JP2000265126A - Adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a simply incineratable adhesive sheet having sufficient flexibility, excellent in follow-up properties to a curved surface and capable of exhibiting excellent decorative actions. SOLUTION: This sheet is obtained by laminating a coating film layer onto one surface of a polyolefin-based resin sheet and further laminating an adhesive mass layer onto the other surface. The polyolefin-based resin sheet is composed of a polyolefin-based resin containing 20-100 wt.% of a polypropylene-based resin having a weight-average molecular weight within the range of 80,000-500,000 and a composition of respective eluted amounts o the resin based on the total amount of the polypropylene-based resin within the range of 45-80 wt.%, 5-35 wt.%, 1-30 wt.% and 3-35 wt.% at >=0 and <=10 deg.C, >10 and <=70 deg.C, >70 and <=95 deg.C and >95 and <=125 deg.C according to a cross fractionating method.

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, there is a risk of generating hydrogen chloride gas and dioxin during incineration and disposal, so that it cannot be treated with simple incineration equipment. There was a problem that durability was reduced. 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.

When an adhesive sheet is used as a marking film, high concealment is required. However, in Japanese Patent Application Laid-Open No. 8-157780, the mixing ratio of titanium oxide is set to 5 to 30 parts by weight with respect to 100 parts by weight of the polyolefin-based resin, and it is difficult to exhibit sufficient concealing properties. There is also a problem that when actually applied, the pattern of the adherend can be seen through from the outside of the adhesive sheet.

Further, a decorative adhesive sheet used for decoration such as an electric signboard uses transmitted light. JP 8
In the decorative adhesive sheet described in 157780,
The light transmittance was low and insufficient for use as a decorative adhesive sheet utilizing transmitted light as described above. That is, since titanium oxide is blended in the polyolefin-based resin film as the sheet base material, the light transmittance is low and sufficient transmitted light cannot be obtained. Further, even if titanium oxide is not blended, the light transmittance of the polyolefin-based resin film itself is low, and it has been difficult to exert a sufficient decorative effect using transmitted light.

Further, when an inorganic filler such as titanium oxide is blended in the polyolefin resin film, there is a problem that the polyolefin resin film is easily torn. Therefore, only a small notch is formed in the polyolefin-based resin film in the construction stage, and the film tends to be torn during handling.

It is also conceivable to use a flexible polyolefin-based copolymer as the polyolefin-based resin film in order to increase flexibility. However, it is difficult to increase the content of α-olefin in the copolymerization stage, and the resulting film has excessive flexibility. On the other hand, a method of increasing flexibility by blending a plurality of polyolefin-based polymers is also conceivable, but it is extremely difficult to uniformly mix the plurality of polymers, and it is very difficult to stably develop a desired mechanical strength. It was difficult.

Also, a method of increasing flexibility by adding a more flexible EPR (ethylene-propylene rubber) to the polyolefin resin is conceivable, but in this case, the dispersibility of the EPR in the resin is not sufficient, and It was very difficult to obtain a uniform polyolefin-based resin film using a screw extruder.

[0016]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, to be able to treat with a simple incineration facility, and to prevent a problem in sanitation or pollution. An object of the present invention is to provide a pressure-sensitive adhesive sheet which uses a sheet, has sufficient flexibility, and is therefore excellent in workability on a curved surface.

Another object of the present invention is to provide a pressure-sensitive adhesive sheet capable of reliably hiding the color and pattern of an adherend and exhibiting an excellent decorative effect. Still another object of the present invention is to provide
An object of the present invention is to provide a pressure-sensitive adhesive sheet which has excellent light transmittance and is suitable as a decorative pressure-sensitive adhesive sheet utilizing transmitted light used for, for example, an electric signboard.

[0018]

The invention according to claim 1 is an adhesive sheet comprising a polyolefin resin sheet having a coating layer on one surface and an adhesive layer on the other surface. The resin sheet has a weight average molecular weight Mw
Is in the range of 80,000 to 500,000, and 0 ° C by the cross fractionation method.
The resin elution amount of not less than 10 ° C. is 45 to 80% by weight of the total amount of the polypropylene resin, and exceeds 10 ° C.
The resin elution amount in the following is 5 to 35% by weight of the total polypropylene resin amount, and exceeds 70 ° C, and the resin elution amount in 95 ° C or less is 1 to 30% of the total polypropylene resin amount.
%, And the resin elution amount at 95 ° C. or higher and 95 ° C. or lower is 3 to 35% by weight based on the total amount of the polypropylene resin.
Of a polypropylene resin having a composition in the range of
It is characterized by comprising a polyolefin-based resin containing 0 to 100% by weight.

According to a second aspect of the present invention, there is provided a pressure-sensitive adhesive sheet in which a coating layer is laminated on one side of a polyolefin-based resin sheet and a pressure-sensitive adhesive layer is laminated on the other side, wherein the polyolefin-based resin sheet is an intermediate layer. And an outer layer made of a polyolefin resin laminated on at least one surface of the intermediate layer, wherein the intermediate layer has a weight average molecular weight Mw in the range of 80,000 to 500,000, Over ℃,
The resin elution amount at 10 ° C or lower is 45 to 80% by weight of the total polypropylene resin amount, and the resin elution amount at 10 ° C or higher and 70 ° C or lower is 5 to 3% of the total polypropylene resin amount.
5% by weight, and the resin elution amount at 70 ° C. or more and 95 ° C. or less is 1 to 30% by weight of the total amount of the polypropylene resin.
And characterized by comprising a polypropylene resin having a composition in which the resin elution amount at 95 ° C. or higher and 95 ° C. or lower is in the range of 3 to 35% by weight of the total polypropylene resin amount.

According to the third aspect of the present invention, in the polyolefin resin sheet, 10 to 300 parts by weight of titanium oxide is added to 100 parts by weight of the specific polypropylene resin.
Parts by weight are added.

