JP2002235052A - Pressure-sensitive adhesive sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a tough decorative pressure-sensitive adhesive sheet having extensibility and excellent cutting suitability and weather and fouling resistances. SOLUTION: The pressure-sensitive adhesive sheet comprises a resin layer comprising a reactional product of (A) an acrylic polymer having >=2 functional groups reactive with isocyanate groups with (B) at least one kind of compound having >=2 functional groups reactive with the isocyanate groups and selected from a polyether, a polyester, a polycarbonate and a polybutadiene and (C) an isocyanate compound having >=2 isocyanate groups and having 20-100 μm thickness, an olefin film having 0.7-2.2 kg/mm2 yield value and 300-900 g tear strength under conditions of 25 deg.C and 30-90 μm thickness, an adhesive mass layer and a mold release sheet successively laminated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive sheet used for decoration or marking outdoors and indoors.

[0002]

2. Description of the Related Art At present, molded articles and exterior panels, interior materials, building materials, various guide boards, traffic signs, indoor / outdoor advertisements, signboards, shutters, windows, etc. of automobiles, motorcycles, motor boats, snowmobiles, home appliances, electronic devices, etc. For example, various plastic sheets are used in the field of so-called marking sheets, which are colored, decorated, and displayed, and impart various surface functions such as weather resistance, antifouling property, and various resistances. Hereinafter, the use of the marking sheet will be described. One side of the colored plastic sheet is subjected to adhesive processing (provided with an adhesive layer and a release sheet), and the desired plots and characters are cut on the colored plastic sheet together with the adhesive layer on the back side by a cutting plotter. (Cutting). After removing unnecessary parts, the design and text are adhered to a slightly adhesive film called application film, and the design and text are transferred from the colored plastic sheet side to the application film together with the adhesive layer on the back surface. . Next, the pressure-sensitive adhesive layer is attached to the adherend, and the application film is peeled off, whereby a pattern, a character, or the like can be easily formed on the adherend. Alternatively, an adhesive layer and a release sheet are provided on one side of a colorless transparent or colored plastic sheet, and a pattern or character is formed on the other side by various printing methods or the like, and an adhesive is provided around the pattern with a cutting plotter. It is also possible to cut the layers one by one and apply the design to the adherend similarly using the application film.

In the field of such marking sheets, semi-rigid or soft vinyl chloride resin compositions are often used as materials for (colored) plastic sheets. However, in order to impart physical properties such as moldability and extensibility to these semi-rigid or soft vinyl chloride resin compositions, low molecular weight compounds, for example, phthalic acid plasticizers and the like are added in large amounts. ing. Since these plasticizers have a large migration property, they migrate to the sheet surface over time to impair the appearance, or migrate to the adherend to reduce the adhesive strength,
There is a problem that blisters and wrinkles are generated due to expansion of the base material. Further, the plasticizer migrates to the surface or the adherend, so that the extensibility of the vinyl chloride resin composition is lost, and the state at the time of molding cannot be maintained. In addition, soft vinyl chloride resin has low hardness,
There was also a problem that the abrasion resistance and the scratch resistance were poor.

[0004] Other (colored) plastic sheet materials include acrylic resins such as polymethyl methacrylate, polyethylene terephthalate, polyethylene, and the like.
Polypropylene and the like are generally known. However, acrylic resins such as polymethyl methacrylate and polyethylene terephthalate have toughness, but are inferior in extensibility. As with vinyl resins, low molecular weight plasticizers must be added. In addition, acrylic resins such as polymethyl methacrylate, polyethylene terephthalate, polyethylene, and polypropylene have a problem that, when the molecular weight is high, the dispersibility of a coloring agent such as a pigment is low, coloring becomes difficult, and decorativeness is significantly impaired. In the case of a low molecular weight, there is a problem that the toughness when formed into a sheet is poor. In addition, as an extensible (colored) plastic sheet material,
A urethane resin, which is a cured product of a polyester diol and an isocyanate compound, is known, but has problems such as poor toughness and low weather resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a decorative pressure-sensitive adhesive sheet which is tough and extensible, and is excellent in cutting suitability, weather resistance and stain resistance.

[0006]

Means for Solving the Problems The present inventors have developed an acrylic polymer (A) having two or more functional groups capable of reacting with isocyanate groups on one surface of an olefin film having specific physical properties, Having two or more functional groups, at least one compound (B) selected from polyether, polyester, polycarbonate, and polybutadiene is crosslinked with an isocyanate compound (C) having two or more isocyanate groups (20 to 100 μm). It has been found that by providing the resin layer of (1), a sheet having better weather resistance than a conventional vinyl chloride-based decorative adhesive sheet can be produced, and the present invention has been accomplished. That is, the first invention is a pressure-sensitive adhesive sheet in which a resin layer, an olefin film, a pressure-sensitive adhesive layer, and a release sheet are sequentially laminated, and the olefin film has a yield value of 0.7 to 2.2 kg at 25 ° C. / mm ^2, tear strength 300～900G, a thickness 30～90Myuemu, the resin layer, a functional group capable of reacting with the acrylic polymer (a) and isocyanate groups having two or more functional groups capable of reacting with isocyanate groups Having two or more, polyether, polyester, polycarbonate, at least one compound selected from polybutadiene (B), containing a reaction product of an isocyanate compound having two or more isocyanate groups (C), glass transition Temperature is 50-120 ℃, 0 ℃
Storage elasticity Er 7.5 × 10 ^{8 to} 5.0 × 10 ⁹ Pa, tan δ
Is 7.0 × 10 ^{−2 to} 2.5 × 10 ⁻¹ , the storage modulus Er at 50 ° C. is 1.0 × 10 ^{8 to} 2.0 × 10 ⁹ Pa, and tan δ is 1.0 × 10 ^{−1 to} 6.
0 × 10 ⁻¹ and a storage elastic modulus Er at 80 ° C. of 8.0
× 10 ^{6 to} 1.3 × 10 ⁸ Pa, and the thickness of the resin layer is 20 to 100
A second aspect of the present invention is the adhesive sheet according to the first aspect, wherein the resin layer is a colored resin layer further containing a coloring agent.

