JP2000136360A - Pressure-sensitive adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide pressure-sensitive adhesive sheets which are good in color development and have satisfactory flexibility and accordingly, are excellent in applicability to curved surfaces notwithstanding use of an olefin resin substrate sheet capable of reducing a load upon being burned. SOLUTION: On one side of an olefin resin substrate sheet composed of 100 pts.wt. olefin resin and 3-90 pts.wt. elastomer having a peak temperature of tan δ in the dynamic viscoelasticity spectrum of -40 to 50 deg.C is laminated a crosslinked colored coated film layer containing at least one resin component selected from the group consisting of an acrylic resin, a urethane resin, a polyester resin and a fluoroplastic and a pigment, and on the other side of the substrate sheet is laminated a pressure-sensitive adhesive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive sheet used as an outdoor or indoor advertising sticker, a display sticker, or a decorative sheet for an electric signboard, and more particularly, to an adhesive sheet having excellent followability to a curved surface. The present invention relates to a pressure-sensitive adhesive sheet that can be incinerated by a simple incineration facility.

[0002]

2. Description of the Related Art Various decorative adhesive sheets such as advertising stickers, display stickers, and decorative sheets for illuminated signboards have been proposed. The conventional decorative adhesive sheet has excellent weather resistance and coloring properties due to the addition of a pigment, and thus has been constituted by using a vinyl chloride resin film as a base material. The production of this type of adhesive sheet
It was done as follows.

[0003] Depending on the purpose, a pigment is kneaded into a substrate made of a vinyl chloride resin film to be colored, or the surface of the substrate is printed. Next, a pressure-sensitive and / or heat-sensitive adhesive according to the application is applied to one surface of the substrate to form a pressure-sensitive adhesive layer. Further, in order to protect the pressure-sensitive adhesive layer, a release material such as release paper is stuck on the pressure-sensitive adhesive layer.

The decorative adhesive sheet is often used outdoors and is used for various purposes. For example, it may be affixed as an advertising sticker on a signboard, an advertising tower, a shutter, a show window, or the like. Also, they are used as decorative stripe stickers in vehicles such as automobiles and motorcycles, and in ships such as motor boats. Further, it is also used for forming display stickers on traffic signs, road signs, information boards, and the like.

[0005] The decorative adhesive sheet is also used for an electric signboard. In this case, the decorative adhesive sheet needs to transmit light, and therefore, a transparent substrate that transmits light is used as the base material.

[0006] Since the above-mentioned various decorative adhesive sheets are often used outdoors, they are excellent in weather resistance and have appropriate flexibility to be attached to a three-dimensional curved surface. Strongly required.

The conventional decorative adhesive sheet has a suitable weather resistance and a sufficient flexibility to be attached to a curved surface because the adhesive sheet for decoration is made of a vinyl chloride resin film as a base material. However, when a vinyl chloride resin film is used as the base material, the incinerator may be damaged due to generation of chlorine gas or hydrogen chloride gas during incineration and disposal. That is, there is a problem in that a burden is imposed on the incinerator, which cannot be processed by a simple incinerator, and furthermore, the durability of the incinerator decreases. Therefore, disposal is often performed by landfill, and the burden on the environment has been a problem.

Accordingly, in recent years, a method of reducing the burden of incineration by using a polyolefin resin film as a base material has been attempted. For example, Japanese Patent Application Laid-Open No. H8-1577
No. 80 discloses a decorative pressure-sensitive adhesive sheet that can reduce the burden of incineration by using a polyolefin-based resin film as a base material.

However, Japanese Patent Application Laid-Open No. 8-157780 only discloses the use of a polyolefin-based resin film, but does not show the specific contents of the polyolefin-based resin film.

When a pressure-sensitive adhesive layer is formed on one side of a commercially available polyolefin-based resin film to form a decorative pressure-sensitive adhesive sheet, flexibility is higher than that of a conventional vinyl chloride-based resin film. It was not enough, and the followability to a curved surface was not enough.

Further, the olefin resin has poor weather resistance as compared with the vinyl chloride resin, and is not suitable for long-term outdoor use. In addition, when molding into a sheet, a number of molding methods such as a calendering method, an extrusion method, and a sol-casting method of dispersing and casting in an organic solvent can be used with a vinyl chloride resin, whereas an olefin resin can be used. Is almost limited to an extrusion method in which the resin is extruded after being melted at 300 ° C. or higher. Therefore, only pigments that do not fade even under heating conditions of 300 ° C. and have excellent heat resistance could be used.

In addition, although the detailed mechanism is unknown, even if the same pigment is added in the same amount, there is a problem that the coloring property is poor as compared with the case where a vinyl chloride resin is used. Furthermore, when the above-mentioned pressure-sensitive adhesive sheet for a decorative sign is constructed using a commercially available olefin-based resin film, if titanium oxide is contained, sufficient transmitted light cannot be obtained, and titanium oxide is mixed. Even when not performed, the light transmittance was low and a clear decorative effect could not be obtained.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and its object is to:
Despite using an olefin-based resin base sheet that can reduce the burden of incineration, it is possible to provide a pressure-sensitive adhesive sheet that has good color developability, has sufficient flexibility, and is therefore excellent in sticking property to a curved surface. It is in. Another object of the present invention is to provide a pressure-sensitive adhesive sheet which is excellent in light transmittance and is therefore suitable as a decorative pressure-sensitive adhesive sheet used for, for example, an electric signboard.

[0014]

According to the first aspect of the present invention, there is provided a pressure-sensitive adhesive sheet comprising 100 parts by weight of an olefin resin and an elastomer having a tan δ peak temperature of −40 to 50 ° C. in a dynamic viscoelastic spectrum. A crosslinked color containing one or more resin components and pigments selected from the group consisting of an acrylic resin, a urethane resin, a polyester resin, and a fluororesin, on one surface of an olefin resin substrate sheet composed of 90 parts by weight. A coating layer is laminated, and an adhesive layer is laminated on the other surface.

According to a second aspect of the present invention, there is provided the pressure-sensitive adhesive sheet according to the first aspect, wherein the olefin-based resin base sheet comprises 100 parts by weight of the olefin-based resin, 3 to 90 parts by weight of the elastomer, and 10 to 10 parts by weight of the titanium oxide. A white sheet containing 200 parts by weight, wherein the crosslinked colored coating layer is 100 parts by weight of at least one resin component selected from the group consisting of an acrylic resin, a urethane-based resin, a polyester-based resin, and a fluororesin. And 5 to 80 parts by weight of a pigment.

