjusting the mixing amount of nitrogen gas, the amount of the suction cup adhesive layer to be formed including the concave shape can be adjusted, and the suction cup adhesive layer can be adjusted. The adhesiveness of the can be adjusted.

The above-mentioned stock solution for forming a suction cup adhesive layer can be appropriately used as long as it is a liquid composition containing an adhesive resin, and in addition to the above-mentioned emulsion, a suspension, a sol, or the like is used. You may. Moreover, you may use these in combination as appropriate.

^{The density of the bubble-containing composition is preferably 0.1 g / cm 3} or more and 0.8 g / cm ³ or less, preferably 0.2 g / cm, from the viewpoint of optimizing the adhesiveness of the sucker adhesive layer after formation to the adherend. ³ or more and 0.7 g / cm ³ or less is more preferable, and 0.3 g / cm ³ or more and 0.6 g / cm ³ or less is further preferable.

Density sucker adhesive layer, from the viewpoint of adhesion to adherends, preferably 0.1 g / cm ³ or more 0.8 g / cm ³ or less, and more is 0.2 g / cm ³ or more 0.7 g / cm ³ or less It is preferable, 0.3 g / cm ³ or more and 0.6 g / cm ³ or less is more preferable.
From the same viewpoint, the average diameter of the concave openings is preferably 1 μm or more and 300 μm or less, more preferably 5 μm or more and 200 μm or less, and further preferably 10 μm or more and 100 μm or less.

The suction cup adhesive layer preferably contains a resin having adhesiveness from the viewpoint of imparting adhesiveness to the suction cup adhesive layer.

Examples of the adhesive resin include acrylic polymer, styrene butadiene polymer (styrene butadiene rubber), polyisoprene, natural rubber, acrylic nitrile butadiene rubber, ethylene propylene rubber (EPR), and ethylene propylene diene ternary copolymer rubber (Ethylene propylene diene ternary copolymer rubber). EPDM), polynorbornene, polybutadiene, nitrile rubber, chloroprene rubber, butyl rubber, butyl halide rubber, ethylene-vinyl acetate rubber (EVA), polyurethane, silicone rubber, fluororubber, ethylene acrylic rubber, polyester elastomer, epichlorohydrin rubber, polysulfide rubber, Chlorinated polyethylene, polyethylene, polystyrene, polyimide, polyvinyl chloride, polypropylene; polyolefin-based, polyurethane-based, polyester-based, polyamide-based, and polystyrene-based thermoplastic elastomers can be mentioned.
Among these, it is preferable to use an acrylic polymer or a styrene-butadiene polymer from the viewpoint of forming the suction cup adhesive layer and developing the adhesiveness.

The weight average molecular weight of the adhesive resin is preferably 250,000 or more and 120,000 or less, more preferably 270,000 or more and 1,000,000 or less, and further preferably 300,000 or more and 8,000,000 or less. preferable. When the weight average molecular weight is 250,000 or more, the strength of the suction cup adhesive layer as a coating film can be easily increased, so that the adhesiveness of the suction cup adhesive layer to the adherend can be easily increased. Further, since the concave shape is easily formed, the removability can be easily improved. Further, by setting the weight average molecular weight to 12,000,000 or less, it is possible to easily impart flexibility to the suction cup adhesive layer, and it is possible to easily improve the adhesiveness to the adherend and the removability.
The weight average molecular weight in the present specification is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

The suction cup adhesive layer may further contain salt. When the suction cup adhesive layer contains salt, it becomes easy to impart rubber elasticity to the suction cup adhesive layer, and the adhesiveness to the adherend can be further improved.
The salt contained in the suction cup adhesive layer is not particularly limited, and salts such as inorganic salts and organic salts can be used.

Inorganic salts include sulfates, sulfites, carbonates, hydrogen carbonates (dicarbonates) such as sodium, magnesium, aluminum, potassium, calcium, iron, nickel, copper, zinc, silver, lead, tin and barium. ), Nitrate, nitrite, chlorate, hypochlorite, chlorite, perchlorate, permanganate, chromate, phosphate, hydrogen phosphate, chloride, bromide, Iodide; ammonium sulfate, ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrate, ammonium chloride, potassium aluminum sulfate (myoban) and the like can be mentioned.