Further, the third invention is directed to a yield value at 25 ° C.
0.7~2.2kg / mm ^2, tear strength 300～900G, thickness 30 to 90
Acrylic polymer (A) having two or more functional groups capable of reacting with isocyanate groups on one side of a μm olefin film, having two or more functional groups capable of reacting with isocyanate groups, polyether, polyester, polycarbonate, At least one compound selected from polybutadiene (B), and a resin composition containing an isocyanate compound having two or more isocyanate groups (C),
Heat cured, glass transition temperature is 50 ~ 120 ℃, 0 ℃
Storage elasticity Er at 7.5 × 10 ^{8 to} 5.0 × 10 ⁹ Pa, tan
δ is 7.0 × 10 ^{−2 to} 2.5 × 10 ⁻¹ , storage elastic modulus Er at 50 ° C. is 1.0 × 10 ^{8 to} 2.0 × 10 ⁹ Pa, tan δ is 1.0 × 10 ⁻¹ to
6.0 × 10 ⁻¹ and the storage elastic modulus Er at 80 ° C.
8.0 × 10 ^{6 to} 1.3 × 10 ⁸ Pa, and the thickness of the resin layer is 20 to
A method for producing a pressure-sensitive adhesive sheet, wherein a resin layer having a thickness of 100 μm is formed, and then a pressure-sensitive adhesive layer and a release sheet are sequentially laminated on the other surface of the olefin film. The method for producing a pressure-sensitive adhesive sheet according to the third invention, wherein a pressure-sensitive adhesive layer separately formed on one surface of a release sheet is laminated on the other surface of the laminated olefin film. , The resin composition is
A method for producing a pressure-sensitive adhesive sheet according to the third or fourth invention, comprising a coloring agent.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The pressure-sensitive adhesive sheet of the present invention can be suitably used as a marking sheet. That is, when the resin layer of the pressure-sensitive adhesive sheet of the present invention contains a coloring agent, a desired plot or character is cut (cut) together with the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet of the present invention using a cutting plotter, which is unnecessary. After removing the debris, the pattern / character part is attached to a slightly adhesive film called an application film, and the pattern /
By transferring the character portion from the pressure-sensitive adhesive sheet side to the application film, and then attaching the pressure-sensitive adhesive layer to the adherend and peeling off the application film, it is possible to easily form a pattern / character on the adherend. . Alternatively, when the resin layer of the pressure-sensitive adhesive sheet of the present invention does not contain a coloring agent, after forming a desired pattern or characters on the surface of the resin layer of the pressure-sensitive adhesive sheet by a method such as silk screen printing, the cutting plotter is used to form the desired pattern or character. The periphery can be cut together with the pressure-sensitive adhesive layer, and a pattern can be attached to an adherend using an application film in the same manner.

Olefin film The olefin film constituting the present invention includes, for example, polyethylene films such as low density polyethylene, medium density polyethylene and high density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene and ethylene-based copolymers such as -α-olefin copolymers. Further, those obtained by mixing a rubber-based or styrene-based elastomer with these olefin-based resins are used. From the viewpoint of durability and heat resistance, a polypropylene film or a film obtained by mixing an elastomer with polypropylene is desirable.

[0010] The olefin film at 25 ° C
JIS yield value when the tensile speed of 300 mm / min according to No. 1 form test piece K7113 is 0.7~2.2kg / mm ^2, tear strength speed 30 mm / min by means of the quadrature-type tearing method JIS K6732 is 300~900g
It is. The yield value is less than 0.7 kg / mm ^2, when cutting out a part of symbols in the cutting plotter, not only can not create a symbol will be film rolled up, attached to the adherend,
The film shrinks when left for a long time. on the other hand,
When the yield value exceeds 2.2 kg / mm ² , not only the cutting edge of the cutting plotter becomes jagged, but also the extensibility is not obtained, and it becomes difficult to perform the application work to a secondary or tertiary curved surface. If the tear strength is less than 300 g, the film may be easily torn at the time of removing debris after cutting, and a required pattern may be damaged. On the other hand, if the amount exceeds 900 g, the cutting by the blade of the cutting plotter becomes worse, so the more preferable range is 500 to 800 g.

[0011] Olefin films are usually manufactured by extrusion molding, and when the thickness is thin, the workability of sticking may be reduced. When the film is thick, the rigidity is increased, and the sticking work on a secondary or tertiary curved surface is difficult. 30 ~ 90
μm, more preferably 40-80 μm
It is.

The olefin film may contain conventionally known ultraviolet absorbers, hindered amine-based light stabilizers, heat stabilizers, flame retardants, pigments, etc. as long as the physical properties are not impaired. Further, the olefin film, for the purpose of improving the adhesiveness with the resin layer described later, or the adhesiveness with the adhesive layer laminated on the interface with the resin layer as needed,
Surface treatment such as plasma treatment, corona treatment, flame treatment, electron beam irradiation treatment, surface roughening treatment, ozone treatment, etc., and dry plating treatment such as vacuum deposition, sputtering, and ion plating may be performed. The olefin film may be, for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer or the like modified with an acid-containing compound such as maleic anhydride, acrylic resin, urethane, depending on the resin layer and the adhesive layer described below. Resins, epoxy resins, polyamide resins, those modified with hydrazine-based compounds, silane coupling agents, titanium coupling agents, coupling agents such as phosphite coupling agents, polyester resins having a hydroxyl group,
One or more adhesive layers made of at least one of polyurethane resin, acrylic resin and a combination of a polyfunctional isocyanate compound, a synthetic rubber compound, and polyethyleneimine may be provided.

Resin Layer The resin layer constituting the pressure-sensitive adhesive sheet of the present invention has a glass transition temperature (hereinafter, referred to as Tg) of 50 to 120 ° C. and a storage modulus Er at 0 ° C. of 7.5 × 10 ^{8 to} 5.0 × 10 ^{8. 9} Pa and tanδ
7.0 × 10 ^{−2 to} 2.5 × 10 ⁻¹ , storage elastic modulus Er at 50 ° C. is 1.0 × 10 ^{8 to} 2.0 × 10 ⁹ Pa, and tan δ is 1.0 × 10 ⁻¹ to
6.0 × 10 ⁻¹ and the storage elastic modulus Er at 80 ° C.
It is important that the pressure is 8.0 × 10 ^{6 to} 1.3 × 10 ⁸ Pa and the film thickness is 20 to 100 μm.

The Tg of the resin layer is determined by
It can be obtained from the temperature of the maximum value of nδ, and it is desirable that the change in texture is as small as possible at the environmental temperature in which the pressure-sensitive adhesive sheet is used, so Tg is preferably 50 to 120 ° C, more preferably 70 ° C. ~ 100 ° C. Tg
Of the resin layer having a temperature of 50 to 120 ° C., within a range of 0 to 50 ° C., Er monotonically decreases and tan δ monotonically increases with increasing temperature.

When the storage elastic modulus Er of the resin layer at 0 ° C. and 50 ° C. is less than the respective lower limit values, the resin layer is too soft to make cutting and sticking work difficult. The surface of the pattern becomes tacky and dirt easily adheres when exposed outdoors for a long period of time.
On the other hand, the storage elastic modulus Er of the resin layer at 0 ° C. and 50 ° C.
However, when each exceeds the upper limit value, although the dirt is not attached to the design surface after pasting, the resin layer is too hard, but the extensibility of the adhesive sheet itself is not sufficiently obtained,
The resin layer breaks before the olefin film,
No longer follows olefin films. As a result, it is difficult to perform the sticking work on the secondary or tertiary curved surface.