According to the fourth aspect of the present invention, in the pressure-sensitive adhesive sheet, JIS K of a polyolefin resin sheet is used.
The total light transmittance according to 7105 is 85% or more.

According to a fifth aspect of the present invention, the coating layer comprises 100 parts by weight of one selected from the group consisting of an acrylic resin, a urethane-based resin, a polyester-based resin, and a fluorine-based resin; 0.5 to 200 parts by weight.

Hereinafter, the present invention will be described in detail. (Polyolefin-based resin sheet according to the first aspect of the invention) In the pressure-sensitive adhesive sheet according to the present invention, three-dimensional curved surface workability is enhanced by using the specific polypropylene-based resin. By the way, the polypropylene-based resin widely includes a polymer having propylene as a main structural unit, and includes a propylene homopolymer and a copolymer of propylene with ethylene or an α-olefin other than propylene.

In the production of the above-mentioned propylene-ethylene copolymer or propylene-α-olefin copolymer, first, a propylene monomer and, if necessary, other than ethylene or propylene are added in the presence of a titanium compound catalyst and an aluminum compound catalyst. Polymerization is carried out using an α-olefin monomer, and the first
To obtain a polypropylene-based polyolefin. Next, the second
As a step, in the presence of the titanium compound catalyst,
The titanium-containing polypropylene-based polyolefin produced in the first step is copolymerized with propylene, ethylene or α-olefin to obtain a second polypropylene-based polyolefin. Hereinafter, similarly, a multi-stage copolymerization reaction may be performed according to the purpose.

Preferably, the polypropylene-based polyolefin produced in the first step is a propylene homopolymer, a propylene-ethylene copolymer or a propylene-
It is an α-olefin copolymer.

The weight average molecular weight of the polypropylene resin used in the present invention can be determined, for example, by using high temperature gel permeation chromatography (GPC) (manufactured by WATERS, Inc.).
(Product number: 150 CV). The weight average molecular weight of the polypropylene resin used in the present invention is in the range of 80,000 to 500,000, preferably 200,000 to 40000.
It is in the range of 10,000. If the weight average molecular weight is less than 80,000, the strength of the polyolefin resin sheet becomes insufficient, and if it exceeds 500,000, it is difficult to obtain sufficient flexibility.

The specific polypropylene-based resin has the above-mentioned specific range in the amount of each resin eluted in the above-mentioned temperature range by the cross separation method. The measurement of the resin elution amount by the cross fractionation method is performed as follows.

The polypropylene resin is first heated to 140 ° C. or at a temperature at which the polypropylene resin is completely dissolved.
The thin polymer layer is dissolved in dichlorobenzene, applied to the surface of an inert carrier prepared in advance, and cooled at a constant speed to form a thin polymer layer in the order of high crystallinity and high molecular weight. Next, the temperature of each generated polymer layer is raised continuously or stepwise, the concentration of the sequentially eluted components is detected, and the composition distribution (crystallinity distribution) is measured. This step is called a temperature rise elution fractionation method. At the same time, the molecular weight and molecular weight distribution of the eluted components are measured by high-temperature GPC.

As an apparatus for performing the above measurement, for example, the above-mentioned temperature rise elution fractionation (TREF = Temperature R)
ising Elution Fractionation) part and a high-temperature GPC part as a system, such as a cross-separation chromatograph, manufactured by Mitsubishi Chemical Corporation, part number: CFC-T15.
0A type.

In the polypropylene resin used in the present invention, the amount of resin eluted at 0 ° C. or more and 10 ° C. or less by the above-mentioned cross fractionation method is 45 to 80% by weight of the entire polypropylene resin. If the elution amount is less than 45% by weight, the flexibility of the polyolefin resin sheet is not sufficient, and if it exceeds 80% by weight, the strength of the sheet does not become sufficiently large.

The resin elution amount at a temperature exceeding 10 ° C. and 70 ° C. or less is 5 to 35% by weight based on the total amount of the polypropylene resin. If the resin elution amount is less than 5% by weight, the flexibility of the polyolefin resin sheet is not sufficient, and if it exceeds 35% by weight, the deformation recovery property of the polyolefin resin sheet decreases.

The resin elution amount above 70 ° C. and 95 ° C. or less is 1 to 30% by weight based on the total amount of the polypropylene resin. If the amount is 1% by weight, the deformation recovery property of the polyolefin-based resin sheet is not sufficient, and if it exceeds 30% by weight, the strength of the polyolefin-based resin sheet does not become sufficiently large.

The resin elution amount at temperatures exceeding 95 ° C. and 125 ° C. or less is 3 to 35% by weight based on the total amount of the polypropylene resin. If it is less than 3% by weight, the strength of the polyolefin resin sheet will not be sufficiently large, and if it exceeds 35% by weight, the flexibility of the polyolefin resin sheet will be reduced.

In the pressure-sensitive adhesive sheet according to the first aspect of the present invention, the polyolefin-based resin sheet is made of a polyolefin-based resin containing a polypropylene-based resin having a composition within the above range at a ratio of 20 to 100% by weight. When the content of the polypropylene-based resin is less than 20% by weight, it is difficult to obtain good physical properties by the above-mentioned specific polypropylene-based resin.

In the polypropylene resin used in the present invention, the fact that the amount of elution in each temperature range is within the above range is very important in controlling physical properties such as elastic modulus, strength and ductility of the polyolefin resin sheet. is important.

In general, in the stress-strain curve of a polypropylene-based resin, the rise at low elongation is steep, yields when the elongation is 20 to 30%, and then becomes 100%.
The stress hardly increases up to about% elongation. That is, after being stretched by 20 to 30%, the stress against strain becomes almost constant in the stress-strain curve. When such a resin is used as the base material of the pressure-sensitive adhesive sheet, if the pressure-sensitive adhesive sheet is strongly pulled, for example, when the pressure-sensitive adhesive sheet is attached to a curved surface, the sheet may be extended completely.