The pressure-sensitive adhesive sheet according to the third aspect of the present invention has an olefin resin of 100 parts by weight and a peak temperature of tan δ in a dynamic viscoelastic spectrum of -40 to 50 ° C.
A relatively low flexibility second olefin resin sheet made of an olefin resin is provided on at least one surface of the first olefin resin sheet having a relatively high flexibility, which is composed of 3 to 200 parts by weight of an elastomer. Acrylic resin on one side of the laminated olefin resin base sheet,
A crosslinked colored coating layer containing at least one resin component and a pigment selected from the group consisting of a urethane-based resin, a polyester-based resin and a fluorine-based resin, and a pressure-sensitive adhesive layer laminated on the other surface. And

According to a fourth aspect of the present invention, in the pressure-sensitive adhesive sheet according to the third aspect, at least one of the first olefin-based resin sheet and the second olefin-based resin sheet has an olefin-based resin weight of 100%. For the department,
It is composed of a white olefin resin sheet containing 10 to 300 parts by weight of titanium oxide, and the crosslinked colored coating film layer is made of an acrylic resin, a urethane resin, a polyester resin and a fluorine resin. 100 parts by weight of at least one resin component selected from the group and pigment 5
It is characterized by containing up to 80 parts by weight.

The pressure-sensitive adhesive sheet according to the fifth aspect of the present invention is suitable for use as, for example, a decorative marking film for an electric sign, and the pressure-sensitive adhesive sheet according to the first or third aspect of the present invention. Wherein the olefin-based resin base sheet mainly comprises a propylene-based resin;
The total light transmittance according to IS K 7105 is 85% or more, the haze value is 5% or less, and the crosslinked colored coating layer is formed of an acrylic resin, a urethane resin, a polyester resin, and a fluorine resin. And at least one resin component selected from the group consisting of 100 parts by weight and 0.5 to 20 parts by weight of a pigment.

In the present invention, as the elastomer, a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or a hydrogenated product thereof is preferably used as described in claim 6. .

Hereinafter, the present invention will be described in detail. (Olefin-based resin base sheet) In the pressure-sensitive adhesive sheet according to the present invention, the olefin-based resin constituting the olefin-based resin base sheet is not particularly limited, and examples thereof include low-density polyethylene, medium-density polyethylene, and high-density polyethylene. Polyethylene such as linear low density polyethylene; polypropylene; ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-α-olefin copolymer; Further, those obtained by mixing an elastomer such as a styrene-based resin with these olefin-based resins can also be used.

Further, it may be constituted by using a mixed resin obtained by uniformly mixing a plurality of different olefin-based resins, or by laminating a plurality of sheets made of different olefin-based resins. That is, as in the invention according to claim 3, the second olefin resin sheet having relatively low flexibility is laminated on at least one surface of the first olefin resin sheet having relatively high flexibility. You may comprise an olefin-type resin base material sheet. In this case, since the first olefin-based resin sheet contains 3 to 200 parts by weight of a specific elastomer described later with respect to 100 parts by weight of the olefin-based resin, the flexibility is enhanced by the inclusion of the elastomer.

In the wide range of the present invention, a pigment may be contained in the olefin-based resin base material sheet. In this case, the pigment is heat-resistant at about 300 ° C., which is the usual extrusion temperature of the olefin-based resin. As long as it has
It can be appropriately selected according to the purpose, for example, azo-based, phthalocyanine-based, sulene-based, dye lake-based, quinacridone-based, dioxazine-based organic pigments; oxides such as titanium oxide described above, molybdate chromate system,
Various inorganic pigments such as sulfide / selenide, ferrocyanide, and calcium carbonate can be appropriately used.
By including these pigments in the olefin-based resin substrate sheet, the color of the adherend can be hidden and the saturation of the colored coating layer can be improved. In this case, a white pigment is desirable for hiding the color of the adherend and improving the color saturation of the colored coating film layer. In particular, titanium oxide is suitably used.

Therefore, according to the second and fourth aspects of the present invention,
In the olefin-based resin base sheet, or at least one of the olefin resin sheets constituting the olefin-based resin base sheet, titanium oxide is blended in the above-described specific ratio, thereby improving the saturation of the colored coating layer. It is possible. It is also possible to easily change the color tone of the pressure-sensitive adhesive sheet by changing the color of the colored coating layer.

That is, since the white olefin-based resin base sheet is used in the second and fourth aspects of the present invention, the white olefin-based resin base sheet is mass-produced and various colored coating films are prepared. By laminating the layers, pressure-sensitive adhesive sheets of various colors and saturations can be easily obtained.
Therefore, it is possible to easily cope with the production of various kinds of pressure-sensitive adhesive sheets in small quantities.

As the above-mentioned titanium oxide, those having a rutile-type crystal and an average particle diameter of 0.01 to 1 μm are preferably used because of good performance of concealing the base and high chroma.

The surface of the titanium oxide particles may be treated with, for example, aluminum, silica, or an organic substance in order to enhance the dispersibility in the olefin resin.

When the addition amount of titanium oxide is small, the concealing property is reduced and the color of the adherend is transmitted, so that the color of the colored coating layer becomes dull and sufficient chroma cannot be obtained. If the amount is too large, the physical properties of the olefin-based resin sheet substrate deteriorate. Therefore, in the invention of claim 2, titanium oxide is added in a ratio of 10 to 200 parts by weight based on 100 parts by weight of the olefin resin. Further, in the invention according to claim 4, in at least one of the first and second olefin-based resin sheets, titanium oxide is blended in a ratio of 10 to 300 parts by weight with respect to 100 parts by weight of the olefin-based resin.

In the pressure-sensitive adhesive sheet according to the fifth aspect of the present invention, the above-mentioned total light transmittance may be 85% or more and the haze value may be 5% or less even if a pigment is contained. It is necessary when used for decoration of an electric sign, and it is therefore desirable that the pigment is not contained.

In the olefin resin substrate sheet of the present invention, an elastomer having a tan δ peak temperature of -40 to 50 ° C. in the above dynamic viscoelastic spectrum is used in the above-mentioned specific ratio in order to enhance flexibility. Here, the peak temperature of tan δ refers to the peak value of tan δ at a frequency of 100 MHz when measuring dynamic viscoelasticity with a dynamic viscoelasticity measuring instrument. When the peak temperature is lower than -40 ° C, the flexibility of the olefin-based resin sheet base material cannot be increased, and the workability for a three-dimensional curved surface becomes insufficient.
The effect of increasing flexibility sharply decreases.

The above elastomer has a peak temperature of tan δ in a dynamic viscoelastic spectrum of −40 to 50.
Although it is not particularly limited as long as it is ° C., it is preferably a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or a hydrogenated product thereof because of its excellent solubility in an olefin resin. The thing is used suitably.

More preferably, as shown in the following structure, it is desirable that styrene and isoprene are polymerized so that 50% or more of the styrene and isoprene have 3,4 bonds.

[0032]

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In order to suppress the fish-eye phenomenon in the case of continuously producing an olefin resin base material sheet, a hydrogenated product of a block polymer of styrene and isoprene is used, and 50% or more of the diene portion of the isoprene is used. Is preferably used.