The tan δ of the resin layer at 0 ° C. and 50 ° C.
However, if each is less than the lower limit, it is too hard to exhibit sufficient extensibility, while the tanδ of the resin layer at 0 ° C. and 50 ° C.
However, if each exceeds the upper limit, the resin layer is too soft,
Causes blocking and poor stain resistance.

Further, the storage elastic modulus E of the resin layer at 80 ° C.
When r is less than 8.0 × 10 ⁶ Pa, dirt is remarkably adhered when exposed outdoors. On the other hand, when the Er of the resin layer at 80 ° C. exceeds 1.3 × 10 ⁸ Pa, the stain resistance is improved, but when the film is stretched while overheating with a drier or the like when applied to a secondary or tertiary curved surface. It becomes difficult to stretch.

Such a resin layer is an acrylic polymer having two or more functional groups capable of reacting with an isocyanate group.
(A), and has at least two functional groups capable of reacting with isocyanate groups, polyether, polyester, polycarbonate, at least one compound selected from polybutadiene (B), and an isocyanate compound having two or more isocyanate groups It can be obtained from the reaction product with (C).

Acrylic polymer (A) used here
Is obtained by copolymerizing a radical polymerizable monomer having a functional group capable of reacting with an isocyanate group with another radical polymerizable monomer, and a part of the radical polymerizable monomer is (meth) ) A copolymer which is an acrylic monomer. The ratio of the (meth) acrylic monomer in the monomers constituting the acrylic polymer is determined based on the total amount of the monomers in view of the toughness of the obtained sheet, processability, and ease of production of the polymer. It is preferably at least 30% by weight, particularly preferably 50 to 80% by weight. As the radical polymerizable monomer,
(Meth) acrylic monomers, aromatic vinyl monomers, olefinic hydrocarbon monomers, vinyl ester monomers, vinyl ether monomers, and the like. Examples of the functional group capable of reacting with the isocyanate group include a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an N-methylol group, and an N-alkoxymethyl group. A hydroxyl group is preferable in terms of reactivity.

Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate,
2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, hydroxystyrene and the like. .

Examples of the (meth) acrylic monomer having an amino group include methylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, butylaminoethyl (meth) acrylate, and t-butylamino. Monoalkylaminoalkyl (meth) acrylates such as ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylamino (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate N, N-dialkylaminoalkyl (meth) acrylate.

Examples of (meth) acrylic monomers having a carboxyl group include acrylic acid and methacrylic acid. Examples of other radically polymerizable monomers having a carboxyl group include crotonic acid. , Itaconic acid, maleic acid and the like. Examples of (meth) acrylic monomers having an epoxy group include glycidyl (meth) acrylate, and examples of other radically polymerizable monomers having an epoxy group include glycidyl cinnamate and glycidyl. Examples include allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, and 1,3-butadiene monoepoxide. Examples of the (meth) acrylic monomer having an N-methylol group include N-methylol (meth) acrylamide.

Examples of (meth) acrylic monomers having an N-alkoxymethyl group include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) (Meth) acrylamide having N-monoalkoxymethyl group such as acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylol (meth) acrylamide, N, N-di (methoxymethyl)
N, such as (meth) acrylamide, N, N-di (ethoxymethyl) (meth) acrylamide, N, N-di (propoxymethyl) (meth) acrylamide, N, N-di (butoxymethyl) (meth) acrylamide (Meth) acrylamide having an N-dialkoxymethyl group is exemplified. The radical polymerizable monomer having a functional group capable of reacting with an isocyanate group is one kind according to required performance.
Alternatively, two or more kinds can be used as a mixture.

Among other radically polymerizable monomers other than the radically polymerizable monomer having a functional group capable of reacting with an isocyanate group, examples of the (meth) acrylic monomer include methyl (meth) acrylate Butyl (meth) acrylate, ethylhexyl (meth) acrylate, stearyl (meth) acrylate and other alkyl (meth) acrylates, benzyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (Meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, perfluorobutylmethyl ( Meta Acrylate, perfluorooctylmethyl (meth) acrylate, perfluorodecylmethyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctylamyl (meth) acrylate, perfluorooctyl Perfluoroalkylalkyl (meth) acrylate having a perfluoroalkyl group having 1 to 20 carbon atoms, such as undecyl (meth) acrylate, hexafluorooctyl (meth) acrylate, octafluorodecyl (meth) acrylate, octafluorononyl (meth) A) partially fluorinated alkylalkyl (meth) acrylates such as acrylates, and polyorganosiloxane compounds containing one terminal (meth) acryloxy group.

Among other radically polymerizable monomers, examples of olefinic hydrocarbon monomers include ethylene, propylene, butadiene, isobutylene, isoprene,
Examples thereof include 1,4-pentadiene and vinyl halide monomers in which some of the hydrogen atoms of these monomers are substituted with halogen atoms. Specific examples of the vinyl halide monomer include vinyl chloride, vinylidene chloride, monofluoroethylene, difluoroethylene, trifluoroethylene and the like. Among other radically polymerizable monomers, examples of the aromatic vinyl monomer include styrene, methylstyrene, ethylstyrene, chlorostyrene and the like. Examples of the vinyl ester monomer include vinyl acetate. Examples of vinyl ether monomers include vinyl methyl ether. Other radically polymerizable monomers can be used alone or in combination of two or more depending on required performance.

The acrylic polymer (A) can be prepared by a known method,
For example, it can be obtained by solution polymerization. As the solvent,
Methanol, ethanol, propanol, butanol,
Alcohols such as ethylene glycol methyl ether and diethylene glycol methyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; carbonization such as hexane, heptane and octane It is possible to use hydrogens, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate. The solvent may be a mixture of two or more. The charged concentration of the monomer during the synthesis is preferably from 0 to 80% by weight.

Examples of the polymerization initiator include ordinary peroxides or azo compounds such as benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate, T-butyl peroctoate, cumene hydroxyperoxide or the like is used, and the polymerization temperature is 50 to 200.
C, especially 70-140C is preferred.

As the acrylic polymer (A), a commercially available product may be used. Specific examples of commercially available acrylic polymers (acrylic polyols) having two or more hydroxyl groups include, for example, Olester Q16 manufactured by Mitsui Chemicals, Inc.
4, Q167-40, Q174, Q171, Q602,
Q602, Q185, Q177, Q166, Q193,
Q182, Q187, Q189, Q186 and Desmophen A160X, A manufactured by Sumitomo Bayer Urethane Co., Ltd.
160SN, A165BA / X, A265BA, A36
5BA / X, A450MPA / X, A450BA, A5
65X, A575X, A665BA / X, Acryt 6519MB, 6TH-419, 6 manufactured by Taisei Kako Co., Ltd.
KR-404T, 6614MA, 6416MA, 6BS
-309L, 6AN-303, 6BF-203, 6LQ
-724, 6KW-713, 6KW-720, 6KW-
801 and the like.