However, since the specific polypropylene resin used in the present invention gives a sheet having excellent flexibility, the polyolefin resin sheet does not extend even if it is strongly pulled when it is attached to a curved surface. . That is, followability and sticking property to a curved surface are improved.

In general, when a plurality of polymers are blended, in order to increase flexibility and stretchability, it is general to blend a rubber component and increase the molecular weight of the rubber component. In the case of the polypropylene resin used in the present invention, the component corresponding to this rubber component is a component generated by the above-described second and subsequent reactions, that is, α-olefin-propylene and ethylene-propylene. Has a high melt viscosity due to its high molecular weight. In addition, this component can be uniformly finely dispersed in the polypropylene resin by using the above-mentioned multi-stage polymerization method.

However, in a polymer blending method using an ordinary extruder or the like, it is difficult to finely disperse such a component having a high molecular weight because the melt viscosity is high when blended. That is, a resin having a finely dispersed morphology, such as the polypropylene resin used in the present invention, cannot be obtained by the ordinary polymer blending method.

Further, in the polypropylene block copolymer obtained by the conventional reaction, the block component such as ethylene and α-olefin to be copolymerized is about 50% of the main component polypropylene due to its production process.
The content of these block components is limited to about 30% by weight. Therefore, it has been very difficult for a polypropylene resin to achieve flexibility like plasticized polyvinyl chloride.

However, the polypropylene resin used in the present invention is obtained by using the above-mentioned specific multi-stage polymerization method.
It can be contained up to 5% by weight. Therefore, the polypropylene resin according to the present invention can exhibit the same excellent physical properties as plasticized polyvinyl chloride.

Specific examples of the above-mentioned specific polypropylene resin which is excellent in flexibility as described above and used in the present invention are those manufactured by Tokuyama Soda Co., Ltd., product numbers: T310E, R
210E, manufactured by Montell JPO, trade name: Cataloy K
S-059P, Cataloy KS-081P, and the like.

In the present invention, a pigment may be contained in the polyolefin-based resin sheet.
As long as it has heat resistance at about 0 ° C., it can be appropriately selected according to the purpose, for example, azo-based, phthalocyanine-based, sulene-based, dye lake-based, quinacridone-based,
Organic pigments such as dioxazine; various inorganic pigments such as the above-mentioned oxides such as titanium oxide, molybdate chromate, sulfide / selenide, ferrocyanide, and calcium carbonate can be appropriately used. By including these pigments in the polyolefin-based resin sheet, the color of the adherend can be concealed and the saturation of the coating layer can be improved. In this case, a white pigment is desirable for hiding the color of the adherend and improving the chroma of the coating layer, and in particular,
Titanium oxide is preferably used.

The thickness of the polyolefin resin sheet is not particularly limited, but when it is used as a decorative adhesive sheet, it is usually 20 to 150 μm, and more preferably 4 to 150 μm.
It is about 0 to 60 μm. If the thickness is less than 20 μm,
The polyolefin-based resin sheet itself becomes soft, which may make construction difficult or insufficient in strength.
If it exceeds μm, the polyolefin-based resin sheet becomes hard, and the followability to a curved surface may be deteriorated.

In the pressure-sensitive adhesive sheet according to the present invention, a hindered amine compound may be added in order to impart weather resistance to the polyolefin resin sheet. Although the hindered amine compound is not particularly limited, the following compounds 1) to 11) 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

Further, other additives may be added to the polyolefin resin sheet as long as the sheet formability and the sheet properties are not impaired. Examples of the additives include an ultraviolet absorber and a heat stabilizer. And the like.

Examples of the above-mentioned ultraviolet absorbent include salicylic acid 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.

The polyolefin-based resin sheet in the pressure-sensitive adhesive sheet according to the present invention is prepared by mixing the above-mentioned additives with the above-mentioned specific polypropylene-based resin and then using a conventional T-die method or inflation method. To form a film.

Since the formed polyolefin resin sheet generally has a low surface tension, it is desirable to improve the adhesion of the coating layer and the pressure-sensitive adhesive layer by surface modification such as corona treatment.

(Polyolefin Resin Sheet According to Claim 2) In the invention according to claim 2, the polyolefin resin sheet comprises an intermediate layer and a polyolefin resin laminated on at least one surface of the intermediate layer. It has a structure in which an outer layer is laminated, and the intermediate layer is made of the polypropylene resin having the specific composition range used in the invention of claim 1.

Since the intermediate layer is formed by using a specific polypropylene resin in the pressure-sensitive adhesive sheet according to the first aspect of the present invention, the description of the polypropylene resin is described in the first aspect. The description of the invention is omitted here.

Also in the pressure-sensitive adhesive sheet according to the second aspect of the present invention, since the intermediate layer is formed by using the above-mentioned specific polypropylene resin, the intermediate layer is excellent in flexibility and has high adhesion to a three-dimensional curved surface. Can be In addition, by using the above-described multi-stage polymerization method, in the polypropylene resin, α-olefin-propylene or ethylene-propylene as a component for enhancing flexibility can be finely dispersed in the polypropylene resin uniformly. it can.

Also in the pressure-sensitive adhesive sheet according to the second aspect of the present invention, titanium oxide is added to the polypropylene-based resin constituting the intermediate layer in the same manner as in the first aspect of the invention. , The intermediate layer can be white, and the surface of the adherend can be concealed reliably,
In addition, the saturation of the coating layer can be increased.

Further, the above-mentioned hindered amine-based compound may be added to the polypropylene-based resin constituting the intermediate layer in order to impart weather resistance, and the above-mentioned other additives may be added to the sheet moldability and sheet properties. You may add in the range which does not impair etc.

The polyolefin resin constituting the outer layer laminated on the intermediate layer is not particularly limited, and polyethylene, polypropylene or an appropriate polyolefin copolymer can be used.