According to the first aspect of the present invention, the elastomer is used in an amount of 3 to 90 parts by weight based on 100 parts by weight of the olefin resin.
It is added in parts by weight. If the blending ratio of the elastomer is less than 3 parts by weight, the flexibility of the olefin-based resin base sheet is not sufficient, and the followability to a curved surface is reduced, and
If the amount exceeds 0 parts by weight, it will be too soft, and actual processing operations such as sticking will be extremely difficult, and the cost of the pressure-sensitive adhesive sheet will be high because the elastomer is expensive.

For the same reason, according to the third aspect of the present invention, in the first olefin resin sheet having relatively high flexibility, 100 parts by weight of the olefin resin is used.
The elastomer is used in a proportion of 3 to 200 parts by weight.

In the third aspect of the present invention, the reason why the upper limit of the blending ratio of the elastomer is high is that the olefin-based resin base material sheet is different from the first olefin-based resin sheet having high flexibility and the flexibility. This is because a low second olefin-based resin sheet is laminated, and the first olefin-based resin sheet contains the above-mentioned elastomer in the above-described specific ratio. That is, even if the blending ratio of the elastomer is 200 parts by weight, the second olefin-based resin sheet is laminated, so that the entire olefin-based resin base sheet does not become too soft.

The above-mentioned elastomer may be contained in the second olefin resin sheet. The thickness of the olefin-based resin substrate sheet in the invention according to claim 1 is not particularly limited, but is preferably 20 to 1
The range of 50 μm is preferred, and more preferably 40 to 1 μm.
00 μm. When the thickness is less than 20 μm, the olefin-based resin base sheet becomes too soft, making the construction difficult and insufficient in strength. When the thickness is more than 150 μm, it becomes difficult to achieve the following, and it follows the adherend such as a three-dimensional curved surface. This is not preferred because the transparency and, in some cases, the transparency are reduced.

According to the third aspect of the present invention, the olefin resin sheet substrate is formed by laminating the first and second olefin resin sheets. In this case, the overall thickness is For the same reason as above, 20-1
A range of 50 μm is desirable, and more preferably 40 to 1 μm.
00 μm.

The thickness of the first and second olefin resin sheets according to the third aspect of the present invention is as follows.
There is no particular limitation, and it may be appropriately determined according to the mode of lamination, the type of material, and the application.

According to the fifth aspect of the present invention, the olefin-based resin base sheet contains a propylene-based resin as a main component and has a total light transmittance of 85 in accordance with JIS K 7105.
% And a haze value of 5% or less are used. The pressure-sensitive adhesive sheet according to the fifth aspect of the present invention is used, for example, as a decorative pressure-sensitive adhesive sheet in an electric signboard, and therefore needs to have a certain degree of transparency. Therefore, the total light transmittance is 85% or more, and the haze value is 5% or less. When the total light transmittance is less than 85%, the color of the transmitted light becomes black even if the colored coating layer is laminated, and the decorative effect is reduced,
If the haze exceeds 5%, the color clarity of light transmitted through the colored coating film layer will be poor.

In the invention according to the fifth aspect, since the olefin-based resin base sheet needs to have the above-mentioned characteristics, a propylene-based resin having excellent transparency as a main component is used. . Here, the propylene-based resin is not particularly limited, and includes a wide range of polymers having propylene as a main structural unit, and may be polypropylene or a mixture of polypropylene and polyethylene. Above all, it is desirable to use a propylene-based resin having excellent heat resistance in order to laminate a crosslinked colored coating film layer.

The thickness of the olefin-based resin base sheet in the pressure-sensitive adhesive sheet according to the fifth aspect of the present invention is as follows:
Preferably, it is 20 to 150 μm, more preferably 40 to 150 μm.
The range is 100 μm. If the thickness is less than 20 μm, the film itself becomes too soft, making the construction difficult or insufficient in strength. If it exceeds 150 μm, it becomes difficult, the ability to follow an adherend having a three-dimensional curved surface is reduced, and the transparency is also reduced.

A hindered amine compound may be added to the olefin resin substrate sheet in order to enhance weather resistance. As the hindered amine compound,
Although not particularly limited, the following compounds 1) to 1
1) can be exemplified.

1) 2,2,4,4-tetramethylpiperidyl-4-benzoate 2) bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate 3) tris (2,2,6, 6-tetramethyl-4-piperidyl) phosphite 4) 1,3,8-triaza-7,7,9,9-tetramethyl-3-n-octylspiro [4,5] decane-2,
4-dione 5) 1,2,3,4-tetra (4-carbonyloxy 2,2,6,6-tetramethylpiperidyl) -butane 6) 1,3,8-triaza-7,7,9,9 -Tetramethyl-2,4-dioxosepyro [4,5] decane 7) tri (4-acetoxy-2,2,6,6-tetramethylpiperidyl) amine 8) 4-acetoxy-2,2,6,6- Tetramethylpiperidine 9) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine 10) 4-benzyloxy-2,2,6,6-tetramethylpiperidine 11) 4-phenylcarbamoyloxy-2,2 , 6,
6-Tetramethylpiperidine In the production of the olefin resin material sheet, in addition to the olefin resin, various components such as the vinyl aromatic polymer described above are mixed, and an appropriate molding method such as a T-die method or inflation molding is performed. Can be used.

In the case where the first and second olefin resin sheets are laminated to form an olefin resin base sheet as in the third aspect of the present invention, the first olefin resin sheet is used. By co-extruding the constituent material and the material forming the second olefin-based resin sheet, an olefin-based resin base sheet can be obtained.

Further, other additives may be added to the olefin-based resin base sheet as long as the sheet formability and sheet properties are not impaired. Examples of the additives include an ultraviolet absorber and a heat absorber. Stabilizers and the like.

Examples of the above-mentioned ultraviolet absorbent include salicylic ester-based, benzophenone-based, benzotriazole-based and cyanoacrylate-based ultraviolet absorbers.

Examples of the heat stabilizer include metal soap heat stabilizers, organotin heat stabilizers, lead heat stabilizers, antimony heat stabilizers, and nonmetal heat stabilizers.

(Colored Coating Layer) In the pressure-sensitive adhesive sheet according to the present invention, a crosslinked colored coating layer is laminated on one surface of an olefin-based resin substrate sheet, and decoration of a desired color is performed by the colored coating layer. The effect is exhibited. The colored coating film layer is configured to include at least one resin component selected from the group consisting of an acrylic resin, a urethane-based resin, a polyester-based resin, and a fluorine-based resin, and a pigment.

In the case where a white olefin resin sheet base material is used as in the invention according to the second and fourth aspects, the resin component and the pigment are mixed with each other.
The pigment is blended in a range of 5 to 80 parts by weight with respect to 0 parts by weight. If the amount is less than 5 parts by weight, the target hue may not be obtained. If the amount is more than 80 parts by weight, the coatability of the composition containing the resin component and the pigment decreases, and the properties of the surface are reduced. Roughness and high unit cost of raw materials increase costs.