The weight average molecular weight in terms of polystyrene of the acrylic polymer (A) is preferably from 5,000 to 50.
0000, more preferably 10,000 to 200,0.
00. If the upper limit is exceeded, the extensibility of the sheet will decrease, and if it exceeds the lower limit, the toughness and chemical resistance of the sheet will decrease. The acrylic polymer (A) can be used as a mixture of two or more kinds according to required performance. In particular, an acrylic polymer having a weight average molecular weight of 10,000 to 50,000 and a weight average molecular weight of 60,000 to 20
It is preferable to use a mixture with 000 acrylic polymer. When a mixture of two or more acrylic polymers having different molecular weights is used, stretchability and toughness can be imparted to the sheet in a more balanced manner.

When the acrylic polymer (A) has a hydroxyl group, its hydroxyl value is preferably 10 to 10 in terms of solid content.
300, more preferably 20 to 150 in terms of solid content. If the upper limit is exceeded, the extensibility of the sheet will decrease. If the lower limit is exceeded, the adhesion to the substrate, the pigment dispersibility and the chemical resistance of the sheet will decrease. The glass transition temperature of the acrylic polymer (A) is preferably 0 to 150 ° C,
More preferably, it is 10 to 100 ° C. If the upper limit is exceeded, the extensibility decreases, and if the lower limit is exceeded, tack remains on the sheet surface, and the chemical resistance and surface hardness of the sheet decrease.

At least one selected from polyethers, polyesters, polycarbonates and polybutadienes having two or more functional groups capable of reacting with isocyanate groups, which is used for forming the resin layer constituting the pressure-sensitive adhesive sheet of the present invention. The compound (B) is used to impart flexibility, extensibility to the sheet, and pigment dispersibility to the colored resin layer. The compound (B) is, for example, a polyester, polyether, polycarbonate, or polybutadiene having at least two functional groups capable of reacting with an isocyanate group at a linear terminal or a branched terminal. Among them,
Polyester is preferred in view of the balance between the extensibility and toughness of the obtained sheet and the moldability.

Examples of the functional group capable of reacting with the isocyanate group include a hydroxyl group, an amino group, a carboxyl group, an N-methylol group, an N-alkoxymethyl group, and the like. And a hydroxyl group is preferred. The number of functional groups capable of reacting with an isocyanate group is particularly preferably three, and extensibility can be obtained with a small amount as compared with the case of two, and the toughness of the coating film is not impaired.

Specific examples of the polyester include a terminal hydroxyl group-containing ester obtained by esterifying at least one dicarboxylic acid and at least one polyol such as a polyhydric alcohol, a polyhydric phenol, or an alkoxy-modified product thereof. A compound, and an amino group at the terminal hydroxyl group,
An ester compound modified to a carboxyl group, an N-methylol group, or an N-alkoxymethyl group may, for example, be mentioned. Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, p-oxybenzoic acid, p- (hydroxy) benzoic acid, 1,4-
Cyclohexanedicarboxylic acid, succinic acid, adipic acid,
Examples include dicarboxylic acids such as azelaic acid, sebacic acid and dodecanedicarboxylic acid.

Examples of polyhydric alcohols include 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,2- Dimethyl-1,4-butanediol, 2-ethyl-1,4-butanediol, 1,5-
Pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,
2,4-trimethyl-1,3-pentanediol, 3-
Ethyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,6-hexanediol, 3
-Methyl-1,6-hexanediol, 1,7-heptanediol, 2-methyl-1,7-heptanediol,
3-methyl-1,7-heptanediol, 4-methyl-
1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 2-ethyl-1,8-octanediol, 3-methyl-1,8-
Octanediol, 4-methyl-1,8-octanediol, 1,9-nonanediol, ethylene glycol,
Propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol,
Examples include trimethylolpropane, 1,1,1-trimethylolpropane ethylene glycol, glycerin, erythritol, xylitol, sorbitol, mannitol and the like.

Examples of polyhydric phenols include catechol, resorcin, hydroquinone, hexylresorcin,
Trihydroxybenzene, dimethylolphenol and the like can be mentioned. Examples of commercially available polyesters (polyester polyols) having two or more hydroxyl groups include, for example, Kuraray polyols P-510 and P-1 manufactured by Kuraray Co., Ltd.
010, P-1510, P-2010, P-3010,
P-4010, P-5010, P-6010, P-20
11, P-2013, P-520, P-1020, P-
2020, P-1012, P-2012, P-530,
P-1030, P-2030, PMSA-1000, P
MSA-2000, PMSA-3000, PMSA-4
000, F-2010, F-3010, N-2010,
PNOA-1010, PNOA-2014, O-201
0, Desmophen 6 manufactured by Sumitomo Bayer Urethane Co., Ltd.
50MPA, 651MPA / X, 670, 670BA,
680X, 680MPA, 800, 800MPA, 85
0, 1100, 1140, 1145, 1150, 115
5, 1200, 1300X, 1652, 1700, 18
00, RD181, RD181X, C200 and the like.

Examples of polyethers include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol;
An ether compound modified to a methylol group or an N-alkoxymethyl group. Examples of commercially available polyethers having two or more hydroxyl groups (polyether polyols) include, for example, Desmophen 250U, 550U, 1600U, and 1900 manufactured by Sumitomo Bayer Urethane Co., Ltd.
U, 1915U, and 1920D.

Examples of the polycarbonate include a polycarbonate diol represented by the following general formula and a carbonate compound in which a terminal hydroxyl group is modified to an amino group, a carboxyl group, an N-methylol group or an N-alkoxymethyl group. . H- (OR-OCO-) n-ROH (R: alkyl chain, diethylene glycol, etc.) Examples of commercially available polycarbonates having two or more hydroxyl groups include Kuraray Polyol PN manufactured by Kuraray Co., Ltd.
OC-1000, PNOC-2000, PMHC-20
50, PMHC-2050R, PMHC-2070, P
MHC-2070R, PMHC-2090R, C-20
90 and the like.

Examples of polybutadiene include α,
Examples thereof include ω-polybutadiene glycol, α, β-polybutadiene glycol, and butadiene compounds in which terminal hydroxyl groups have been modified to amino groups, carboxyl groups, N-methylol groups, or N-alkoxymethyl groups. Examples of commercially available polybutadienes having two or more hydroxyl groups include, for example, NISSO-PB G-10 manufactured by Nippon Soda Co., Ltd.
00, G-2000, G-3000, GI-1000,
GI-2000, GI-3000, GQ-1000, G
Q-2000 and the like.