The ratio of the thickness of the intermediate layer to the thickness of the outer layer is not particularly limited as long as the characteristics of the specific polypropylene resin constituting the intermediate layer are not impaired. Layer thickness = 20 to 1-1
It is about one to one.

The outer layer may be laminated on both sides of the intermediate layer. In this case, as for the thickness of the outer layer, the total thickness of both outer layers preferably falls within the above range.

Further, the total thickness of the polyolefin resin sheet in the pressure-sensitive adhesive sheet according to the second aspect of the present invention is preferably about 20 to 100 μm, and more preferably 40 to 60 μm. If it is less than 20 μm, the polyolefin-based resin sheet itself becomes too soft, making it difficult to perform the work or causing insufficient strength. If it exceeds 100 μm, on the other hand, it becomes hard, and the followability to an adherend having a three-dimensional curved surface may decrease.

(Polyolefin resin sheet of pressure-sensitive adhesive sheet according to the third aspect of the invention) In the pressure-sensitive adhesive sheet according to the third aspect of the invention, the polyolefin-based resin sheet is oxidized with respect to 100 parts by weight of the polypropylene-based resin. Titanium is added in a ratio of 10 to 300 parts by weight. In addition, when titanium oxide is added to the pressure-sensitive adhesive sheet according to the invention according to claim 2, with respect to 100 parts by weight of the specific polypropylene resin constituting the intermediate layer,
Titanium oxide is blended in the above specific ratio.

According to the third aspect of the present invention, in the polyolefin-based resin sheet, titanium oxide is blended in the above-described specific ratio, whereby the chroma of the coating layer can be improved. Further, by changing the color of the coating layer, it is possible to easily change the color tone of the pressure-sensitive adhesive sheet.

That is, in the invention according to claim 3, since a white polyolefin resin sheet is used, the white polyolefin resin sheet is mass-produced and various coating layers are laminated. 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 adhesive sheets in small quantities.

As the titanium oxide, it is particularly preferable to use rutile type or anatase type titanium oxide. More preferably, rutile-type titanium oxide having an average particle diameter of 0.01 to 1 μm, which itself has weather resistance and excellent resin dispersibility, is suitably used.

The amount of titanium oxide added is preferably in the range of 10 to 300 parts by weight based on 100 parts by weight of the specific polypropylene resin containing the propylene copolymer copolymerized by the reactor blending method. , More preferably 30 to 100 parts by weight, still more preferably 50 to 100 parts by weight. If the amount of titanium oxide is too small, the concealing property is deteriorated, and if it is too large, the concealing property is saturated and the dispersibility of the titanium oxide may be reduced.

When titanium oxide is blended, it is preferable to mix the titanium oxide with a masterbatch which is used as a general-purpose formulation for improving the dispersibility of titanium oxide in a polypropylene resin.

(Polyolefin resin sheet of pressure-sensitive adhesive sheet according to claim 4) In the pressure-sensitive adhesive sheet according to claim 4, the polyolefin resin sheet has a total light transmittance of 85 in accordance with JIS K7105. % Or more. That is, the polyolefin resin sheet has sufficient transparency. Therefore, for example, it can be suitably used as a decorative adhesive sheet used by using transmitted light in an electric signboard or the like. 85% total light transmittance
If it is less than 1, the transparency is not sufficient, and when used for such an application, it is difficult to exhibit a good decorative effect using transmitted light.

(Coating Layer) In the pressure-sensitive adhesive sheet according to the present invention,
A coating layer is laminated on one surface of the polyolefin-based resin sheet, and the decorative effect of a desired color is exhibited by the coating layer. The coating film layer is constituted by containing one kind 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.

The acrylic resin, urethane resin, polyester resin and fluorine resin have an acrylic polymer, urethane polymer, polyester polymer or various fluorine polymers as main chains, respectively. Depending on the required functions such as strength and
Various polyols, melamine, silanol, hydroxyl group structure, alicyclic epoxy compound or glycidyl methacrylate inside, isocyanate as a cross-linking component, melamine, or configured to have a three-dimensional cross-linked structure by silane, etc. Is given. Further, the adhesion and weather resistance can be enhanced by blending the main chain itself with an acid-modified, silicone-modified, fluorinated or vinylidene fluoride according to the required quality. As the fluorine-based resin, fluoroethylene-based, vinylidene fluoride-based, fluoroethylene vinyl ether-based, a product obtained by grafting a compound or a fluororesin, an alkyl fluoride graft product on an acrylic main chain, or the like can be used.

Examples of the material used as the curing agent include isocyanates, melamines, and methylols, but aliphatic isocyanates are preferably used due to the problem of yellowing due to light. Usually, a curing component and, if necessary, a curing accelerating catalyst are blended in the main resin solution, and the mixture is used in a pot life where the liquid does not cure, and a colored coating film is formed after curing.

The acrylic resin, urethane resin, polyester resin and fluorine resin act to enhance the weather resistance and flexibility of the coating layer. The mixing ratio of the resin and the pigment in the coating layer is 0.5 to 300 parts by weight of the pigment based on 100 parts by weight of the resin. If the blending ratio of the pigment is less than 0.5 parts by weight, the decorative effect due to the blending of the pigment may not be sufficiently obtained, and if it exceeds 300 parts by weight, the flexibility of the coating layer is impaired, and the three-dimensional Followability to a curved surface may be reduced.

However, when titanium oxide is contained in the polyolefin resin sheet and a white polyolefin resin sheet is used, 100 parts by weight of the resin is used.
It is desirable that the pigment is blended in the range of 5 to 80 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 and the pigment is reduced, and the surface properties are reduced. Costly.