Organic salts include, for example, formic acid (methanoic acid) salts, acetic acid (ethanoic acid) salts, propanoic acids such as sodium, magnesium, aluminum, potassium, calcium, iron, nickel, copper, zinc, silver, lead, tin and barium. Examples thereof include carboxylic acid salts having 1 to 18 carbon atoms such as salts, butane salts and pentanates; ammonium salts of carboxylic acids having 1 to 18 carbon atoms. In addition, examples of the organic salt include ionic liquids such as ammonium-based, pyridinium-based, imidazolium-based, pyrrolidinium-based, choline-based, phosphonium-based, sulfonium-based, and pyrazolium-based.

The salt contained in the suction cup adhesive layer may be used alone or in combination of two or more from the above-mentioned organic salt and inorganic salt.

The suction cup adhesive layer of the present invention may be appropriately added with an additive as long as the function of the suction cup adhesive layer is not impaired. Additives include, for example, surfactants; defoaming agents; foaming agents (foaming agents); foaming aids; foam stabilizers; foam inhibitors (foaming agents, defoaming agents); emulsifiers; dispersants; wetting agents. Defoamer; Thickener; Hardener; Cross-linking agent; Polymerization initiator; Coloring agent such as pigments and dyes; Plasticizer; Adhesive agent; Filling agent; Antifouling agent; Viscoelasticity adjusting agent; Antiseptic agent; Slip agent ; Dryer; Stabilizer; UV absorber; Antibacterial / antifungal agent; Flame retardant, etc.

Coating amount after formation of the sucker adhesive layer is preferably 13 g / ^{m 2} or more, more preferably 15 g / ^{m 2} or more, more preferably 18 g / ^{m 2} or more, 20 g / ^{m 2} or more is particularly preferable. When the coating amount after forming the suction cup adhesive layer is 13 g / m ² or more, a concave shape is easily formed and a sufficient opening diameter can be obtained, so that the adhesive property and removability to the adherend can be obtained. It becomes easier to secure.
The coating amount after formation of the sucker adhesive layer is preferably 100 g / ^{m 2} or less, more preferably 85 g / ^{m 2,} more preferably 75 g / ^{m 2} or less, particularly preferably 70 g / ^{m 2} or less. When the amount of the suction cup adhesive layer applied after formation is 100 g / m ² or less, it is possible to prevent the suction cup adhesive decorative sheet from becoming too thick, and it is possible to further improve the workability during the pasting work. ..

<Other functional layers>
The suction cup adhesive decorative sheet of the present invention may further have other functional layers, if necessary. Examples of other functional layers include a primer layer, a peeling base material layer, an antireflection layer, an antifouling layer, an antistatic layer, and an antifog layer.

<Primer layer>
The suction cup adhesive decorative sheet of the present invention may further have a primer layer, if necessary. The primer layer is, for example, a layer formed to improve the adhesion between the layers constituting the suction cup adhesive decorative sheet. The primer layer is preferably formed between the base material layer and the design layer from the viewpoint of improving the adhesion between the base material layer and the design layer. Further, from the viewpoint of improving the adhesion between the base material layer and the suction cup adhesive layer, it is preferably formed between the base material layer and the suction cup adhesive layer.
By forming it at the above-mentioned location, the weather resistance and durability of the suction cup adhesive decorative sheet can be further enhanced.

The primer layer preferably contains a cured product of the curable resin composition from the viewpoint of processability and adhesion of each layer.

As the cured product of the curable resin composition contained in the primer layer, the cured product of the curable resin composition exemplified in the above-mentioned protective layer can be used. Among them, from the viewpoint of adhesion of each layer, it is preferable to include a cured product of the thermosetting resin composition, and among these, a cured product of the thermosetting resin composition containing an acrylic resin is preferable, and the acrylic resin is isocyanated. A cured product of a thermosetting resin composition that has been cross-cured with a curing agent is more preferable.
The thickness of the primer layer is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less, and further preferably 3 μm or more and 6 μm or less from the viewpoint of processability and adhesion to the design layer.

<Release base material layer>
From the viewpoint of improving handleability, the suction cup adhesive decorative sheet of the present invention may further have a release base material layer on the surface of the suction cup adhesive layer opposite to the base material layer side.
By arranging the release base material layer on the surface of the suction cup adhesive layer, the suction cup adhesive layer is protected, and when the suction cup adhesive decorative sheets are stored in a roll or stacked, the suction cup adhesive decorative sheets block each other. It is formed to make it easier to prevent it from being stowed away.
Further, the release base material layer is peeled off and removed from the surface of the suction cup adhesive layer when the suction cup adhesive decorative sheet is attached to an adherend or the like.