When a transparent olefin resin substrate sheet suitable for an electric sign is used as in the invention of claim 5, 100 parts by weight of the resin component is contained in the crosslinked colored coating film layer. It is desirable that the pigment is blended in a ratio of 0.5 to 20 parts by weight with respect to parts. If the blending ratio of the pigment is less than 0.5 parts by weight, a target hue cannot be obtained.
If the amount exceeds 20 parts by weight, the concealing property of the colored coating film layer becomes too high, and for example, when used for an illuminated signboard, the decorative effect by transmitted light cannot be sufficiently exhibited.

The pigment used in the colored coating layer is not particularly limited, but the above-mentioned organic pigments generally used and excellent in weather resistance can be suitably used. In applications requiring further weather resistance, the use of inorganic fired pigments can further improve weather resistance.

The resin component is at least one resin selected from the group consisting of an acrylic resin, a urethane resin, a polyester resin and a fluorine resin, and these resins are capable of forming a flexible film. It is suitable. Specifically, an acrylic polymer, a urethane-based polymer, a polyester-based polymer, and a fluorine-based polymer having a plurality of cross-linking points such as a hydroxyl group, a glycidyl group, and an amino group in a molecule are used as main-chain polymers. The required function is imparted by forming a three-dimensional crosslinked structure by crosslinking with a crosslinking agent having a plurality of reactive functional groups in the molecule.

In order to further impart weather resistance and strength, if necessary, various polyols, melamine, silanol, a hydroxyl group structure, an alicyclic epoxy compound and glycidyl (meth) acrylate are arranged inside, and a crosslinking component is provided. A three-dimensional cross-linked structure can be formed with isocyanate, melamine, silane, or the like to impart a function. In addition, by blending the main chain itself with acid-modified, silicone-modified, fluorinated, vinylidene fluoride, etc. according to the required quality,
Adhesion and weather resistance functions can also be provided.

Examples of the fluororesin include, for example, vinylidene fluoride polymers, fluoroethylene polymers, fluoroethylene vinyl ether polymers,
A polymer obtained by grafting a fluorine-based polymer to another polymer such as a polymer obtained by grafting an alkyl fluoride onto a polymer having an acrylic main chain can be used. Examples of the cross-linking agent include isocyanates, melamines, and methylols, and aliphatic isocyanates are preferably used for the purpose of suppressing problems such as yellowing due to light.

Hereinafter, the acrylic resin will be described in detail. The acrylic resin is obtained by cross-linking an acrylic polyol having a large number of hydroxyl groups in a molecule with a polyisocyanate compound in a network, and is usually a solution containing an acrylic polyol and a solution containing a polyisocyanate compound. Are used within the limits of the pot life, and become an acrylic resin after curing.

More specifically, when the colored coating layer is formed, the polyisocyanate compound and the organic solvent capable of crosslinking the acrylic polyol in a network form in a base material coating solution comprising an acrylic polyol, a pigment and an organic solvent. After adding a cross-linking agent solution consisting of, and thoroughly mixing, coating and drying, a colored coating layer can be formed.

The above-mentioned acrylic polyol has a large number of hydroxyl groups bonded as side chains to the main chain made of an acrylic polymer, and improves the flexibility of the colored coating film layer. Unlike the case where the pigment is contained in the production of the olefin-based resin base sheet, the pigment does not particularly require heat resistance, and specific examples include all the above-mentioned pigments.

The above-mentioned organic solvent is used for facilitating uniform mixing of components such as an acrylic polyol, a pigment and a polyisocyanate compound, and at the same time, adjusting the viscosity of the coating layer by adjusting the viscosity. An organic solvent having an active hydrogen capable of reacting with the isocyanate group of the compound cannot be used in principle.

Examples of usable organic solvents include, but are not limited to, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, tetrahydrofuran, and cyclohexanone. Not something.

If the amount of the organic solvent added after uniformly mixing the above-mentioned constituents is small, the viscosity of the coating solution becomes high and streaks may occur. The organic solvent is preferably added in an amount of 20 to 100 parts by weight, more preferably 30 to 70 parts by weight, based on 100 parts by weight of the total of the acrylic polyol and the polyisocyanate compound.

As the above polyisocyanate compound,
For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPD)
I), p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate, lysine diisocyanate (LDI), tetramethyl xylene diisocyanate (TMXDI), triphenylmethane triisocyanate, tris (Isocyanate phenyl) thiophosphate, lysine ester triisocyanate, polyisocyanates such as undecane triisocyanate, and adduct type, buret type, and isocyanurate type of these trimethylolpropanes. Absent.

A crosslinking agent solution was added to the base material coating solution,
The method of mixing is not particularly limited, but mechanical high-speed mixing is preferred because the polyisocyanate compound may be deactivated by moisture in the air.

Other additives may be added to the colored coating layer mainly composed of the acrylic resin as long as the physical properties are not deteriorated. Examples of such additives include an ultraviolet absorber and a light stabilizer. Agents and the like.

The method for laminating the colored coating layer on the olefin-based resin substrate sheet is not particularly limited, and various coating methods can be used. For example, a bar coater,
Examples include a reverse coater, a spray gun coater, a knife coater, a rotary screen, screen printing, a gravure coater, and a kiss coater.

In order to enhance the anchoring property between the olefin-based resin substrate sheet and the colored coating layer, the surface of the olefin-based resin substrate sheet may be subjected to a treatment such as a corona discharge treatment or application of a primer. .

When the glass transition temperature of the above-mentioned colored coating film layer is low, a tacky feeling appears on the surface and blocking may occur, and when the glass transition temperature is high, the coating film layer becomes difficult and the workability may decrease. Therefore, the glass transition temperature is 20
To 100 ° C, more preferably 30 to 70 ° C,
Particularly preferably, it is 40 to 60 ° C.

When the coating thickness of the colored coating layer is reduced, the weather resistance may be reduced. When the coating thickness is increased, the drying property is reduced, and a tackiness may appear on the surface due to the residual solvent, and blocking may occur. is there. Therefore, the coating thickness of the colored coating layer is preferably 5 to 50 μm, more preferably 10 to 40 μm, and particularly preferably 15 to 35 μm.

(Pressure-Sensitive Adhesive Layer) In the present invention, a pressure-sensitive adhesive layer is laminated on one surface of the olefin-based resin substrate sheet obtained as described above to form a pressure-sensitive adhesive sheet.

Here, the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer is not particularly limited, and a conventionally used acrylic or rubber-based pressure-sensitive adhesive can be used. However, when used as a decorative adhesive sheet, it is often used outdoors, so it is desirable to use an acrylic adhesive excellent in weather resistance.