When a transparent polyolefin-based resin sheet suitable for an electric sign is used, in the coating layer, the pigment is 0.5 to 20 parts by weight based on 100 parts by weight of the resin.
It is desirable to mix in parts by weight. If the amount is less than 0.5 part by weight, the target hue may not be obtained,
If the amount exceeds 0 parts by weight, the concealing property of the coating film layer becomes too high, and for example, when used for an illuminated signboard, the decorative effect by transmitted light may not be sufficiently exhibited.

The pigment used in the coating layer is not particularly limited, but the above-mentioned organic pigments generally used and excellent in weather resistance can be preferably used.

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

The method of laminating the coating layer on the polyolefin resin sheet is not particularly limited, and various coating methods can be used. For example, a bar coater, reverse coater, spray gun coater, knife coater, rotary screen, screen printing, gravure coater, kiss coater and the like can be mentioned.

Further, when the coating thickness of the coating film layer is reduced, the weather resistance may be reduced, and when the coating thickness is increased, the drying property is reduced, and the surface may be tacky due to the residual solvent, and blocking may occur. . Therefore, the thickness of the coating layer is 5
５０50 μm is preferred, more preferably 10-40 μm
m, particularly preferably 15 to 35 μm.

(Pressure-sensitive adhesive layer) In the present invention, the pressure-sensitive adhesive layer is laminated on the surface of the polyolefin resin sheet obtained as described above, which is opposite to the surface on which the coating layer is formed.

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 containing a homopolymer of alkyl (meth) acrylate or a copolymer of 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 tackiness and cohesion, etc., the homopolymer generally has an alkyl (meth) acrylate having a glass transition temperature (Tg) of -50 ° C. or lower as a main component, and 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.

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 (meth)
Examples include hydroxyl-containing vinyl monomers such as acrylate, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and caprolactone-modified (meth) acrylate.

When the pressure-sensitive adhesive layer is formed 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 polyolefin-based resin sheet. In this case, the method for laminating the pressure-sensitive adhesive layer is not particularly limited. That is, a method of applying an adhesive to the surface of a release material such as release paper by a quantitative coating method, drying by heating, and then laminating on one surface of a polyolefin resin sheet, or an adhesive on one surface of a polyolefin resin sheet. Can be applied directly.

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

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 a polyolefin-based resin sheet as described above. Then, 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 attached to the entire adherend to be decorated, or may be cut into desired figures and characters by a cutting machine controlled by a computer, and then unnecessary portions may be cut off. 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 polyolefin resin sheet as the base material has a weight average molecular weight within the above-mentioned specific range, and the resin elution amount distribution by the cross fractionation method is as described above. 20 to 100% by weight of a specific polypropylene resin having a composition in a specific range
Since it contains, it has sufficient flexibility. Therefore, in the pressure-sensitive adhesive sheet according to the present invention, in which the coating layer is laminated on one surface of the polyolefin-based resin sheet and the pressure-sensitive adhesive layer is laminated on the other surface, the followability to a three-dimensional curved surface is improved.

In the pressure-sensitive adhesive sheet according to the second aspect of the present invention, the intermediate layer is made of the specific polypropylene resin, and a polyolefin resin layer is formed outside the intermediate layer. Since it is made of a polypropylene-based resin and has sufficient flexibility, the polyolefin-based resin sheet has sufficient flexibility. Therefore, claim 1
As in the invention described in (1), the followability of the pressure-sensitive adhesive sheet to an adherend having a three-dimensional curved surface is improved.

The pressure-sensitive adhesive sheets according to the first and second aspects of the present invention can be incinerated with simple equipment and reduce environmental pollution, unlike the case where a vinyl chloride resin film is used. .

Further, since a coating layer is laminated on one surface of the polyolefin resin sheet, various decorative effects are exhibited by the coating layer. In this case, various decorative effects can be exhibited by changing the coating layer.

In the pressure-sensitive adhesive sheet according to the third aspect of the present invention, the polyolefin resin sheet is a white sheet in which 10 to 300 parts by weight of titanium oxide is blended with respect to 100 parts by weight of the polypropylene resin. Therefore, the color of the adherend can be effectively hidden. In addition, the saturation of the coating layer can be improved, and the decorative effect of the coating layer can be effectively exhibited.

In the pressure-sensitive adhesive sheet according to the fourth aspect, since the total light transmittance is 85% or more, the transparency of the polyolefin-based resin sheet is enhanced. Therefore,
For example, when used for an adhesive sheet for an illuminated signboard, a decorative effect by transmitted light can be favorably exhibited.

[0095] In the pressure-sensitive adhesive sheet according to the fifth aspect, the coating layer contains 100 parts by weight of one resin selected from the group consisting of an acrylic resin, a urethane resin, a polyester resin and a fluorine resin. And 0.5 to 200 parts by weight of the pigment, it is excellent in weather resistance and exhibits a good decorative effect.

[0096]

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.

(Example 1) The weight-average molecular weight was 250,000, and the resin elution amount at each temperature by the cross fractionation method was 0 ° C or more,
At 0 ° C. or less, 50% by weight of the total polypropylene resin weight,
The resin elution amount exceeding 10 ° C. and 70 ° C. or less is 15% by weight,
10% by weight of resin eluted above 70 ° C and 95 ° C or less
Polypropylene resin having a resin elution amount of more than 5 ° C and 125 ° C or less and having a resin elution amount of 25% by weight (manufactured by Montell JPO, product number KS-059P, rubber component 45% by weight, ethylene content in the rubber component 20% by weight or more, crystal Degree of conversion = 40%, density =
0.89 g / cm ³ , MFR = 10/10 min.) 60 parts by weight, MFR 4.5 random polypropylene 40 parts by weight, and titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., product number: CR-6)
0) 50 parts by weight of a polypropylene-based composition
It was molded by a die method and cooled by a cooling roll set at a temperature of 30 ° C. to obtain a polyolefin resin sheet of 40 μm.