The peel strength between the peeling base material layer and the suction cup adhesive layer is preferably 10 mN / 25 mm or more, more preferably 20 mN / 25 mm or more, and further preferably 30 mN / 25 mm or more. When the peel strength is 10 mN / 25 mm or more, it is possible to prevent the peeling base material layer from peeling from the suction cup adhesive layer at an unintended timing. The peel strength between the peeling base material layer and the suction cup adhesive layer is preferably 90 mN / mm or less, more preferably 80 mN / mm or less, and further preferably 70 mN / mm or less. When the peel strength is 90 mN / mm or less, it becomes easy to prevent the suction cup adhesive layer from being coagulated and broken when the peeling base material layer is peeled off and removed.

In the present specification, the peel strength can be measured according to the 180 degree peel test of JIS Z 0237: 2009. The atmosphere for measuring the peel strength is preferably 23 ° C. and a humidity of 40 to 65%. Further, it is preferable to allow the sample to acclimatize to the atmosphere for 30 minutes before measuring the peel strength. The measurement is carried out three times per sample, and the average value is taken as the peel strength.

The release base material layer is not particularly limited as long as it can be peeled off from the suction plate adhesive layer, and various forms such as a release film, a separate paper, a separate film, a separate paper, a release film, and a release paper are appropriately used. For example, high-quality paper, coated paper, impregnated paper, plastic film, or the like having a release layer formed on one side or both sides may be used.

The release layer is not particularly limited as long as it is a material having releasability, but for example, silicone resin, organic resin modified silicone resin, fluororesin, aminoalkyd resin, melamine resin, acrylic resin, polyester resin and the like. Can be mentioned. As these resins, any of emulsion type, solvent type and solvent-free type can be used.

When a release film having a release layer is used, for example, a silicone release type PET (polyethylene terephthalate) film, an untreated PET film, a PP (polypropylene) film, a silicone release type paper, or the like should be used. Can be done.

The thickness of the release base material layer is preferably 10 μm or more and 200 μm or less, more preferably 20 μm or more and 150 μm or less, and further preferably 30 μm or more and 125 μm or less. When the thickness of the peeling base material layer is 10 μm or more, the peeling base material layer can have elasticity and can be easily peeled off. Further, when the thickness of the peeling base material layer is 200 μm or less, it is possible to prevent the peeling base material layer from becoming too stiff, and it becomes easy to improve the workability at the time of sticking.

<Manufacturing method of suction cup adhesive decorative sheet>
The method for producing a suction cup adhesive decorative sheet of the present invention includes a step of forming a suction cup adhesive layer on a release base material layer, a step of forming a base material layer on the suction cup adhesive layer, and a step of forming a design layer on the base material layer. , And at least include the step of forming a protective layer on the design layer.

(Sucker adhesive layer forming process)
The suction cup adhesive layer forming step is a step of forming a suction cup adhesive layer on the release base material layer.
As a method for forming the suction cup adhesive layer, it can be formed by applying the above-mentioned bubble-containing composition on the release base material layer by a known coating method and drying it. As a known coating method, for example, a comma coater can be used for coating.

When the applied bubble-containing composition is dried, the drying temperature is preferably 60 ° C. or higher and 140 ° C. or lower, more preferably 80 ° C. or higher and 130 ° C. or lower, and further preferably 100 ° C. or higher and 120 ° C. or lower. preferable. The drying time is preferably 30 seconds or more and 10 minutes or less, preferably 1 minute or more and 5 minutes or less, and further preferably 1 minute 30 seconds or more and 3 minutes or less. Further, when the bubble-containing composition is dried, it may be dried while blowing air.
By drying the bubble-containing composition under the above-mentioned conditions, the bubbles are easily broken and a part of the shape of the bubbles is likely to remain at a sufficient timing when the resin in the bubble-containing composition is dried. .. As a result, a concave shape can be more easily formed on the surface of the bubble-containing composition, and a suction cup adhesive layer having a concave shape is formed.

If the bubbles burst in a state where the resin in the bubble-containing composition is insufficiently dried, the shape of the bubbles is unlikely to remain and the concave shape is difficult to form. Further, if the resin is dried too much before the bubbles are bubbled, the bubbles cannot be bubbled and it becomes difficult to form a concave shape.
Therefore, in order to form a concave shape on the suction cup adhesive layer, it is important that the timing of bubble rupture and drying of the resin is balanced, and the suction cup adhesive layer having the above-mentioned concave shape is formed. It is preferable to dry under the above-mentioned drying conditions.