The average weight molecular weight in terms of polystyrene of the compound (B) is preferably from 100 to 10,000, more preferably from 1,000 to 5,000. If the upper limit is exceeded, the solubility in the solvent will decrease and the extensibility of the sheet will decrease. If the lower limit is exceeded, the compatibility with other components is reduced, making it difficult to form a uniform and smooth sheet, and the toughness of the sheet is reduced. The compound (B) can be used singly or in combination of two or more depending on required performance. When used for exterior use, it is preferable to use an alicyclic or aliphatic compound from the viewpoint of yellowing.

The mixing ratio (weight ratio) of the acrylic polymer (A) and the compound (B) is preferably (A) :( B) = 9
5: 5 to 20:80, more preferably (A) :( B)
= 90:10 to 40:60. When the ratio of the acrylic polymer (A) exceeds the upper limit, the pigment dispersibility, the extensibility, flexibility, and moldability of the sheet decrease, and when the ratio exceeds the lower limit, the toughness and chemical resistance of the sheet decrease. Is less effective.

The polyisocyanate compound (C) having two or more isocyanate groups constituting the present invention includes the acrylic polymer (A) and the compound (B), the acrylic polymer (A) and the acrylic polymer (A), and the compound (C). It is used for crosslinking each of B) and the compound (B) to form a tough and extensible sheet. When the obtained sheet is used for exterior use, it is preferable to use only an alicyclic or aliphatic compound in order to prevent the sheet from discoloring from yellow to brown over time.

Examples of the alicyclic polyisocyanate compound include polyvalent isocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated 4,4'-diphenylmethane diisocyanate. As the aliphatic polyisocyanate compound, for example, trimethylhexamethylene diisocyanate,
4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like.

Examples of the aromatic polyisocyanate compound include diphenylmethane diisocyanate, toluylene diisocyanate, naphthylene-1,5-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, triphenylmethane triisocyanate and polyphenyl isocyanate. Examples include methylene polyphenyl isocyanate. As the polyisocyanate compound, an isocyanate adduct at both ends of the above compound and a glycol or a diamine, a modified biuret, or a modified isocyanurate may be used.

In particular, it is preferable that the polyisocyanate compound (C) contains a modified isocyanurate, particularly a triisocyanate having an isocyanurate ring, since a sheet having higher toughness and extensibility can be obtained.
Specific examples of the isocyanurate ring-containing triisocyanate include isocyanurate-modified isophorone diisocyanate (for example, Desmodur Z4470 manufactured by Sumitomo Bayer Urethane Co., Ltd.) and isocyanurate-modified hexamethylene diisocyanate (for example, Sumidur manufactured by Sumitomo Bayer Urethane Co., Ltd.) 3300), isocyanurate-modified toluylene diisocyanate (for example, Sumidur FL-2 manufactured by Sumitomo Bayer Urethane Co., Ltd.)
FL-3, FL-4, HL BA).

Further, the isocyanate group of the above polyisocyanate compound is replaced with, for example, methanol, ethanol,
n-pentanol, ethylene chlorohydrin, isopropyl alcohol, phenol, p-nitrophenol,
A block modified product which has been blocked by reacting with a blocking agent such as m-cresol, acetylacetone, ethyl acetoacetate, and ε-caprolactam may be used.

Further, as the compound (C), at least one compound (a) selected from polyether, polyester, polycarbonate, or polybutadiene having two or more functional groups capable of reacting with an isocyanate group, and an isocyanate group at both terminals And a diisocyanate compound (b) having an isocyanate prepolymer having both ends. When the compound (C) contains the above-mentioned isocyanate prepolymer at both ends, extensibility can be obtained with a small amount, and the toughness of the coating film is not impaired. It also has the effect of improving the compatibility between the acrylic polymer (A) and the compound (B). The terminal isocyanate prepolymer preferably has an isocyanate group content of 1 to 1, based on the total amount of isocyanate groups in the composition.
% To 50%, particularly preferably 5% to 30%. If the upper limit is exceeded, the solubility in a solvent and the compatibility with other components decrease, and it becomes difficult to obtain a uniform and smooth sheet, and tack remains on the sheet surface. If the lower limit is exceeded, the effect of improving the extensibility of the sheet will not be sufficiently exhibited.

As the compound (a), the same compound as the compound (B) can be used. As the compound (b), for example, tolylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate,
Lysine diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate and the like can be mentioned.

The isocyanate prepolymer at both ends is compound (a) and compound (a) at a ratio such that the isocyanate group of compound (b) is larger than 1 with respect to the functional group 1 capable of reacting with the isocyanate group of compound (a). It is obtained by mixing (b), heating and stirring to react. The weight average molecular weight of the prepolymer in terms of polystyrene is preferably from 1,000 to 50,000, and more preferably from 100 to 50,000.
0 to 10,000. If the upper limit is exceeded, the solubility in a solvent and the compatibility with other components will decrease. If the lower limit is exceeded, the toughness and extensibility of the sheet will be insufficient.

According to the required performance, the total amount of the isocyanate groups in the compound (C) is preferably 0.1 times the total amount of the functional groups of the acrylic polymer (A) and the functional groups of the compound (B). To 3.0 times, more preferably 0.5 times to 2.times.
One kind or a mixture of two or more kinds can be used in such a ratio as to be 0 times. The compound (B) and the compound (C) may be reacted in advance to form a terminal isocyanate prepolymer. In this case, the colored resin layer is a composition containing the acrylic polymer (A) and a terminal isocyanate prepolymer obtained by reacting the compound (B) with the compound (C).

In order to accelerate the crosslinking reaction between the acrylic polymer (A) and the compound (B) with the compound (C), the resin layer constituting the pressure-sensitive adhesive sheet of the present invention has various functions depending on the respective functional groups. Can be included. Representative crosslinking catalysts include organometallic compounds, acids and their ammonium salts, lower amine salts, polyvalent metal salts, amines, organic peroxides, and the like. Specific examples of the organic metal compound include sodium acetate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin dioctate, dibutyltin dilaurate, and dibutyltin. Malate dibutyltin di (2-ethylhexoate), diethylzinc, tetra (n-butoxy) titanium and the like can be mentioned.

Specific examples of the acid include trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid ester of β-hydroxyethyl (meth) acrylate, monoalkyl phosphorous acid, dialkyl phosphorous acid, −
Examples include toluenesulfonic acid, phthalic anhydride, benzoic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, acetic acid, propionic acid, itaconic acid, oxalic acid, and maleic acid. Specific examples of the amines include dicyclohexylamine, triethylamine, N, N-dimethylbenzylamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, diethanolamine, triethanolamine, cyclohexylethylamine, and the like. Is mentioned.

Examples of the organic peroxide include hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, diacetyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethyl. Hexanoate,
t-butyl peroxylaurate and the like.

When the functional group of the acrylic polymer (A) or the compound (B) is a hydroxyl group among these cross-linking catalysts, it is preferable to use acids and their ammonium salts, lower amine salts, polyvalent metal salts and the like. . In the case of an amino group, use of an organic peroxide, acid anhydride, carboxylic acid, zinc oxide-magnesium oxide or the like is preferable. In the case of a carboxyl group, the use of acids and their ammonium salts, lower amine salts, polyvalent metal salts and the like is preferred. In the case of an epoxy group,
The use of organometallic compounds, amines and the like is preferred. N-
In the case of a methylol group or an N-alkoxymethyl group, use of an acid, an ammonium salt thereof, a lower amine salt, a polyvalent metal salt or the like is preferable. Two or more of these crosslinking catalysts may be used, and the total amount used is 0.01 to 10% by weight based on 100% by weight of the total amount of the acrylic polymer (A), the compound (B) and the compound (C). Preferably 0.1
-5% by weight.

The resin layer constituting the pressure-sensitive adhesive sheet of the present invention may contain various coloring agents such as pigments and dyes for coloring, but not for the purpose of forming a transparent film. But it doesn't matter. As the pigment, conventionally known pigments can be used, and among them, pigments having high light resistance and weather resistance are preferable. Specifically, for example, quinacridone, anthraquinone, perylene, perinone, diketopyrrolopyrrole, isoindolinone, condensed azo, benzimidazolone, monoazo, insoluble azo, naphthol, Organic pigments such as flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthuanthrone, dioxazine, phthalocyanine, and indanthrone, and metals such as nickel dioxin yellow and copper azomethine yellow Complex, titanium oxide,
Metal oxides such as iron oxide and zinc oxide; metal salts such as barium sulfate and calcium carbonate; inorganic pigments such as carbon black, aluminum and mica; metal fine powders such as aluminum and mica fine powders. Examples of the dye include azo, quinoline, stilbene, thiazole, indigoid, anthraquinone, and oxazine dyes. The colorant may be used as it is, or may be used after being processed into a color paste, a color pellet or the like in advance.

In order to increase the strength of the sheet, the resin layer constituting the pressure-sensitive adhesive sheet of the present invention contains various materials other than the acrylic polymer (A) and the compound (B) as long as the effects of the present invention are not impaired. A thermoplastic resin may be contained.
Such thermoplastic resins include, for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer, polyisobutylene, polybutadiene, polystyrene, polycarbonate, polymethylpentene, ionomer, acrylonitrile-butadiene-styrene, acrylic resin, polyvinyl alcohol, Examples thereof include polyamide resin, polyacetal, and polyester.

Acrylic polymer (A) and compound (B)
The content of the thermoplastic resin other than 5 is 5 parts per 100 parts by weight of the total of the acrylic polymer (A) and the compound (B).
0 parts by weight or less is preferable, and 30 parts by weight or less is more preferable. If the upper limit is exceeded, the compatibility with other components and the adhesion to the olefin film decrease. In the resin layer, if necessary, an ultraviolet absorber, an ultraviolet stabilizer, a radical scavenger, a filler, a thixotropic agent, an antioxidant, an antioxidant, as long as the effects of the present invention are not impaired. Antistatic agent, flame retardant, thermal conductivity improver, plasticizer, sagging agent, antifouling agent, antiseptic, bactericide, defoamer, leveling agent, antiblocking agent, curing agent, thickener, pigment dispersion And various additives such as a silane coupling agent.

Next, a method for producing the pressure-sensitive adhesive sheet of the present invention will be described. First, the acrylic polymer (A) described above,
A resin composition obtained by mixing the compound (B), the compound (C), and, if necessary, a colorant, a crosslinking catalyst, an additive, and a solvent is obtained, and then (1) the resin composition is formed on the olefin film. Apply the material directly, heat and cure to form a film,
(2) The above-mentioned resin composition is once applied onto a process release treatment sheet, heated and cured to form a film, and then the cured resin composition layer and the olefin film are laminated and adhered at a temperature of 40 to 120 ° C. A laminate of an olefin film and a resin layer is obtained by such a method as described above, and then a pressure-sensitive adhesive layer and a release sheet are sequentially laminated on the olefin film surface of the laminate.

First, a resin composition containing the acrylic polymer (A), the compound (B), the compound (C) and, if necessary, a colorant will be described. The method of mixing the acrylic polymer (A), the compound (B), the compound (C), and the coloring agent, if necessary, is not particularly limited. ,
What is necessary is just to mix the compound (B), the compound (C) and other components and stir them with a stirring blade, a shaking stirrer, a rotary stirrer or the like. Further, mixing may be performed using a sand mill, a three-roll, a two-roll, or the like. In order to improve coatability, a solvent may be further added or concentrated.

When a colorant, especially a pigment, is added, first, a pigment paste is prepared by mixing a colorant, a dispersing resin, and if necessary, a dispersing agent and a solvent, and then mixing with other components. Is preferred. As the dispersing resin, it is preferable to use the compound (B), but it is not particularly limited, and has a polar group excellent in pigment dispersibility, for example, a hydroxyl group, a carboxyl group, a thiol group, an amino group, an amide group, a ketone group and the like. , An acrylic resin, a polyurethane resin, a polyurea resin, a polyester resin, or the like. Examples of the dispersant include a pigment derivative, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a titanium coupling agent, a silane coupling agent, and the like.
Further, the surface of the pigment can be modified by a metal chelate, a resin coat, or the like.

Solvents used in the above resin composition include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether and diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, Dioxane, ethylene glycol dimethyl ether, ethers such as diethylene glycol dimethyl ether, hexane, heptane, hydrocarbons such as octane, benzene, toluene,
Among the aromatics such as xylene and cumene, and the esters such as ethyl acetate and butyl acetate, an appropriate one is used according to the composition of the colored resin layer. Two or more solvents may be used.

As a method for applying the above resin composition to an olefin film or a process release sheet, a conventionally known method, for example, a gravure coating method, a kiss coating method,
Examples include a die coating method, a lip coating method, a comma coating method, a blade coating method, a roll coating method, a knife coating method, a curtain coating method, a slot orifice method, a spray coating method, and a bar coating method. The resin composition may be applied several times or may be applied once. Further, a plurality of different coating methods may be combined. The resin composition is applied so that the thickness of the resin layer after heat curing is 20 to 100 μm. When containing a colorant, the thickness of the resin layer is 20 μm
If less, the coloring power is inferior. On the other hand, if the thickness of the resin layer is larger than 100 μm, the resin layer lacks extensibility. Further, from the viewpoint of drying property and coating stability, a preferable film thickness is 20 to 50 μm. Heat curing of the resin composition, the type of resin composition, release sheet, heat resistance of the olefin film, film thickness, and heating temperature according to the application,
It may be carried out for a heating time, and usually at room temperature to 350 ° C.