A coating layer is formed on one side of the polyolefin resin sheet, and an adhesive layer and a release paper layer are formed on the opposite side.
An adhesive sheet was obtained. The structures of the coating layer and the pressure-sensitive adhesive layer used are as follows.

Coating layer: 100 parts by weight of an acrylic paint (manufactured by Dainippon Paint Co., Ltd., trade name: Planit U # 700) and a curing agent (manufactured by Nippon Polyurethane Co., trade name: Coronate 20)
94) and 6.5 parts by weight of a composite pigment (cyanine blue,
(Including quinacridone red, polyazo yellow and cyanine green) was applied using a spray gun coater so that the thickness after drying was 20 μm. The compounding amount of the composite pigment was 40 parts by weight as shown in Table 1 below.

Pressure-sensitive adhesive layer: The surface of the two-liquid cross-linkable acrylic pressure-sensitive adhesive (manufactured by Toyo Ink Co., Ltd., trade name: BPS: 5520) is silicone-treated using a comma coater so that the thickness after drying becomes 40 μm. Was applied to the release paper. The pressure-sensitive adhesive layer applied to the release paper was laminated on the surface of the polyolefin resin sheet obtained as described above, which was opposite to the side on which the coating layer was formed.

Example 2 The weight-average molecular weight was 250,000, and the resin elution amount at each temperature by the cross-separation method was 0 ° C. or more.
48% by weight below 0 ° C, 19% above 10 ° C and below 70 ° C
5% by weight, above 95 ° C and below 95 ° C, 95 ° C
And a polypropylene-based resin having a content of 28% by weight at 125 ° C. or less (manufactured by Montell JPO, part number: KS-081)
P, rubber component 45% by weight, ethylene content in rubber component 2
0% by weight or more, crystallinity 40%, density 0.89 g / cm
³ , 50 parts by weight of MFR = 10/10 minutes) and homopolypropylene (manufactured by Nippon Polyolefin Co., Ltd., weight average molecular weight 2)
Except that a polypropylene-based composition consisting of 50 parts by weight of 30,000, MFR 7.0 / 10 minutes) and 100 parts by weight of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., product number: CR-60) was used. In the same manner as in Example 1, an adhesive sheet was obtained.

(Example 3) Except for using a fluororesin paint (manufactured by Nippon Paint Co., Ltd., trade name: Duflon Puree Clear) instead of an acrylic paint as a material constituting the coating film layer, In the same manner as in Example 1, an adhesive sheet was obtained.

(Example 4) Except for using another acrylic paint (trade name: Reseric TC, manufactured by Fujikura Kasei Co., Ltd.) instead of the acrylic paint as the paint constituting the coating film layer, A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1.

Example 5 Adhesion was performed in the same manner as in Example 1 except that a polyester paint (trade name: Planit U # 500, manufactured by Dainippon Paint Co., Ltd.) was used instead of the acrylic paint. I got a sheet.

Comparative Examples 1 and 2 As shown in Table 2 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 sheet having a thickness of 60 μm. A coating layer was formed on one surface of the obtained vinyl chloride resin sheet in the same manner as in Example 1, and the pressure-sensitive adhesive layer and release paper were cleaned on the other surface.

(Example 6) The weight-average molecular weight was 200,000, and the resin elution amount in each temperature range by the cross separation method was 0 ° C or more and 10 ° C or less and exceeded 69% by weight of the total polypropylene resin amount and exceeded 10 ° C. 11% by weight at 70 ° C or less, more than 70 ° C, 2% by weight at 95 ° C or less, more than 95 ° C, 125 ° C
A polypropylene resin (manufactured by Tokuyama Corporation, product number: T310E) of 18% by weight is extruded, and a polyolefin resin sheet having a thickness of 50 μm is obtained with a T-die. Processing was performed. A coating layer was formed on one side of the polyolefin-based resin sheet obtained as described above, and a pressure-sensitive adhesive layer and a release paper layer were formed on the opposite side to obtain a pressure-sensitive adhesive sheet. In addition, the total light transmittance of the polyolefin-based resin sheet obtained as described above was 91% as shown in Table 3 below.

Example 7 An adhesive sheet was obtained in the same manner as in Example 1 except that the mixing ratio of the pigment in the coating layer was changed to 10 parts by weight. The total light transmittance of the polyolefin resin sheet in Example 2 was 90%.

Example 8 The weight average molecular weight was 250,000, and the resin elution amount in each temperature range by the cross fractionation method was 48% by weight at 0 ° C. or more and 10 ° C. or less, exceeding 10 ° C. and 19% by weight at 70 ° C. or less. Extrude a polypropylene resin (manufactured by Montell JPO, product number: Cataloy KS-081P), which is 5% by weight at 70 ° C., 5% by weight at 95 ° C. or less, and 28% by weight at 125 ° C. or less, and T-die. To form a film,
A polyolefin-based resin sheet having a thickness of 50 μm was obtained, and corona treatment was performed in-line on both sides under the condition of 42 dyne / cm. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 6, except that the obtained polyolefin-based resin sheet was used and that the blending ratio of the pigment in the coating layer was 15 parts by weight. The total light transmittance of the polyolefin resin sheet obtained in Example 8 was 89%.

Comparative Example 3 The same polypropylene-based resin as in Example 8 was used and extruded with a T-die in the same manner as in Example 8 to obtain a polyolefin-based resin sheet having a thickness of 50 μm. A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 8, except that the obtained polyolefin-based resin sheet was used as a resin base material layer and the content ratio of the composite pigment was 25 parts by weight. In addition, the total light transmittance of the polyolefin resin sheet in Comparative Example 3 was 88%.

(Comparative Example 4) A low-density polyethylene (manufactured by Nippon Polychem Co., Ltd., product number: UF840) was extruded with a T-die to form a 50-μm low-density polyethylene sheet.
Both surfaces were corona-treated under the condition of 42 dyne / cm in-line. In this way, a low-density polyethylene sheet was used as a sheet substrate, and a coating layer was formed on one side, and an adhesive layer and release paper were formed on the opposite side in the same manner as in Example 1. The compounding ratio of the composite pigment in the coating layer was 10%.
Parts by weight were used. The low-density polyethylene sheet obtained in Comparative Example 4 had a total light transmittance of 80%.