(Base material layer forming process)
The base material layer forming step is a step of forming a base material layer on the suction cup adhesive layer. As a method for forming the base material layer, it can be formed by laminating the base material layer to the suction cup adhesive layer, and for example, it can be formed by laminating by a known laminating method.

(Design layer forming process)
The design layer forming step is a step of forming a design layer on the base material layer. As a method for forming the design layer, a known printing method can be used, and among them, it is preferably formed by an inkjet printing method. By forming the design layer by the inkjet printing method, as described above, multicolor and higher-definition printing can be performed, and the suction cup adhesive decorative sheet can easily impart high design. Further, it is suitable for easy application in the case of producing a large number of varieties little by little, or in the case of small-quantity production in which only the damaged part is replaced with a suction cup adhesive decorative sheet whose color is matched to the color tone of the surrounding design layer.

(Protective layer forming process)
The protective layer forming step is a step of forming a protective layer on the design layer. As a method for forming the protective layer, it can be formed by a known coating method, for example, by a gravure coat.

(Primer layer forming step)
The method for producing a suction cup adhesive decorative sheet of the present invention may further include a primer layer forming step before the above-mentioned base material layer forming step, if necessary. When a primer layer is formed between the base material layer and the suction cup adhesive layer, the primer layer is formed on the surface of the base material layer in contact with the suction cup adhesive layer. When a primer layer is formed between the base material layer and the design layer, the primer layer is formed on the surface of the base material layer in contact with the design layer.

Further, the method for producing a suction cup adhesive decorative sheet of the present invention may further include a primer layer forming step before the above-mentioned design layer forming step, if necessary. When the primer layer forming step is included before the design layer forming step, the primer layer forming step is a step of forming a primer layer between the base material layer and the design layer. In this case, the primer layer is formed on the surface side of the base material layer in contact with the design layer.

When the method for producing a suction cup adhesive decorative sheet of the present invention includes a primer layer forming step, the primer layer may be formed on only one side of the base material layer, if necessary, and the primer layers are formed on both sides of the base material layer. You may. When the primer layer is formed on only one side of the base material layer, the primer layer formation step may be included either before the base material layer forming step or before the design layer forming step. When the primer layers are formed on both sides of the base material layer, the primer layers may be formed on both sides of the base material layer before the base material layer forming step, or before the base material layer is formed and before the design layer is formed. The primer layer may be formed in two steps. When the primer layer is formed in two steps, in the primer layer forming step before the base material layer is formed, the primer layer is formed on the surface of the base material layer on the side in contact with the suction cup adhesive layer.
When the primer layers are formed on both sides of the base material layer, each primer layer may be formed from the same composition or may be formed from different compositions.

The method of forming the primer layer can be formed by a known coating method, for example, by a gravure coat.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the embodiments described in the examples.

1. 1. Measurement and evaluation 1-1. Measurement of Melting Point of UV Absorbent Regarding the melting point of the UV absorber used in Examples and Comparative Examples, the UV absorber was placed in a glass container and allowed to stand in an oven, and the oven was kept at a predetermined temperature for 1 hour. When liquefaction started, the predetermined temperature was set as the melting point. When the ultraviolet absorbers LA-46 (ultraviolet absorber 1), Tinuvin 1600 (ultraviolet absorber 2), and Tinuvin 479 (ultraviolet absorber 3) used in this example and the comparative example were put into an oven at 70 ° C., respectively. A photographic image of the appearance is shown in FIG. It can be seen that Tinuvin 479 is liquefied, and the temperature at which such a state began to be liquefied was defined as the temperature at which liquefaction began, and this was defined as the melting point. The results of melting point measurement are summarized in Table 1.