As the above-mentioned acrylic pressure-sensitive adhesive, those having an alkyl (meth) acrylate homopolymer or a copolymer of an alkyl (meth) acrylate and another vinyl monomer as a main component are preferably used.

As the alkyl (meth) acrylate, an alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is used. Specifically, examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, Lauryl (meth) acrylate and the like can be mentioned.

These alkyl (meth) acrylates may be used alone or in combination of two or more. However, considering the balance between the adhesiveness and the cohesiveness and the like, the homopolymer usually has an alkyl (meth) acrylate having a glass transition temperature (Tg) of -50 ° C. or lower as a main component, and the homopolymer has a methyl ( It is desirable to use an alkyl (meth) acrylate having a small number of carbon atoms in the alkyl group, such as meth) acrylate or ethyl (meth) acrylate.

Further, in addition to the above-mentioned alkyl (meth) acrylate, a vinyl monomer copolymerizable therewith may be copolymerized. Such copolymerized vinyl monomers include (meth) acrylic acid, maleic acid,
Carboxyl group-containing vinyl monomer such as fumaric acid or itaconic acid or anhydride thereof; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, modified caprolactone Examples include hydroxyl group-containing vinyl monomers such as (meth) acrylate.

When the pressure-sensitive adhesive layer is formed by using the above-mentioned acrylic pressure-sensitive adhesive, the above-mentioned acrylic copolymer may be used as a main component, and further, a known tackifying resin may be contained. The acrylic pressure-sensitive adhesive may be a solvent-type acrylic pressure-sensitive adhesive polymerized in a solvent, or may be an emulsion-type acrylic pressure-sensitive adhesive polymerized in water. Further, a block polymerization type pressure-sensitive adhesive obtained by irradiating the monomer mixture with ultraviolet light may be used.

In the pressure-sensitive adhesive sheet according to the present invention, the pressure-sensitive adhesive layer is laminated on one surface of the olefin-based resin base material sheet. In this case, the method for laminating the pressure-sensitive adhesive layer is not particularly limited. That is, a method of applying a pressure-sensitive adhesive to the surface of a release material such as release paper by a quantitative coating method, heating and drying, and then laminating one surface of the olefin-based resin base sheet, or A method of directly applying an adhesive on one surface can be employed.

The thickness of the pressure-sensitive adhesive layer is not particularly limited. However, when the pressure-sensitive adhesive layer is used as a decorative pressure-sensitive adhesive sheet and the adhesion strength to an adherend and the ability to follow a curved surface are taken into consideration, the thickness is in the range of about 10 to 50 μm. It is desirable to do.

As described above, the pressure-sensitive adhesive sheet according to the present invention has a structure in which a pressure-sensitive adhesive layer is laminated on one surface of an olefin-based resin base material sheet. To do so, the pressure-sensitive adhesive layer is covered with a release material. Such a release material is not particularly limited, but for example, release paper that has been subjected to silicone treatment can be used.

The pressure-sensitive adhesive sheet obtained above may be affixed to the entire surface of the adherend to be decorated, or may be cut into desired figures or characters by a computer-controlled cutting machine. It may be scraped and transferred to an adherend using an application adhesive tape.

(Function) In the pressure-sensitive adhesive sheet according to the first aspect of the present invention, the peak temperature of tan δ in the dynamic viscoelasticity spectrum is-
Since an olefin-based resin substrate sheet containing 3 to 90 parts by weight of an elastomer having a temperature of 40 to 50 ° C. is used, the peak temperature of tan δ in the dynamic viscoelastic spectrum is −40 to 50 ° C. By containing the olefin resin base sheet, the olefin resin base sheet has sufficient flexibility.
Therefore, the ability to follow a three-dimensional curved surface of the adhesive sheet is improved.

Further, unlike the case where a vinyl chloride resin film is used, incineration can be performed with simple equipment, and the burden on the environment can be reduced. Further, a crosslinked colored coating layer containing at least one resin component and a pigment selected from the group consisting of an acrylic resin, a urethane resin, a polyester resin and a fluorine resin on one surface of the olefin resin substrate sheet. Are stacked, various decorative effects are exhibited by the colored coating layer. In this case, various decorative effects can be exhibited by changing the colored coating layer.

In the pressure-sensitive adhesive sheet according to the second aspect of the present invention, in the olefin-based resin base sheet, titanium oxide is further added to 100 parts by weight of the olefin-based resin.
0 to 200 parts by weight are blended into a white sheet,
Since the crosslinked colored coating layer contains 100 parts by weight of at least one resin component selected from the group consisting of an acrylic resin, a urethane-based resin, a polyester-based resin, and a fluorine-based resin and 5-80 parts by weight of a pigment, The color of the body can be effectively hidden, the chroma of the colored coating layer can be improved, and the decorative effect of the colored coating layer can be effectively exhibited.

In the pressure-sensitive adhesive sheet according to the third aspect of the present invention, at least one surface of the first olefin resin sheet having relatively high flexibility has a relatively low flexibility of the second olefin resin. The olefin-based resin base material sheet is configured by laminating the system-based resin sheets. Here, in the first olefin-based resin sheet, the above-mentioned specific elastomer is blended in the above-mentioned specific ratio with respect to the olefin-based resin. The ability to follow an adherend having a three-dimensional curved surface is improved.

In the pressure-sensitive adhesive sheet according to the fourth aspect of the present invention, at least one of the first and second olefin-based resin sheets is mixed with 10 to 300 parts by weight of titanium oxide per 100 parts by weight of the olefin-based resin. Since the resin sheet is a white resin sheet, the adherend can be effectively concealed, and the color saturation of the colored coating layer can be increased. Further, the crosslinked colored coating film layer contains 5 to 80 parts by weight of a pigment with respect to 100 parts by weight of at least one resin component selected from the group consisting of an acrylic resin, a urethane-based resin, a polyester-based resin and a fluorine-based resin. Because of this configuration, a good decorative effect is exhibited.

According to the fifth aspect of the present invention, since the olefin-based resin base sheet mainly contains a propylene-based resin, the olefin-based resin base sheet is excellent in heat resistance. Less is. Further, the olefin-based resin base sheet has a total light transmittance of 85% or more according to JIS K7105 and a haze value of 5% or less, and thus has excellent light transmittance. When used for an adhesive sheet for a signboard, 0.5 to 20 parts by weight of a pigment based on 100 parts by weight of at least one resin component selected from the group consisting of an acrylic resin, a urethane-based resin, a polyester-based resin, and a fluorine-based resin. The decorative effect of the compounded crosslinked colored coating layer is well exhibited.