(Comparative Example 5) 50 parts by weight of an ethylene-vinyl acetate copolymer resin (manufactured by Mitsubishi Yuka, part number: EVA20E) and ethylene-propylene rubber (manufactured by Mitsui Petrochemical Industries, trade name: Tuffmer P-) [0280] 50 parts by weight were optimally blended, and a film was formed by a T-die using the blended resin as a raw material to obtain a 50 µm sheet, and both sides were corona-treated in-line at 42 dyne / cm. A coating layer was formed on one side of the resin sheet thus obtained, and a pressure-sensitive adhesive layer and a release paper layer were formed on the opposite side in the same manner as in Example 1. The compounding ratio of the composite pigment in the coating layer was 10 parts by weight. Comparative Example 5
The total light transmittance of the resin sheet obtained in the above was 80%.

(Example 9) The intermediate layer was treated with a weight average molecular weight of 2
100,000, the resin elution amount in each temperature range by the cross fractionation method is 60% by weight at 0 ° C or more and 10 ° C or less, more than 10 ° C, 11% by weight at 70 ° C or less, more than 70 ° C, and 95% or less. 2% by weight, polypropylene resin exceeding 95 ° C. and 18% by weight at 125 ° C. or less (manufactured by Tokuyama Corporation, product number:
R210E) 100 parts by weight, and 60 parts by weight of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., product number: CR-60). For the outer layer constituting both sides of the intermediate layer, MI =
3.9 g / 10 min homopolypropylene was used. The above-described resin composition for forming an intermediate layer and the resin for forming an outer layer are multilayer-extruded by a multilayer extrusion T-die machine to form a polyolefin resin sheet having a thickness of 50 μm in which outer layers are laminated on both sides of the intermediate layer. 42 dyne / cm on both sides inline
Corona treatment was performed under the following conditions. A coating layer was laminated on one side of the obtained polyolefin-based resin sheet and a pressure-sensitive adhesive layer and release paper were laminated on the other side in the same manner as in Example 1, to obtain a pressure-sensitive adhesive sheet. In the obtained pressure-sensitive adhesive sheet, the thickness of the intermediate layer was 34 μm.
m, and the thickness of the outer layers on both sides was 8 μm.

Example 10 The mixing ratio of titanium oxide was 25
A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 9, except that the amount was 0 parts by weight and the compounding ratio of the composite pigment in the coating layer was 20 parts by weight.

(Example 11) As the polypropylene resin constituting the intermediate layer, the weight average molecular weight was 250,000, and the resin elution amount in each temperature range by the cross separation method was 0 ° C or more.
At 10 ° C or less, 48% by weight of the total polypropylene resin, 1
More than 0 ° C, 19% by weight below 70 ° C, more than 70 ° C 9
5% by weight at 5 ° C or less, more than 95 ° C, 2% at 125 ° C or less
8% by weight of a polypropylene resin (Montel JPO
Manufactured by Cataloy KS-081P), and the compounding ratio of the composite pigment contained in the coating layer was 1
An adhesive sheet was obtained in the same manner as in Example 9 except that the amount was 80 parts by weight.

(Comparative Examples 6 to 8) Example 9 was repeated except that the mixing ratio of titanium oxide in the intermediate layer and the mixing ratio of the composite pigment in the coating layer were changed as shown in Table 4 below.
In the same manner as in the above, an adhesive sheet was obtained.

(Comparative Example 9) As materials constituting the intermediate layer, 50 parts by weight of an ethylene-vinyl acetate copolymer resin (manufactured by Mitsubishi Yuka Co., Ltd., product number: EVA20E) and ethylene-propylene rubber (manufactured by Mitsui Chemicals, Inc.) Product name: Toughmer P-0
280) using a resin composition obtained by mechanically blending 50 parts by weight, a titanium oxide compounding ratio in the intermediate layer being 100 parts by weight, and a composite pigment content ratio in the coating layer being 50 parts by weight. Except having changed it, the adhesive sheet was obtained like Example 9.

[0117]

[Table 1]

[0118]

[Table 2]

[0119]

[Table 3]

[0120]

[Table 4]

(Evaluation of Examples and Comparative Examples) Each of the pressure-sensitive adhesive sheets of Examples and Comparative Examples obtained as described above, when used as a marking film, has a curved surface workability, a film handling property, a film formability, and the like. The base concealing property, coating film formability, weather resistance of the coating film, transmitted light decoration property, incineration property, and tear property were evaluated in the following manner.
The results are shown in Tables 5 to 7 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, and no problem was encountered in the application to a curved adherend. 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: Due to insufficient flexibility, construction on a curved adherend was somewhat difficult. 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 five-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: Difficult to handle because the base sheet was too soft. 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 moldability: Moldability in a T-die molding machine when molding an olefin resin base material sheet was evaluated. The meanings of the evaluation symbols are as follows. 〇: 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 concealing property: 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. 〇: 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.

Formability of coating film: The coating properties and the appearance after coating were evaluated when coating the coating layer with a spray gun on an olefin resin substrate sheet.
The meanings of the evaluation symbols are as follows. 〇: 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 coating layer could not be formed.

Weather resistance of coating film: The appearance change of the coating film layer after exposure for 2,000 hours with a xenon weather meter (black panel 63 ° C., rainfall 12 minutes / 60 minutes) was visually evaluated. The contents of the evaluation symbols are as follows. A: Almost no change in appearance was observed. …: Slight fading was observed, and a decrease in gloss was observed. X: Large change in color and gloss was observed.