The pressure-sensitive adhesive sheet of the present invention is obtained by laminating a pressure-sensitive adhesive layer and a release sheet sequentially on the olefin film surface of the laminate of the olefin film and the resin layer obtained as described above. The adhesive layer and the release sheet are
For example, they can be laminated as follows. (1) Apply an adhesive on the release sheet, heat and cure,
A laminate is formed of the pressure-sensitive adhesive layer and the release sheet, and the pressure-sensitive adhesive layer surface of the laminate and the olefin film surface of the separately obtained laminate of the olefin film and the resin layer are brought into facing contact with each other. ). (2) An adhesive is applied on the process release sheet and cured by heating to form a laminate of the adhesive layer and the process release sheet,
The surface of the pressure-sensitive adhesive layer of the laminate and the surface of the olefin film of the laminate of the resin layer and the olefin film separately obtained are brought into facing contact with each other and laminated (laminated). Next, the process release sheet is peeled off, the release sheet is brought into facing contact with the pressure-sensitive adhesive layer, and laminated (laminated). (3) A pressure-sensitive adhesive is applied to the olefin film surface of the laminate of the olefin film and the resin layer, and is cured by heating to form a pressure-sensitive adhesive layer. ).

Examples of the adhesive used here include general natural rubber, synthetic isoprene rubber, recycled rubber, styrene-butadiene rubber, polyisoprene rubber,
Rubber-based pressure-sensitive adhesives containing styrene-isoprene-styrene rubber or the like as a main component, and (meth) acrylic acid esters (C2-
An acrylic adhesive, a urethane-based adhesive, a silicone-based adhesive, and the like, mainly composed of a polymer obtained by copolymerizing monomers such as C12) with acrylic acid, methacrylic acid, acrylamide, vinyl acetate, and styrene. Can be used, applications,
An object having an appropriate adhesive force according to the material of the adherend can be selected.

The pressure-sensitive adhesive can be prepared by various methods known in the art, for example, a kiss coat method, a die coat method, a lip coat method, a comma coat method, a blade coat method, a bar coat method, etc. Utilizing the method, it can be applied to a release sheet, a process release sheet, or an olefin film as described above.

As the release sheet constituting the pressure-sensitive adhesive sheet of the present invention, or a process release sheet to be used in the production of the pressure-sensitive adhesive sheet, conventionally known ones can be used.

The pressure-sensitive adhesive sheet obtained in this manner was
Various decorations such as interior materials, building materials, various information boards, traffic signs, indoor and outdoor advertisements, signs, shutters, windows,
As a coloring and display material, furthermore, weather resistance, stain resistance,
It is used as a sheet that imparts various surface functions such as various resistances.

[0067]

Hereinafter, the present invention will be described in detail with reference to examples. All parts and percentages in the examples are parts by weight and percentage by weight. (Synthesis Examples A1 to A3) A monomer and a solvent shown in Table 1 were charged into a four-necked flask equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube based on a blending ratio (weight ratio). The temperature was raised to 80 ° C. while stirring under a nitrogen atmosphere, and azobisisobutyronitrile was added at 80% of the blending ratio shown in Table 1 to obtain a mixture.
The polymerization reaction was carried out for an hour, and then azobisisobutyronitrile was added at 20% of the mixing ratio (weight ratio) shown in Table 1, and the polymerization reaction was carried out for another 2 hours to obtain an acrylic polymer solution. Table 1 shows the weight average molecular weight, glass transition temperature, and hydroxyl value (only those having a functional group of a hydroxyl group) of the obtained acrylic polymer.

[0068]

[Table 1]

(Synthesis Example C1) A polyester having two or more hydroxyl groups (“Kuraray Polyol P-2010” manufactured by Kuraray Co., Ltd.) was placed in a four-necked flask equipped with a cooling pipe, a stirrer, a thermometer, a nitrogen introduction pipe, and a dropping funnel. ") 100 copies,
22 parts of isophorone diisocyanate and 122 parts of methyl ethyl ketone (MEK) were charged and heated to 80 ° C. while stirring under a nitrogen atmosphere, followed by heating and stirring for 1 hour.
An isocyanate prepolymer C1 having both ends was obtained with a weight average molecular weight of 2500.

(Production of Resin Composition Coating Liquid) The commercially available or synthesized acrylic polymer (A), compound (B), compound (C) and pigment shown in Table 2 were converted into the solid content ratio shown in Table 2. And toluene / butyl acetate =
50/50 (weight ratio) mixed solvent with solid concentration of 60%
To prepare a coating solution.

Examples 1 to 6 and Comparative Examples 1 to 6 (Production of a laminate of an olefin film or the like and a resin layer) In the combinations shown in Table 3, the obtained resin composition coating liquid was subjected to corona treatment on both sides. It is applied on a 60 μm-thick olefin film or polyethylene terephthalate film (hereinafter referred to as a PET film) having various physical properties with a comma coater so that the thickness after drying and curing becomes about 30 to 50 μm. Heat in oven for 2 minutes and dry,
The mixture was cured and aged at 40 ° C. for another week to prepare a laminated sheet of an olefin film and the like and a resin layer.

(Production of pressure-sensitive adhesive sheet) A pressure-sensitive adhesive solution (two-component curable acrylic pressure-sensitive adhesive / curing agent = 100 / 8.7) was
Using a comma coater, a 100 μm-thick release sheet (“TSM-110K” manufactured by Kite Kagaku Co., Ltd.) is applied so that the thickness after drying and curing becomes about 30 μm, and the film is placed in an oven at 80 ° C. It was heated and dried and cured for 2 minutes, and the resulting pressure-sensitive adhesive layer was laminated and bonded to the olefin film surface of a laminate sheet of an olefin film or the like and a resin layer to form a pressure-sensitive adhesive sheet. The obtained pressure-sensitive adhesive sheet was evaluated for elongation, cutting suitability, weather resistance, and stain resistance. The results are shown in Table 3.

[Physical Properties of Olefin Film and PET Film] <Yield Value> A No. 1 test piece of JIS K7113 was punched out of an olefin film or a PET film, and a tensile tester (“REO METER NRM-20” manufactured by Fudo Kogyo Co., Ltd.)
10J-CW "), range 10kg, speed 30
It was pulled under the condition of 0 mm / min, and the yield value was determined. <Tear strength>: A test piece was punched out of an olefin film or a PET film using JIS K6301 tear B type.
Tensile tester ("REO METER" manufactured by Fudo Industry Co., Ltd.)
NRM-2010J-CW ") and range 1
The test piece was pulled under the conditions of 0 kg and a speed of 300 mm / min, and the tear strength (rupture stress × range) was measured from the maximum load when the test piece was torn.

[Physical Properties of Resin Layer] A resin composition coating solution containing an acrylic polymer (A), a compound (B), a compound (C) and a pigment and having a solid content of 60% was adjusted to a thickness of 100 μm. Release sheet (“P” manufactured by Lintec Corporation
ET100X "), using a comma coater, so that the film thickness when dried is about 30 to 50 µm.
Drying and curing by heating in a gas oven at 2 ° C for 2 minutes,
After further aging at 25 ° C. for one week, the release sheet was peeled off to obtain a resin layer sheet for evaluating physical properties. <Storage elastic modulus Er and tan δ (loss elastic modulus Ei / storage elastic modulus Er)> Dynamic viscoelasticity measuring device (DVA manufactured by Shimadzu Corporation)
300), while applying a 10 Hz vibration to the resin layer sheet obtained as described above by tension, the temperature is raised from -150 ° C.
The temperature is raised to 150 ° C at 5 ° C / min, and the storage modulus Er and tan δ (loss modulus Ei / storage modulus Er) are increased every 1 ° C.
And the storage elastic modulus Er and tan at 0 ° C. and 50 ° C.
δ and the storage modulus Er at 80 ° C. were determined.

[Evaluation of pressure-sensitive adhesive sheet] <Extensibility>: A test piece having a width of 1 cm and a length of 5 cm was cut out from the pressure-sensitive adhesive sheet, and a tensile tester ("REO METER NRM-2010J-CW" manufactured by Fudo Kogyo KK)
And stretched under the conditions of a range of 10 kg and a speed of 300 mm / min, and elongation until at least one of the olefin film or the resin layer of the base material forming the test piece or the resin layer is broken (the length of the original test piece) (Extended length with respect to).

<Cutability test>: The pressure-sensitive adhesive sheet was cut into various patterns using a cutting tester (“CM24” manufactured by Roland), and the cutting accuracy was visually observed in five stages (5: excellent, 4). : Good, 3:
Acceptable, 2: bad, 1: extremely poor).

<Weather resistance test>: JI for adhesive sheet
An ultraviolet carbon arc lamp type weather resistance tester (manufactured by Suga Test Instruments Co., Ltd.) specified by SB7750, according to JIS K540
0 A test in accordance with 6.17 was performed, and the appearance change after 1000 hours was visually observed in five stages (5: no change, 4:
(Slight change, 3: change, 2: deterioration, 1: remarkable deterioration).

<Stain resistance test>: Peel off the release sheet of the adhesive sheet, affix it to a stainless steel plate, and incline 45
° fixed on a slope and exposed outdoors for one month. The degree of dirt on the exposed adhesive sheet was visually evaluated in five stages (5: excellent, 4:
Good, 3: acceptable, 2: poor, 1: extremely poor).

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

According to the present invention, a sheet having toughness and extensibility, and excellent cutting suitability, weather resistance and stain resistance can be obtained.

[0082]

[Brief description of the drawings]

FIG. 1 shows the results of dynamic viscoelasticity measurement of a resin layer sheet used in Example 1.

FIG. 2 shows a result of dynamic viscoelasticity measurement of a resin layer sheet used in Comparative Example 3.

FIG. 3 shows the results of dynamic viscoelasticity measurement of the resin layer sheet used in Comparative Example 4.

Claims (5)

[Claims] 1. A resin layer, an olefin film, and an adhesive
Layer and release sheet are sequentially laminated.
The olefin film has a yield value of 0.7 to 25 ° C.
2.2kg / mm^TwoWith a tear strength of 300 to 900 g and a thickness of 30 to 90 μm.
The resin layer has a functional group capable of reacting with an isocyanate group.
Acrylic polymer having two or more (A) and isocyanate
Polyethers having two or more functional groups that can react with
, Polyester, polycarbonate, polybutadiene
At least one compound selected from (B) and two or more
An isocyanate compound having an isocyanate group (C) and
Containing a reaction product having a glass transition temperature of 50 to 120 ° C.
Yes, storage elasticity Er at 0 ° C. is 7.5 × 10⁸~ 5.0 × 10
⁹Pa, tanδ is 7.0 × 10^-2~ 2.5 × 10^-1At 50 ° C
Storage elasticity Er is 1.0 × 10⁸~ 2.0 × 10⁹Pa, tanδ is 1.0
× 10 ^-1~ 6.0 × 10^-1And storage elasticity at 80 ° C
Rate Er 8.0 × 10⁶~ 1.3 × 10⁸Pa, the thickness of the resin layer
A pressure-sensitive adhesive sheet having a thickness of 20 to 100 μm. 2. The pressure-sensitive adhesive sheet according to claim 1, wherein the resin layer is a colored resin layer further containing a colorant. 3. An olefin film having a yield value of 0.7 to 2.2 kg / mm ^{2 at} 25 ° C., a tear strength of 300 to 900 g, and a thickness of 30 to 90 μm, on which one or more functional groups capable of reacting with isocyanate groups are provided. Acrylic polymer having (A), having two or more functional groups capable of reacting with isocyanate groups, polyether, polyester, polycarbonate, at least one compound selected from polybutadiene (B), and having two or more isocyanate groups A resin composition containing an isocyanate compound (C) is applied and cured by heating, and has a glass transition temperature of 50 to
120 ° C., and the storage elastic modulus Er at 0 ° C. is 7.5 × 10 ⁸ to
5.0 × 10 ⁹ Pa, tan δ is 7.0 × 10 ^{-2 to} 2.5 × 10 ^-1 and 50
Storage elastic modulus Er at 1.0 ° C. is 1.0 × 10 ^{8 to} 2.0 × 10 ⁹ Pa, ta
nδ is 1.0 × 10 ^{−1 to} 6.0 × 10 ⁻¹ , and the storage modulus Er at 80 ° C. is 8.0 × 10 ^{6 to} 1.3 × 10 ⁸ Pa, and the resin layer has a thickness of 20 to 100 μm. And then sequentially laminating a pressure-sensitive adhesive layer and a release sheet on the other surface of the olefin film. 4. The method for producing a pressure-sensitive adhesive sheet according to claim 3, wherein a pressure-sensitive adhesive layer separately formed on one surface of a release sheet is laminated on the other surface of the olefin film obtained by laminating the resin layer. 5. The method for producing a pressure-sensitive adhesive sheet according to claim 3, wherein the resin composition contains a coloring agent.