In the invention according to claim 6, since the styrene-butadiene block copolymer, the styrene-isoprene block copolymer or a hydrogenated product thereof is used as the elastomer, the flexibility of the olefin-based resin base sheet is improved. Is sufficiently increased, the followability to the three-dimensional curved surface of the pressure-sensitive adhesive sheet is enhanced, and the occurrence of fish eyes during continuous production can be suppressed.

[0087]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to specific embodiments. However, the present invention is not limited to the following examples.

(Materials used) In the following Examples and Comparative Examples, the following olefin resins and elastomers were used.

Olefin resin: low density polyethylene (manufactured by Nippon Polychem Co., Ltd., product numbers: UF840, MFR1.5
g / 10 min) Olefin resin: Polypropylene (manufactured by Japan Polyolefin Co., Ltd., product number: FA465, MFR 7.0 g / 10)
Minute) Elastomer: Styrene-isoprene block copolymer which is a vinyl aromatic elastomer (manufactured by Kuraray Co., Ltd., trade name: Hibler, product number: VS-1, tan δ peak temperature = 20 ° C.)

Elastomer: Styrene-isoprene block copolymer (manufactured by Kuraray Co., Ltd., trade name: Hibler, product number: HVS-3, tan δ peak temperature = -5 ° C.) Elastomer: styrene-isoprene block copolymer (manufactured by Shell Chemical Co., Ltd.) , Part number: TR1107, tan δ peak temperature = −72 ° C.) Elastomer: styrene-butadiene block copolymer (manufactured by Asahi Kasei Corporation, trade name: Tuftec, part number: H105)
1, tan δ peak temperature = 95 ° C)

Example 1 As shown in Table 1 below,
Olefin resin (manufactured by Nippon Polychem Co., Ltd., product number: UF8
40) 100 parts by weight, 12 parts by weight of a vinyl aromatic elastomer (manufactured by Kuraray, part number: VS-1) and 50 parts by weight of titanium oxide (manufactured by Ishihara Sangyo, part number: CR-60) Composition having a thickness of 50 μm by the T-die method.
And corona discharge treatment (42 dyne / cm) was performed on both surfaces in-line.

On one side of the obtained olefin-based resin base material sheet, a paint (product name: Planit U # 700, manufactured by Dainippon Paint Co., Ltd.) 1 comprising an acrylic polyol and an organic solvent was applied.
00 parts by weight, 6.5 parts by weight of a curing agent (manufactured by Nippon Polyurethane Co., trade name: Coronate 2094), and 50 parts by weight of a composite pigment (including cyanine blue, quinacridone red, polyazo yellow and cyanine green) Was applied with a spray gun coater to form a crosslinked colored coating film layer having a thickness of 20 μm after drying. In the table, a base resin composed of an acrylic polyol and a curing agent is referred to as an acrylic urethane-based resin.

On the other hand, a two-part crosslinkable acrylic pressure-sensitive adhesive (trade name: BPS5520, manufactured by Toyo Ink Co., Ltd.) was applied to a release paper having a surface treated with silicon so that the thickness after drying was 40 μm using a comma coater. Coated. The pressure-sensitive adhesive layer applied to the release paper is laminated on the surface opposite to the side on which the crosslinked colored coating film layer of the olefin resin substrate sheet obtained as described above is formed, An adhesive sheet of Example 1 was obtained.

(Examples 2 to 10) The contents of the olefinic resin, the elastomer, and the pigment in the colored coating layer used were changed as shown in Tables 1 and 2 below. In, an adhesive sheet was obtained in the same manner as in Example 1 except that titanium oxide was not blended. In Table 2, for Examples 7 to 10, the total light transmittance and the haze value of the olefin-based resin substrate sheets obtained as described above are also shown.

(Comparative Examples 1 to 8) Olefin resins and elastomers were blended as shown in Tables 1 and 2 below, and the pigment content in the colored coating layer was determined as shown in Tables 1 and 2 below.
Example 1 except for the changes as shown in Table 2.
In the same manner as in the above, an adhesive sheet was obtained.

Comparative Examples 5 to 8 correspond to Examples 7 to 10, in which no titanium oxide was used. Therefore, the total light transmittance and haze value of the olefin-based resin substrate sheet were also determined. Shown.

(Comparative Examples 9 and 10) As shown in Table 3 below, an organosol was prepared by blending a vinyl chloride resin, a plasticizer, a stabilizer, a white pigment and a solvent. The obtained organosol was applied on paper of an alkyd resin coating process using a comma coater, and dried at a temperature of 180 ° C. for 7 minutes to obtain a vinyl chloride resin base sheet having a thickness of 60 μm. On one surface of the obtained vinyl chloride resin base material sheet, a crosslinked colored coating film layer was formed in the same manner as in Example 1,
An adhesive layer and a release paper were laminated on the other surface.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

Example 11 As shown in Table 4 below, an olefin resin (manufactured by Nippon Polychem Co., Ltd., product number: U
F840) 100 parts by weight, 5 parts by weight of a vinyl aromatic elastomer (manufactured by Kuraray, product number: VS-1) and 20 parts by weight of titanium oxide (manufactured by Ishihara Sangyo, product number: CR-60) Resin as an outer layer composition (product number: UF840, manufactured by Nippon Polychem Co., Ltd.)
Using a composition containing 15 parts by weight of elastomer and 60 parts by weight of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., product number: CR-60) as an intermediate layer composition in 100 parts by weight, using a multilayer extrusion T-die machine, An olefin-based resin base sheet having a total thickness of 50 μm was obtained in which the thickness of the intermediate layer was 32 μm and the thickness of the outer layers provided on both surfaces was 9 μm, respectively.

A crosslinked colored coating layer, pressure-sensitive adhesive layer and release paper were laminated in the same manner as in Example 1 except that the olefin resin base sheet obtained as described above was used. An adhesive sheet was used.

(Examples 12 to 16) Table 4 shows the types and amounts of the olefin resin and the elastomer constituting the outer layer and the intermediate layer constituting the laminated olefin resin base material sheet, and the mixing ratio of titanium oxide. In the same manner as in Example 11, except that the content was changed as shown in Table 4, and the content of the composite pigment contained in the crosslinked colored coating film layer was changed as shown in Table 4 below. An adhesive sheet was obtained.

(Comparative Examples 11 to 13) The olefin-based resins and elastomers used, and the mixing ratios thereof and the content ratio of titanium oxide were changed as shown in Table 4 below. An adhesive sheet was obtained in the same manner as in Example 11, except that the pigment content in the coating layer was changed as shown in Table 4 below.

[0105]

[Table 4]

(Example 17) 100 parts by weight of a paint (product name: Planit U # 500, manufactured by Dainippon Paint Co., Ltd.) composed of a polyester polyol and an organic solvent was applied to one surface of the obtained olefin-based resin base material sheet. 6.5 parts by weight of a curing agent (manufactured by Nippon Polyurethane Co., trade name: Coronate 2094) and a composite pigment (including cyanine blue, quinacridone red, polyazo yellow and cyanine green) 5
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that a paint consisting of 0 parts by weight was applied using a spray gun coater, and a crosslinked colored coating layer having a thickness of 20 μm after drying was formed. In the table, the base resin is referred to as a polyester resin.

(Example 18) On one surface of the obtained olefin resin base material sheet, a fluororesin paint (manufactured by Nippon Paint Co., Ltd., trade name: Duflon Pure Clear) and a composite pigment (cyanine blue, quinacridone red) , Containing polyazo yellow and cyanine green) in the same manner as in Example 1 except that a paint consisting of 50 parts by weight was applied with a spray gun coater to form a crosslinked colored coating layer having a thickness of 20 μm after drying. To obtain a pressure-sensitive adhesive sheet. In the table, the base resin is referred to as a fluororesin.

(Comparative Example 14) On one surface of the obtained olefin resin base material sheet, 100 parts by weight of an uncrosslinked acrylic resin paint (trade name: Reseric TC, manufactured by Fujikura Kasei Co., Ltd.) and a composite pigment (cyanine) Including blue, quinacridone red, polyazo yellow and cyanine green) 5
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that a paint consisting of 0 parts by weight was applied using a spray gun coater, and a crosslinked colored coating layer having a thickness of 20 μm after drying was formed. In the table, the base resin is referred to as an uncrosslinked acrylic resin.

[0109]

[Table 5]

(Evaluation) With respect to the pressure-sensitive adhesive sheets of Examples and Comparative Examples obtained as described above, when used as a marking film, curved workability, film handling property,
Film formability, substrate concealing property, coating film formability, transmitted light decorative property, incineration property, tearability, weather resistance, etc. were evaluated in the following manner. The results are shown in Tables 6 to 9 below.

Curved surface workability: Each adhesive sheet is placed on the upper surface of the corrugated plate 1 shown in a sectional view in FIG.
First, an adhesive sheet was pushed in with a special tool for a wrench so as to adhere to the valley, and then adhered. After leaving at a temperature of 23 ° C. for 3 days, the floating state of the pressure-sensitive adhesive sheet was visually evaluated on a 5-point scale. The evaluation criteria are as follows.

5 points: moderate flexibility, no problem in the construction of the adherend having a curved surface. 4 points: Although it has moderate flexibility, it feels a little uncomfortable in softness or hardness, but there was no problem with construction on a curved adherend.

3 points: The application to a curved adherend was somewhat difficult, probably because of insufficient flexibility. 2 points: Due to insufficient flexibility, it was extremely difficult to construct a curved adherend. 1 point: Due to insufficient flexibility, construction on a curved adherend could not be performed.

Film handleability: The handleability of the pressure-sensitive adhesive sheet itself after peeling the pressure-sensitive adhesive sheet from the release paper was evaluated on a 5-point scale. The evaluation criteria are as follows. 5 points: The pressure-sensitive adhesive sheet had appropriate flexibility, and there was no problem in handleability. 4 points: I feel a little strange in the flexibility of the adhesive sheet,
There was no problem.

3 points: The base sheet was too soft, so it was difficult to handle. The self-adhesion phenomenon due to the bending of the base sheet sometimes occurred. 2 points: Since the base sheet was too soft, careful handling was required. The self-adhesion phenomenon due to the bending of the base sheet frequently occurred. 1 point: The handling was substantially impossible because the base sheet was too soft.

Film Formability: The moldability of a T-die molding machine when forming an olefin resin substrate sheet was evaluated. The meanings of the evaluation symbols are as follows. …: The resin film could be molded without any problem. Δ: Uneven thickness (single meat) occurred due to high rigidity of the resin. X: The resin was too rigid and could not be extruded from the T-die.

Substrate concealability: The degree of color concealment when the pressure-sensitive adhesive sheet was adhered to the adherend (the adherend) was evaluated. The evaluation symbols are as follows.

…: When the adhesive sheet was stuck, the color of the base was not picked up at all. Δ: When the pressure-sensitive adhesive sheet was stuck, the color of the base was slightly recognized. C: When the pressure-sensitive adhesive sheet was affixed, the color of the base was considerably recognized, and the decorativeness was significantly reduced.

Film formability: The coating properties and the appearance after coating were evaluated when coating the colored film layer on the olefin resin base material sheet with a spray gun. The meanings of the evaluation symbols are as follows.

…: There was no problem in coating properties, and the appearance after coating was good. Δ: Coating unevenness occurred slightly, and the appearance after coating was rough. X: The spray gun was clogged during coating, and a colored coating layer could not be formed.

Transmitted light decorative property: The pressure-sensitive adhesive sheet was irradiated with light to evaluate the color clarity and the like due to the transmitted light. The contents of the evaluation symbols are as follows. …: The color was clear and the light was not cloudy. Δ: The color sharpness was slightly inferior, and the color was apt to be cloudy. X: The color was not clear and the transmitted light was dark and cloudy.

Burnability: Adhesive sheets were each 5 cm ×
The sample was cut into a size of 5 cm. This sample was burned in a closed vessel, and the generated gas was collected in a syringe, and the presence or absence of hydrogen chloride and chlorine gas was measured by gas chromatography. The meanings of the evaluation symbols are as follows. …: No hydrogen chloride or chlorine was detected. ×: Hydrogen chloride or chlorine was detected.

Tearability: The tearability of the pressure-sensitive adhesive sheet was evaluated according to the Elmendorf method of JIS K 7128, except that the sheet thickness was converted to 60 μm. 200-400
gf / 16 is the optimal value.

Weather resistance: The appearance change of the colored coating layer after irradiation for 2000 hours with a sunshine weather meter was visually measured. The meanings of the evaluation symbols are as follows. A: Almost no change in appearance was observed. …: Slight fading and decrease in gloss were observed. X: Large changes in color and gloss were observed.

[0125]

[Table 6]

[0126]

[Table 7]

[0127]

[Table 8]

[0128]

[Table 9]

[0129]

In the pressure-sensitive adhesive sheet according to the first aspect of the present invention, the olefin-based resin is blended with an elastomer having a tan δ peak temperature of −40 to 50 ° C. in a dynamic viscoelastic spectrum at the above-mentioned specific ratio. Since the olefin-based resin base sheet is used, the adherence to the adherend having a three-dimensional curved surface of the pressure-sensitive adhesive sheet is improved, and therefore, the adhesive sheet can be easily applied to adherends of various shapes. For example, a decorative adhesive sheet suitable for the above application can be formed. Also, a crosslinked colored coating layer containing at least one resin component and a pigment selected from the group consisting of an acrylic resin, a urethane resin, a polyester resin and a fluorine resin on one surface of the olefin resin substrate sheet. Since the decorative effect is exhibited by being laminated, it is possible to easily provide a pressure-sensitive adhesive sheet having a different decorative effect by appropriately changing the colored coating film layer, and to cope with a small quantity and variety of decorative adhesive sheets. it can.

Further, the olefin resin base sheet is
Compared to a vinyl chloride resin-based substrate, it can be incinerated with a simple incineration facility, so that the environmental burden can be reduced. In the pressure-sensitive adhesive sheet according to the second aspect of the present invention, in the olefin-based resin base sheet, titanium oxide is further contained at the above-described specific ratio to form a white sheet, so that the color of the adherend is concealed. The crosslinked colored coating layer is
At least one selected from the group consisting of acrylic resins, urethane resins, polyester resins, and fluororesins
Since it has a configuration in which the pigment is blended with the specific resin component in the above-described specific ratio, it is possible to exhibit a good decorative effect with excellent chroma.

According to the third aspect of the present invention, the second olefin resin sheet having low flexibility is laminated on at least one surface of the first olefin resin sheet having high flexibility to form the olefin resin base sheet. Since the specific elastomer is blended in the specific ratio in the first olefin-based resin sheet, followability to an adherend having a three-dimensional curved surface is improved. Therefore, similarly to the first aspect of the present invention, it can be easily attached to adherends having various shapes. Further, since the olefin resin is mainly used, it can be incinerated by a simple incinerator, and the environmental burden can be reduced.

Further, the pressure-sensitive adhesive sheet which can exhibit various decorative effects by using the crosslinked colored coating layer and can easily exhibit different decorative effects only by changing the crosslinked colored coating layer. Can be provided.

According to a fourth aspect of the present invention, in the pressure-sensitive adhesive sheet according to the third aspect, at least one of the first and second olefin-based resin sheets contains titanium oxide in the above-described specific ratio. Since it is a white olefin-based resin sheet, the adherend can be effectively concealed, and the crosslinked colored coating layer is formed of an acrylic resin,
Since the pigment is contained in at least one of the resin components selected from the group consisting of a urethane-based resin, a polyester-based resin, and a fluorine-based resin at the above-described specific ratio, a good decorative effect with excellent chroma is exhibited.

According to the fifth aspect of the present invention, since the total light transmittance and the haze of the olefin-based resin base sheet are within the above-mentioned specific ranges, the olefin-based resin base sheet has excellent transparency and a crosslinked colored coating layer. Since it has a configuration in which the pigment is blended with the resin component in the above-described specific ratio, when used as a decorative adhesive sheet for an illuminated signboard, for example, it exhibits an excellent decorative effect by transmitted light. In addition, since the olefin-based resin base sheet is mainly composed of propylene-based resin, it is excellent in heat resistance and can provide a decorative pressure-sensitive adhesive sheet which is hardly deteriorated by heat when used for an electric signboard. .

In the invention according to claim 6, since the elastomer is composed of a styrene-butadiene block copolymer, a styrene-isoprene block copolymer or a hydrogenated product thereof, the olefin resin base material sheet Is effectively enhanced, and application to an adherend having a three-dimensional curved surface is further facilitated.

Further, since the colored coating film layer is cross-linked, the weather resistance is also good. In particular, the use of a fluorine resin as a resin component can further improve the weather resistance.

[Brief description of the drawings]

FIG. 1 shows evaluations of pressure-sensitive adhesive sheets of Examples and Comparative Examples.
Sectional drawing which shows the cross section of the corrugate board prepared as an adherend.

 ────────────────────────────────────────────────── ─── front page of continued F-term (reference) 4F100 AA21A AK03A AK03D AK06 AK07A AK07D AK12A AK12J AK17B AK25B AK28A AK28J AK41B AK51B AK73A AL09A AR00C BA03 BA04 BA07 BA13 CA13B CB05C EJ05B GB90 HB00B JK13D JK17D JL10B JL13C YY00A YY00B 4J002 BB031 BB051 BB061 BB071 BB151 BP012 FD030 FD050 GJ00 4J004 AA05 AA10 AB01 CA04 CC02 CC03 CC05 CD05 CD06 FA01

Claims (6)

[Claims] 1. An olefin resin of 100 parts by weight and a peak temperature of tan δ in a dynamic viscoelasticity spectrum of -4.
One or more resins selected from the group consisting of acrylic resins, urethane resins, polyester resins, and fluororesins on one surface of an olefin resin base sheet comprising 3 to 90 parts by weight of an elastomer at 0 to 50 ° C. A pressure-sensitive adhesive sheet comprising a crosslinked colored coating layer containing components and pigments laminated thereon, and a pressure-sensitive adhesive layer laminated on the other surface. 2. The olefin-based resin base sheet is a white sheet containing 100 parts by weight of an olefin-based resin, 3 to 90 parts by weight of an elastomer, and 10 to 200 parts by weight of titanium oxide, and the crosslinked colored coating film layer is made of an acrylic resin. The pressure-sensitive adhesive sheet according to claim 1, comprising 100 parts by weight of at least one resin component selected from the group consisting of a resin, a urethane-based resin, a polyester-based resin, and a fluorine-based resin, and 5 to 80 parts by weight of a pigment. . 3. The olefin resin of 100 parts by weight and a peak temperature of tan δ in a dynamic viscoelasticity spectrum of -4.
A relatively low-softness second olefin made of an olefin-based resin on at least one surface of a relatively high-flexibility first olefin-based resin sheet comprising 3 to 200 parts by weight of an elastomer at 0 to 50 ° C. One side of the olefin resin base sheet on which the base resin sheet is laminated is cross-linked including one or more resin components and pigments selected from the group consisting of acrylic resin, urethane resin, polyester resin and fluorine resin. A pressure-sensitive adhesive sheet, characterized in that the colored coating layer is laminated on another surface with a pressure-sensitive adhesive layer. 4. A first olefin resin sheet and a second olefin resin sheet.
At least one of the olefin-based resin sheets is based on 100 parts by weight of the olefin-based resin, and
A white olefin-based resin sheet in which 0 parts by weight are blended, wherein the crosslinked colored coating layer is at least one selected from the group consisting of an acrylic resin, a urethane-based resin, a polyester-based resin and a fluorine-based resin. The pressure-sensitive adhesive sheet according to claim 3, comprising 100 parts by weight of a resin component and 5 to 80 parts by weight of a pigment. 5. An olefin-based resin base sheet mainly comprising a propylene-based resin, having a total light transmittance of 85% or more according to JIS K 7105 and a haze value of 5%.
The following, the crosslinked colored coating layer is an acrylic resin,
4. The composition according to claim 1, comprising 100 parts by weight of at least one resin component selected from the group consisting of a urethane-based resin, a polyester-based resin and a fluorine-based resin, and 0.5 to 20 parts by weight of a pigment. 5. Adhesive sheet. 6. The pressure-sensitive adhesive sheet according to claim 1, wherein the elastomer is a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, or a hydrogenated product thereof. .