1-2. Reworkability The suction cup adhesive decorative sheet (size: length 400 mm, width 900 mm) obtained in the examples and comparative examples is pasted with a polyolefin wallpaper (thickness 0.6 mm, manufactured by Sangetsu Co., Ltd., trade name "EB cloth EB2002"). The combined gypsum board (thickness 9.5 mm, manufactured by Yoshino Gypsum Co., Ltd., trade name "Tigerboard 3 x 6 version") was pasted on a polyolefin wallpaper and left at 60 ° C. for 1 week.
After being left under the above conditions, the suction cup adhesive sheet was peeled off, and the reworkability when affixed to the polyolefin wallpaper of a newly prepared gypsum board was evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 1.
<Evaluation criteria>
A: At the time of peeling, there was no adhesive residue on the polyolefin wallpaper, and it was possible to reattach it on the polyolefin wallpaper of the newly prepared gypsum board.
C: At the time of peeling, the adhesive remained on the polyolefin wallpaper and the suction cup adhesive decorative sheet itself was torn, so that it could not be peeled cleanly. Or, even if it could be peeled off cleanly, it could not be reattached on the polyolefin wallpaper of the newly prepared gypsum board.

1-3. Evaluation of weather resistance Accelerated weather resistance test by metal halide lamp (MWOM) on the suction cup adhesive decorative sheets obtained in Examples and Comparative Examples (after irradiating with ultraviolet rays for 20 hours under the following irradiation conditions, 4 under the following dew condensation conditions The step of performing time dew condensation was set as one cycle, and the test (test in which the cycle was repeated) was carried out for 1600 hours. After the accelerated resistance test, the appearance of the suction cup adhesive decorative sheet was visually confirmed and evaluated according to the following criteria. The evaluation results are summarized in Table 1. The test equipment, irradiation conditions, and dew condensation conditions for the accelerated weather resistance test are as follows.
<Evaluation criteria>
1: No change in appearance was confirmed.
2: A slight change in appearance was confirmed, but there was no problem in practical use.
3: A large change in appearance was confirmed.
4: A remarkable change in appearance was confirmed.

<Test equipment>
Made by Daipla Wintes, trade name "Daipla Metal Weather"
<Irradiation conditions>
Illuminance: 65mW / cm ² , Black panel temperature: 63 ° C, Humidity in tank: 50% RH, Time: 20 hours <Condensation conditions>
Illuminance: 0 mW / cm ² , humidity in the tank: 98% RH, time: 4 hours

2. Method for Making Sucker Adhesive Decorative Sheet [Example 1]
A bubble-containing composition prepared as follows on a polyethylene terephthalate film (thickness 40 μm, manufactured by Mitsui Chemicals Tohcello Co., Ltd., trade name “SP-PET PET-O3-BU”) whose surface has been peeled off as a peeling base material layer. The product was applied so that the coating amount after drying was 30 g / m ² , and dried at 100 ° C. for 1 minute to form a suction cup adhesive layer. The density of the suction cup adhesive layer formed was 0.4 g / cm ³ .

<Bubble-containing composition>
An acrylic emulsion containing an acrylic polymer (manufactured by DIC, trade name "DCNAL MFP-20", acrylic polymer concentration: 50%, solvent: water) is placed in a stirrer, and the mixture is stirred while mixing nitrogen gas in the acrylic emulsion. Then, bubbles were contained in the acrylic emulsion to prepare a bubble-containing composition.

Next, a polyvinyl chloride sheet having a thickness of 150 μm (20 parts by mass of DINP (diisononyl phthalate) added as a plasticizer to 100 parts by mass of the polyvinyl chloride resin) is laminated on the suction cup adhesive layer to form a base material layer. bottom.

Next, a design having a thickness of 10 μm was printed on the base material layer by inkjet printing using an inkjet printer (manufactured by EFI, trade name “VUTEk GS5500LXrpro”, ink used: EFI VUTEk GSLXr 3M SuperFlex UV ink (ultraviolet curable type)). A layer was formed.

Next, the coating liquid for forming a protective layer according to the following formulation was applied onto the design layer and dried to form a protective layer having a thickness of 5 μm to obtain a suction cup adhesive decorative sheet of Example 1.

<Coating liquid for forming a protective layer>
-Thermosetting resin: 100 parts by mass (two-component curable acrylic-urethane resin)
-Ultraviolet absorber 1 (hydrophenyltriazine-based ultraviolet absorber): 2 parts by mass (manufactured by ADEKA Corporation, trade name "ADEKA STUB LA-46", melting point: 106 ° C., compound represented by the above chemical formula (2))
-Ultraviolet absorber 2 (hydrophenyltriazine-based ultraviolet absorber): 2 parts by mass (manufactured by BASF, product surface "Tinuvin 1600", melting point: 120 ° C., compound represented by the above chemical formula (3))

[Examples 2 to 5]
The suction cup adhesive decorative sheets of Examples 2 to 5 were obtained in the same manner as in Example 1 except that the types and amounts of the ultraviolet absorbers in the protective layer were as shown in Table 1.

[Comparative Example 1]
Implemented except that a non-sucker adhesive layer (coating amount after drying: 30 g / m ² , density 1.0 g / cm ³ ) was formed using an acrylic emulsion containing no air bubbles instead of the suction cup adhesive layer. A suction cup adhesive decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1.

[Comparative Examples 2 to 7]
The suction cup adhesive decorative sheets of Comparative Examples 2 to 7 were obtained in the same manner as in Example 1 except that the types and amounts of the ultraviolet absorbers in the protective layer were as shown in Table 1.

The ultraviolet absorbers 1 to 3 in Table 1 are as follows.
-UV absorber 1 (hydrophenyltriazine-based UV absorber):
Made by ADEKA Corporation, trade name "ADEKA STAB LA-46", melting point: 106 ° C
(Compound represented by the above chemical formula (2))
-UV absorber 2 (hydrophenyltriazine-based UV absorber):
Made by BASF, product surface "Tinuvin 1600", melting point: 120 ° C
(Compound represented by the above chemical formula (3))
-UV absorber 3 (hydrophenyltriazine-based UV absorber):
Made by BASF, trade name "Tinuvin 479", melting point: 70 ° C
(Compound represented by the above chemical formula (5))

From the results in Table 1, the suction cup adhesive decorative sheets of Examples 1 to 5 having the characteristics of the present invention were excellent even under extremely severe conditions of performing an accelerated test with a metal halide lamp (MWOM) for 1600 hours. Since it has weather resistance, it was confirmed that it has excellent weather resistance even when used outdoors for a long period of time.
In Comparative Example 1, since a non-sucker adhesive layer having no concave shape was used instead of the suction cup adhesive layer, it could not be peeled off cleanly from the polyolefin wallpaper, resulting in poor reworkability.
The suction cup adhesive decorative sheet of Comparative Examples 2 to 5 in which the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is small with respect to the total amount of the ultraviolet absorber used in the protective layer is a hydroxyphenyltriazine-based ultraviolet absorber (UVA3: Tinuvin479). Even if it was used, it could not be said that it was excellent in terms of weather resistance. Further, the suction cup adhesive decorative sheet of Comparative Example 6 in which the content of the ultraviolet absorber in the protective layer is too large is the amount of the ultraviolet absorber retained in the protective layer even if the ultraviolet absorber having a melting point of 90 ° C. or higher is used. Due to the large amount of UV rays, the cross-linking density of the protective layer cannot be sufficiently obtained and sufficient durability cannot be ensured, and bleed-out occurs to cause deterioration of the appearance, which can be the starting point of deterioration. It was not excellent in terms of points.

Since the sucker adhesive decorative sheet of the present invention has excellent weather resistance, interior members of buildings such as walls, ceilings and floors or exterior members such as outer walls, roofs, eaves ceilings, fences and gates, window frames, etc. Various doors such as entrance doors, handrails, skirts, surrounding edges, window frames, door frames, fittings such as malls or building members, general furniture such as stools, shelves, desks, kitchen furniture such as dining tables and sinks, or It is suitably used as a surface decorative plate for cabinets of light electrical products, OA equipment, etc., interior or exterior members of vehicles, advertisements, posters, and the like. Further, the decorative material of the present invention is preferably used as the above-mentioned various members, especially as a member used in an environment exposed to direct sunlight.

1 Sucker adhesive decorative sheet 10 Protective layer 20 Design layer 30 Base material layer 40 Sucker adhesive layer 41 Concave shape

Claims (3)

It has a protective layer, a design layer, a base material layer, and a suction cup adhesive layer in this order.
The protective layer contains an ultraviolet absorber and contains
The content of the ultraviolet absorber with respect to 100 parts by mass of the resin forming the protective layer is 1 part by mass or more and 10 parts by mass or less.
A suction cup adhesive decorative sheet in which the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber. The suction cup adhesive decorative sheet according to claim 1, wherein the suction cup adhesive layer has a concave shape at least on a surface opposite to the surface on the base material layer side. The suction cup adhesive decorative sheet according to claim 1 or 2, wherein the amount of the suction cup adhesive layer applied after formation is 13 g / m ² or more and 100 g / m ^{2 or less.}

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