Transparent light decoration property: The pressure-sensitive adhesive sheet was irradiated with light, and the clearness of color by the transmitted light was evaluated. The contents of the evaluation symbols are as follows. 〇: 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.

[0130] Incineration property: Adhesive sheets were each 5 cm x
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.

Tear property: The tear property 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.

[0132]

[Table 5]

[0133]

[Table 6]

[0134]

[Table 7]

[0135]

According to the pressure-sensitive adhesive sheet according to the first aspect of the present invention, the specific polypropylene resin is used in an amount of 20 to 100.
Since the polyolefin-based resin sheet contained in the proportion of weight% is used, it has sufficient flexibility and the followability to an adherend having a three-dimensional curved surface is enhanced.
Therefore, it can be easily applied to adherends of various shapes, and for example, a decorative adhesive sheet suitable for various uses can be formed.

Further, since a coating layer is laminated on one surface of the polyolefin resin sheet to exhibit a decorative effect, by appropriately changing the coating layer, an adhesive sheet having a different decorative effect can be easily provided. obtain. Therefore, it is possible to cope with a small number and variety of decorative adhesive sheets. Furthermore, since the polyolefin-based resin sheet is used as the base material, it can be incinerated by a simple incineration facility, and the environmental burden can be reduced.

In the pressure-sensitive adhesive sheet according to the second aspect of the present invention, the intermediate layer is made of the above-mentioned specific polypropylene resin, and an outer layer made of a polyolefin resin is laminated on at least one surface of the intermediate layer to form a base material. It is configured. Since the intermediate layer is formed using the specific polypropylene-based resin, the intermediate layer has excellent flexibility and is suitable for an adherend having a three-dimensional curved surface, similarly to the pressure-sensitive adhesive sheet according to the first aspect of the present invention. Followability is enhanced. Therefore,
Similarly to the first aspect of the present invention, it can be easily attached to adherends having various shapes.

Also, by appropriately changing the coating layer,
Adhesive sheets having different decorative effects can be easily provided, and it is possible to easily cope with a small number and variety of decorative adhesive sheets.
In addition, since polyolefin resins are mainly used, incineration can be performed with simple incineration equipment, and environmental burden can be reduced.

[0139] In the pressure-sensitive adhesive sheet according to the third aspect of the present invention, the white sheet is formed by mixing 10 to 300 parts by weight of titanium oxide with respect to 100 parts by weight of the polypropylene resin. Is effectively hidden. In addition, the saturation of the coating layer is enhanced, and the decorative effect of the coating layer is more effectively exhibited.

In the invention according to claim 4, since the total light transmittance of the polyolefin-based resin sheet is 85% or more, the decorative effect utilizing transmitted light can be exhibited well, and the adhesive for an electric signboard can be obtained. A decorative adhesive sheet suitable for a sheet or the like can be provided.

[0141] In the pressure-sensitive adhesive sheet according to the fifth aspect of the present invention, the coating layer comprises 100 parts by weight of one resin selected from the group consisting of an acrylic resin, a urethane resin, a polyester resin and a fluororesin. And 0.5 to 200 parts by weight of a pigment, so that it is excellent in weather resistance and the flexibility of the coating layer is enhanced, so that it is easier to apply to an adherend having a three-dimensional curved surface. Become.

[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.

Claims (5)

[Claims] 1. A pressure-sensitive adhesive sheet comprising a polyolefin resin sheet having a coating layer on one surface and a pressure-sensitive adhesive layer laminated on the other surface, wherein the polyolefin resin sheet has a weight average molecular weight Mw of 80,000 to 50. The resin elution amount from 0 ° C to 10 ° C by the cross fractionation method is 45 to 80% by weight of the total amount of the polypropylene resin, and the resin elution amount at more than 10 ° C and 70 ° C or less is 5 to 35% by weight of the amount of the polypropylene resin, the resin elution amount at 70 ° C or higher and 95 ° C or lower is 1 to 30% by weight of the total amount of the polypropylene resin, and the resin at a temperature of more than 95 ° C and 125 ° C or lower It comprises a polyolefin resin containing 20 to 100% by weight of a polypropylene resin having a composition within a range of 3 to 35% by weight of the total amount of the polypropylene resin. And a pressure-sensitive adhesive sheet. 2. A pressure-sensitive adhesive sheet in which a coating layer is laminated on one side of a polyolefin-based resin sheet and a pressure-sensitive adhesive layer is laminated on the other side, wherein the polyolefin-based resin sheet has an intermediate layer and at least one side of the intermediate layer. The intermediate layer has a weight average molecular weight Mw in the range of 80,000 to 500,000, and is 0 ° C. or more and 10 ° C. or less by a cross fractionation method. The resin elution amount is 45 to 80% by weight of the total polypropylene resin amount, exceeds 10 ° C, and the resin elution amount at 70 ° C or less is 5 to 35% by weight of the total polypropylene resin amount, and exceeds 70 ° C. The resin elution amount at 95 ° C. or lower is 1 to 30% by weight of the total polypropylene resin amount, and the resin elution amount at 95 ° C. or higher and 125 ° C. or lower is 3% of the total polypropylene resin amount. Adhesive sheet characterized by comprising a polypropylene resin having a composition within the range of 35 wt%. 3. The pressure-sensitive adhesive sheet according to claim 1, wherein 10 to 300 parts by weight of titanium oxide is added to 100 parts by weight of the polypropylene-based resin in the polyolefin-based resin sheet. 4. The JI of the polyolefin resin sheet
The pressure-sensitive adhesive sheet according to claim 1, wherein the total light transmittance according to SK7105 is 85% or more. 5. The coating layer comprises 100 parts by weight of at least one resin selected from the group consisting of an acrylic resin, a urethane-based resin, a polyester-based resin and a fluorine-based resin, and 0.5 to 200 parts by weight of a pigment. The pressure-sensitive adhesive sheet according to any one of claims 1 to 4, comprising: