JP3050702B2 - Composite marking sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite marking sheet having a transparent resin layer, a colored resin layer and an adhesive layer. The present invention relates to a composite marking sheet that can be beautifully finished.

[0002]

2. Description of the Related Art As a method of coloring a metal surface to enhance the decorativeness (design) of the surface, there has been conventionally known a method of applying a paint having a desired color to a metal surface. Have been. By applying the paint to the metal surface in this way, the metal surface is prevented from rusting and its decorativeness is enhanced.

[0003] However, there has been a problem that, for example, a paint applied to a metal surface deteriorates with time, cracks and the like, peels off from the metal surface, and makes it impossible to make use of the luster of the undercoat peculiar to the metal surface. .

[0004] Further, in order to make use of the luster of the underlayer on the metal surface, it is necessary to apply a thin coating of paint.
There has been a problem that coating unevenness occurs and the scratch resistance and weather resistance are poor.

On the other hand, there is a method in which a coloring film is applied to a metal surface to make up for the weakness of the paint. This method comprises an outer wall material, an inner wall material, a roof material, a ceiling material, and the like made of a metal such as stainless steel, aluminum, and iron. Building materials, civil engineering materials such as tunnel inner wall materials and road side wall materials, and household goods such as refrigerators, air conditioners, range hoods, bath units, and toilets.

However, the surface of the metal on which the colored film is adhered is completely concealed by the colored film, so that the gloss of the metal surface cannot be fully utilized, and the surface of the colored film becomes dusty. There is a problem that the surface is not easily retained for a long time because the surface is easily contaminated by dust and the like and the surface is easily damaged.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an excellent weather resistance, abrasion resistance and stain resistance, and to impart a glossy color to the surface without unevenness of color by utilizing the gloss of the metal surface. It is to provide a composite marking sheet that can be finished.

[0008]

The present inventors have conducted various studies on a coloring method which can impart weather resistance, scratch resistance and stain resistance, and can make use of the gloss of the underlayer. It has been found that the above problem can be solved by applying a colored sheet having the same to a metal surface.

The present invention has been made on the basis of the above findings, and has a thickness of 5 which transmits 90 to 95% of light having a wavelength of 550 nm and substantially blocks light in a wavelength region of at least 360 nm and below. A transparent crosslinked acrylic or crosslinked urethane resin layer having a thickness of 20 to 200 μm and a colorant containing 0.01 to 200% by weight of a colorant, which is covered with the transparent resin layer; An object of the present invention is to provide a composite marking sheet having an adhesive layer applied to the colored resin layer and having a thickness of 20 to 100 μm.

[0010] The transparent resin layer in the present invention has a transparency of transmitting 90-95%, preferably 91-94%, more preferably 91-93% of light having a wavelength of 500 nm.
When the transmittance is less than 90%, it becomes difficult to visually recognize the coloring state of the colored resin layer described later, and when the transmittance exceeds 95%, there are places where it is substantially difficult to prepare a resin layer having such transparency.

[0011] The transparent resin layer is formed as a layer that substantially blocks at least a light beam having a wavelength of 360 nm or less, and more preferably absorbs ultraviolet light having a wavelength of 360 nm or less and transmits ultraviolet light. By blocking or shielding 80%, preferably 90%, more preferably 100%, the colored resin layer described below is prevented from being deteriorated by ultraviolet rays.

Further, the transparent resin layer has a thickness of 5 to 5.
It is 100 μm, preferably 10 to 30 μm, more preferably 15 to 25 μm. If the film thickness is less than 5 μm, 36
It becomes difficult to protect the colored resin layer described below from light having a wavelength of 0 nm,
If it exceeds 100 μm, it becomes difficult to secure the above-mentioned transmittance, and there is a possibility that the cost may increase.

The synthetic resin forming the transparent resin layer is not particularly limited as long as it is a synthetic resin having the above-mentioned transmittance. Examples of such a synthetic resin include a crosslinked urethane resin and a crosslinked acrylic resin. No. Examples of the urethane-based resin include polyurethane, a mixture of polyurethane and another resin component, and a modified polyurethane.

The crosslinked polyurethane is not particularly limited, and any one can be used. Other resin components to be mixed with the polyurethane include, for example, phenol resin, furan resin, urea resin, melamine resin, guanamine resin, polyester resin, epoxy resin, silicon resin, polyimide resin, vinyl chloride resin, chloride resin Vilinidene resin, vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, alkyd resin, polystyrene, A
Examples include S resin, ABS resin, AXS resin, methacrylic resin, acrylate resin, EVA resin, polyamide, cellulose resin, and petroleum resin.

Examples of the modified polyurethane include a graft polymer obtained by the action of a polymerization component (modified component), and a mixture or reaction product of the graft polymer and other components. As the polymerization component,
For example, alkyl (meth) acrylates, alkylamino (meth) acrylates, oxyalkyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N-vinylpyrrolidone, acrylonitrile, styrene And vinyl monomers such as acrylamide, vinyltoluene and vinyl acetate.

When the modified product is a graft polymer, other components to be mixed or reacted with the graft polymer include, for example, phenol resin, furan resin, urea resin, melamine resin, guanamine resin, polyester resin , Epoxy resin, silicon resin, polyimide resin,
Vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, alkyd resin, polystyrene, AS resin, ABS resin, A
XS resin, methacrylic resin, acrylate resin,
EVA resin, polyamide, cellulose resin and petroleum resin can be mentioned.

Among the above-mentioned modified polyurethanes, particularly effective ones are those comprising a graft polymer obtained by grafting a polyurethane and an amino resin-based cross-linking agent. Examples of the chain include those in which the chain is formed of a copolymer of a mixed monomer containing at least a hydroxyl group-containing α-β ethylene monomer and a carboxy group-containing α-β ethylene monomer.

The urethane resin (modified product of polyurethane or the like) will be described in more detail.
Polyurethane which is generally used in the fields of paints, moldings, printing inks and the like, is synthesized from polyesterdiol and diisocyanate, and has a molecular weight of 5,000 to 100. 000,
Preferably, it is in the range of 8,000 to 50,000.
Those having 2-3, preferably 0.5-2 α-β ethylenically unsaturated bonds are preferred.

As a method for introducing an α-β ethylenically unsaturated bond into the above-mentioned polyurethane, the following method is used.
When synthesizing the polyester diol, a method of condensing an appropriate amount of maleic acid, itaconic acid or the like as a part of the raw material can be used.

Examples of the polyol used for the production of the polyurethane include the polyester having an α-β ethylenically unsaturated bond, the polyester polyol having no α-β ethylenic unsaturated bond, and the polyol Such as caprolactone diol, polyetherdiol, polycarbonate diol, ethylene glycol, propylene glycol, butanediol, hexanediol, cyclohexanedimethanol, and neopentyl glycol; Other bifunctional alcohols may be used as a mixture.

When the molecular weight is increased, tri- or higher-functional alcohols such as trimethylolpropane, trimethylolethane and pentaerythritol may be partially used. However, it is needless to say that the amount must be set within a technically allowable range in consideration of gelation by three-dimensional formation.

Examples of the isocyanate used for producing the above polyurethane include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
And diisocyanates generally used, such as hexamethylene diisocyanate and isophorone diisocyanate, which are preferably non-yellowing isocyanates. These may be used alone or in combination of two or more. can do.

In the production of polyurethane, monoalcohols such as methanol, ethanol and propanol, monoamines such as diethylamine, dipropylamine and dibutylamine, monoethanolamine, diethanolamine, etc. Alkanolamines such as monopropanolamine and dipropanolamine can also be used as chain extenders.

In the case of synthesizing a graft chain constituting the above graft polymer, a hydroxyl group-containing α-β ethylene monomer can be mixed and used. Examples of the -β ethylene-based monomer include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; and those of these hydroxyalkyl (meth) acrylates. Caprolactone modified product (trade name: Praxel FM Series Daicel Chemical Industries, Ltd.), (meth) acrylic acid ester of polyetherdiol, ie, hydroxypolyalkylene ether terglycol mono (meth) acrylate And the like.

The above-mentioned hydroxyl group-containing α-β ethylene monomer is used in an amount of 5 to 80 mol%, preferably 10 to 5 mol%, in the above-mentioned mixed monomer in order to make the crosslinked structure described in detail later uniform.
It is preferable to contain it in a range of 0 mol%.

Examples of the carboxy group-containing α-β ethylene monomer contained in the above-mentioned mixed monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid and the like. From the viewpoint of improving the compatibility with the crosslinking agent and forming a uniform clear film, the carboxyl group-containing α-β ethylene-based monomer is used in an amount of 1 to 40 mol%, preferably 2 to 40 mol%, in the mixed monomer. It is preferable to contain it in the range of 20 mol%.

Further, in addition to the above-mentioned two essential monomers, monomers generally used in the production of an acrylic copolymer, such as methyl (meth) acrylate and ethyl (meth) Acrylate, propyl (meth)
Alkyl (meth) acrylates such as acrylate and butyl (meth) acrylate, alkylamino (meth) acrylates such as dimethylaminoethyl (meth) acrylate, and oxyalkyl phosphate (meth) Acrylate,
One or more of dicyclopentenyl (meth) acrylate, N-vinylpyrrolidone, acrylonitrile, styrene, acrylamide, vinyltoluene, vinyl acetate and the like can be mixed as necessary.

The mixed monomer to be reacted with the polyurethane or the like is preferably up to 1: 1 from the viewpoint of maintaining the toughness of the coating film.

However, if the amount is too small, the compatibility with the cross-linking agent is reduced and the formation of the clear film is hindered. Therefore, the amount of the mixed monomer is 2 parts by weight or more with respect to 100 parts by weight of the polyurethane or the like. Preferably, it is at least 4 parts by weight. α-β ethylenically unsaturated bond

The grafting reaction of the polyurethane or the like can be carried out by causing a mixture of the polyurethane or the like and the above-mentioned mixed monomer to carry out polymerization in the presence of a reaction catalyst. Reaction catalysts that can be used at that time include, for example, azobisisobutyronitrile, benzoyl peroxide, digital butyl peroxide,
Examples thereof include those used in ordinary radical polymerization reactions such as cumene hydroperoxide.

In the production of the above-mentioned polyurethane and graft polymer used as an intermediate material of the urethane-based resin, it is possible to appropriately adjust the viscosity to one or more kinds of organic solvents. It goes without saying that you can do it.

In order to produce the urethane-based resin,
Examples of the amino resin-based cross-linking agent used together with the graft polymer include amino resin derivatives obtained by subjecting an amino resin such as a melamine resin, a benzoguanamine resin, or a urea resin to methylolation, methoxylation, or butoxylation. be able to.

The mixing ratio of the graft polymer and the amino resin-based cross-linking agent is preferably from the viewpoint of maintaining a balance between improvement in water resistance and toughness of the coating film.
The amount of the crosslinking agent is preferably 5 to 60 parts by weight, more preferably 10 to 40 parts by weight, based on 00 parts by weight.

In preparing the urethane resin, in addition to the graft polymer and the crosslinking agent, a diluting solvent, a leveling agent, and the like, which are generally used in the coating technology field, are added. Needless to say, it can be prepared by adding a curing catalyst or the like.

As a method for forming the present resin layer using the urethane-based resin, for example, a solution of the urethane-based resin is added, and a desired component is added thereto to prepare a polymer solution. Commonly used coating methods such as spray coating, curtain floor coating, roll coater coating, doctor knife coating, dip coating, flow coating, brush coating and the like can be mentioned.

The cross-linked acrylic resin forming the transparent resin layer is, for example, at least 50% by weight or more, preferably 80% by weight or more of polyacrylic resin.
And / or polymethacrylate as a component.

As the polyacrylate, for example,
Monomers of acrylate, methyl acrylate, propyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, etc.
Examples of the polymethacrylate include, for example, those obtained by polymerizing methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate as a monomer, and the like. Can be mentioned.

The cross-linkable acrylic or urethane-based transparent resin layer is preferably a resin having an appropriate degree of cross-linking, for example, preferably 70% or more, particularly preferably 80% or more, more preferably 80% or more in terms of gel fraction. Is 90% or more.

If the gel fraction is too low, the blocking resistance, solvent resistance, stain resistance, workability and weather resistance tend to be inferior, making it difficult to ensure the excellent function of the product of the present invention. Therefore, it is preferable that the gel fraction is high, but it is not necessary to set the gel fraction to 100%. Because the transparent resin layer originally contains additives such as an ultraviolet absorber not included in the constituents of the cross-linkable resin, and in order to increase the gel fraction of these additives,
This is because when chemically bonded to the crosslinked resin, the performance may be rather deteriorated.

The transparent resin layer has a thickness of 0.1 to 10
The above-mentioned blocking properties are exhibited by containing an ultraviolet absorber in an amount of 0.5% by weight, preferably 0.5 to 8% by weight. The ultraviolet absorber is not particularly limited as long as it is conventionally known. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based and cyanoacrylic-based.
G-type is preferred. Examples of the benzophenone type include, for example, 2,3'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone Can be mentioned.

Examples of the above-mentioned benzotriazole-based compounds include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) -5 , 6-dichlorobenzotriazole), 2-
(2'-hydroxy-5'-t-butylphenyl), benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t-butylphenyl) benzotriazole, 2- (2'- Hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole and 2- (2'-hydroxy-5'-phenylphenyl)-
5-chlorobenzotriazole, 2- (2'-hydroxy-3 ',
5'-di-t-butylphenyl) -5-chlorolobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazo- ,

2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- {2'-hydroxy-3 '-(3 ", 4", 5 ", 6"-
Tetrahydrophthalimidomethyl) -5'-methylphenyl {benzotriazole, 2- {2-hydroxy-3,5-bis
(α, α'-dimethylbenzyl) phenyl} -2-hydroxybenzotriazole and the like can be mentioned. Particularly, as the ultraviolet absorber, those represented by the following general formula are preferable.

[0043]

Embedded image

In the above formula, R ₁ and R ₂ are the same or different and each represents a lower or higher alkyl group, particularly a branched lower alkyl group or an aryl group, especially a phenyl group, and furthermore an alkyl group. The aryl group may have a functional group such as a hydroxyl group or an amino group, and X is a type represented by a hydrogen atom or a halogen atom, particularly a chlorine atom.

Examples of the cyanoacrylates include ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate and the like. Can be mentioned.

Further, the colored resin layer in the present invention is covered with the above-mentioned transparent resin layer and protected from ultraviolet rays having a wavelength of 360 nm or less as described above. The colored resin layer has a thickness of 20 to 200 μm, preferably 25 to 1 μm.
It is 00 μm, more preferably 30 to 75 μm. When the film thickness is less than 20 μm, the strength of the colored resin layer is weakened, the colored resin layer is easily broken, and the attaching work becomes difficult, and
If it exceeds 200 μm, the flexibility of the colored resin layer may be reduced and the workability may be impaired, and the cost may be increased, which is not preferable, and if the film thickness is out of the above range, color unevenness may occur. is there.

Further, the colored resin layer may be 0.01-20.
It contains 0% by weight, preferably 0.05 to 100% by weight, more preferably 0.1 to 50% by weight of colorant.
If the content is less than 0.01% by weight, the coloring property of the colored resin layer is inferior, and the significance of coloring is unfavorably reduced.
If the content is more than 10% by weight, the physical properties of the colored resin layer are inferior, and it is difficult to obtain beautiful decorativeness.

As the colorant, any colorant can be used, but a weather-resistant colorant that can be used for a long period of time is preferable. Specifically, The Society of Dyers
Color Index 3rd Editi published by andColourists
on (1971) and Supplements (1975). The colorant names shown below are based on the Color Index Generic Name specified in the same book. For example, Y-1
CIPigment Yellow1 and O means orange (Orang
e), R is red, V is purple (Violet), B is blue (Blu
e), C is green (Green), Br is brown (Brown), Bk is black
(Black) and W represent white.

As the color of the colorant, any color tone such as yellow, orange, red, purple, blue, green, brown, black and white can be used. Hereinafter, each preferred coloring agent will be specifically exemplified. Preferred examples of the yellow colorant include, for example, azo pigments, condensed polycyclic pigments, metal complex salt pigments, and inorganic pigments.

Preferred azo pigments include, for example,
Insoluble monoazo pigments (Y-97, Y-116, Y-120, Y-151, Y-154),
Disazo pigments (Y-81, Y-83, Y-155), condensed azo pigments (Y-93, Y
-94, Y-95, Y-128). Preferred examples of the condensed polycyclic pigment include, for example, anthraquinone pigments (Y-24, Y-108, Y-147, Y-123, Y-99), isoindolinone pigments (Y-109, Y-110, Y-173), isoindoline pigments (Y-13
9), quinophthalone pigments (Y-138), and as preferred metal complex salt-based pigments, for example, the same azomethine pigments (Y-117, Y-129), nickel nitroso pigments (Y-138)
153) and nickel azo pigment (G-10).
Further, as preferred inorganic pigments, for example, iron oxide yellow- (Y-42), titanium-antimony-nickel oxide
(Y-53) and the like.

Preferred orange pigments include, for example, azo pigments and condensed polycyclic pigments.
As preferred azo pigments, for example, insoluble monoazo pigments (O-36, O-5, O-38, O-60, O-62), disazo pigments
(O-34) and condensed azo pigments (O-31).
Further, as preferred condensed polycyclic pigments, for example, perylene pigments (O-43), anthraquinone pigments (O-40, O-5
1), isoindolinone pigments (O-42) and quinacridone pigments (O-48, O-49).

Examples of preferred red pigments include azo pigments, condensed polycyclic pigments, and inorganic pigments.

Preferred azo pigments include, for example,
Insoluble monoazo pigments (R-2, R-6, R-7, R-9, R-10, R-12, R-1
4, R-112, R-146, R-147, R-170, R-171, R-175, R-185, R-187,
R-188, R-208), azo lake pigments (R-52: 2, R-115, R-151,
R-243), condensed azo pigments (R-144, R-166, R-214, R-220, R-2
21, R-242), disazo pigments (R-38, R-37),

Preferred examples of the condensed polycyclic pigment include anthraquinone pigments (R-168, R-177, R-21).
6), thioindigo pigment (R-88), perinone pigment (R-19
4), perylene pigments (R-123, R-149, R-178, R-179, R-190, R
-224), quinacridone pigments (V-19, R-122, R-202, R-207, R
-209, R-206).

Further, a diketopyrrolopyrrol-based pigment (Irgadine DPP Red BO manufactured by Ciba-Geigy) is used as a new pigment.
Preferable inorganic pigments include red iron oxide (red iron oxide R-101), zinc / iron oxide
(R-225) and the like.

Preferred violet pigments include, for example, azo pigments, condensed polycyclic pigments, and inorganic pigments.

Preferred azo pigments include, for example,
Monoazo pigments (V-50) and the like can be mentioned, and preferred condensed polycyclic pigments include, for example, perylene pigments
(V-29), anthraquinone pigments (V-31, V-33), thioindigo pigments (V-38, V-36), quinacridone pigments (V-19),
Dioxazine pigments (V-23, V-37) can be mentioned,
Further, as preferred inorganic pigments, for example, cobalt phosphate (V-14: 1), ferrolite violet pigment
(V-18), cobalt lithium vanadium phosphate
And pigment (V-47).

Examples of preferred blue pigments include phthalocyanine pigments, condensed polycyclic pigments, and inorganic pigments.

Examples of preferred phthalocyanine pigments include α-type copper phthalocyanine pigments (B-15: 1, B-1
5: 2), β-type copper phthalocyanine pigment (B-15: 3, B-15: 4) ε
Type phthalocyanine pigments (B-15: 6), and metal-free phthalocyanine pigments (B-16) .Examples of preferable condensed polycyclic pigments include, for example, indatron pigments (B-60, B-21, B-22, B-64),

Preferred inorganic pigments include, for example, dark blue (B-27), ultramarine blue (B-29), cobalt-aluminum oxide pigment (B-28), and cobalt-chromium-aluminum oxide pigment. Pigment (B-36) and the like can be mentioned.

Examples of preferred green pigments include phthalocyanine pigments, condensed polycyclic pigments, and inorganic pigments.

Examples of preferable phthalocyanine pigments include medium chlorinated copper phthalocyanine pigment (G-37),
High chlorobrominated copper phthalocyanine pigments (G-7), high chlorobrominated copper phthalocyanine pigments (G-36) and the like can be cited.Preferred condensed polycyclic pigments include, for example, -N (G-47), and preferred inorganic pigments include, for example, chromium oxide pigments (G-17),
Cobalt-titanium-nickel-zinc oxide pigment (G-1
9), and a cobalt-titanium pigment (G-50).

Examples of preferable brown pigments include azo pigments, condensed polycyclic pigments, and inorganic pigments.

Preferred azo pigments include, for example,
Monoazo pigment _{(B r -25, B r -32} ), metal complex salt azo pigments (B
_r -5, B _r -2), there may be mentioned condensed azo pigments (B _r -23), Preferred pigments condensed polycyclic, for example, anthraquinone pigments (B _r -28), perylene mention may be made of pigment (B _r -26),

Preferred inorganic pigments include, for example,
Iron oxide pigments ( _Br- 6), iron-chromium oxide pigments ( _Br- 2
9), zinc - can be mentioned iron oxide pigment (B _r -31). Further, preferred black pigment, there are organic pigments, inorganic pigments, preferred pigments organic, for example, aniline black (B _k -1), cited perylene black (B _k -31), etc. It is possible,

[0066] Preferred examples of inorganic pigments, for example, mosquitoes - carbon black (B _k -31), mosquito - carbon black (B _k
-7), mosquito - carbon black (B _k -9), iron black (B _k -11), cobalt oxide pigment (B _k -13), and the like.

Preferred white pigments are inorganic pigments such as zinc white (W-4), zinc sulfide (W-7), titanium dioxide (W-6) and calcium carbonate (W-4). -18),
Cray (W-19), barium sulfate (W-21), alumina white
(W-24), silica (W-27), muscovite (W-20), tank (W-26) and the like.

Other particularly preferred pigments include, for example, titanium dioxide-coated mica, which is known as a pearl pigment, preferably having a particle size of 2 to 200 μm, more preferably 4 to 150 μm. Particularly preferably, it is 5 to 100 μm. Further, the titanium oxide of the coating layer is preferably of a rutile type from the viewpoint of weather resistance.

Further, it may be colored with a coloring agent such as iron oxide or the like, or may show an interference color.
Tone or milk tone.

Commercial products include those manufactured by Merck, those manufactured by Irio Zinmar, and highlights. The colored resin layer may contain mica and aluminum powder in addition to the pigment, as long as the transparency and weather resistance are not affected.

The synthetic resin formed by the colored resin layer is preferably a vinyl chloride resin. The vinyl chloride resin is not particularly limited as long as it is a resin composition containing a single vinyl chloride resin or a vinyl chloride resin containing a copolymer component as a resin component. The resin composition may contain various additives such as a stabilizer, an antioxidant, an ultraviolet absorber, a modified resin, and a coloring agent as needed within a range satisfying the above conditions. Particularly, those having weather resistance are preferable.

The following resin compositions (A) to (A)
(C) for molding semi-rigid vinyl chloride resin,
A resin composition having a yield stress of 1 to 6 kg / mm ² is preferable.

(A) 100 parts by weight of a vinyl chloride resin containing 0 to about 20% by weight of a copolymer component,

(B) about 1 to about 20 parts by weight of a liquid polyester plasticizer having a number average molecular weight (Mn) of about 1,500 or more, and 0 to about 30 parts by weight of another plasticizer for vinyl chloride resin;

(C) In the main chain consisting of ethylene / vinyl ester of saturated carboxylic acid / carbon monoxide copolymer resin, It comprises about 45 to about 350% by weight based on the weight.

The vinyl chloride resin (A) is not particularly limited, and may be appropriately selected and used as long as it is generally used for molding. As the vinyl chloride resin, in addition to a polymer of vinyl chloride alone, about 20% by weight or less, preferably about 10% by weight or less, particularly preferably about 6% by weight or less.
It may be a copolymer containing a copolymer component of not more than weight%. Such a copolymer component is a vinyl chloride monomer.
It is not particularly limited as long as it is a vinyl monomer copolymerizable with the above.

The content of the liquid polyester plasticizer (B) is about 1 to 20 parts by weight, preferably about 1 to about 15 parts by weight, based on 100 parts by weight of the vinyl chloride resin (A). More preferably about 2 to about 10 parts by weight, and the content of the other vinyl chloride resin plasticizer (B) is 0 to about 10 parts by weight, preferably 1 to 100 parts by weight of the vinyl chloride resin. To 8 parts by weight, more preferably 2 to 5 parts by weight.

Examples of the liquid polyester plasticizer include:
The number average molecular weight (Mn) is about 1,500 or more, preferably about 1,500 to about 6,000, more preferably about 1,500
To about 4,000, more preferably from about 2,000 to about 4.0.
00.

Examples of the liquid polyester plasticizer include a liquid polyester derived from a dibasic acid having 4 to 15 carbon atoms and a divalent alcohol having 2 to 20 carbon atoms. Acid, phthalic acid, maleic acid, propylene glycol
And liquid polyester derived from 1 to 3 kinds selected from propylene glycol, dipropylene glycol, hexanediol and butanediol.

As a preferable plasticizer for a vinyl chloride resin that can be used in combination, for example, a plasticizer such as a phthalate ester or an epoxy compound can be exemplified.

The content of the ethylene / vinyl ester resin (C) is about 45 to 350% by weight, preferably about 50 to about 300% by weight, based on the total amount of the plasticizer (B).

The copolymer resin (C) and its production method are known (for example, JP-B-55-50063; JP-A-48-26228), and further commercially available (for example, trade name; Elvaloy).・ Dupont, USA).

The vinyl used in the production of the resin (C)
As the ester, for example, vinyl acetate, propion
Acid esters can be mentioned. The above resin composition
The yield stress of the object is 1-6kg / mm^Two, Preferably 1-5 kg / m
m^Two , More preferably 1.2 to 4.5 kg / mm^TwoIt is.

The colorant layer has a thickness of 500 to 700 nm.
It is preferable that the maximum transmittance of the light having the wavelength of 20 to 93% and the minimum transmittance have a transparency of half or more of the maximum transmittance. If the maximum transmittance is less than 20%, the reflected light from the substrate of the adherend is difficult to recognize, which is not desirable in terms of design, and if the minimum transmittance is less than half of the maximum transmittance, the substrate of the adherend is undesired. In combination with the reflected light from the light, the color is overemphasized and the sense of quality is impaired, which is not desirable in design.

The adhesive layer in the present invention is formed so as to be applied to the colored resin layer so that the colored resin layer and the transparent resin layer can be bonded to an adherend as a marking sheet. . In other words, the colored resin layer is interposed between the transparent resin layer and the adhesive layer. The adhesive layer has a thickness of 20 to 100 μm, preferably 30 to 70 μm, more preferably 30 to 45 μm.
It is. If the film thickness is less than 20 μm,
In addition, the workability such as bending of the adherend is deteriorated due to peeling off, and it is not preferable. In addition, when the film thickness exceeds 100 μm, the adhesive strength becomes too high, the adhesiveness is poor, and the cost may increase. .

The adhesive strength of the above-mentioned adhesive layer was measured by a peeling test using a Tensilon tensile tester after bonding to an adherend with the composite sheet having a width of 25.4 mm and leaving it to stand for 24 hours.
The measured value when peeling back by 0 ゜ is 1.0kg / 25.
Those having a diameter of 4 mm or more are preferred. The bond strength is 1.0k
If the thickness is less than g / 25.4 mm, there is a possibility that the sheet may be peeled off from the adherend when the adherend on which the composite marking sheet is adhered is bent and formed.

Examples of the material for forming the adhesive layer include a two-part adhesive, a pressure-sensitive adhesive, a heat-sensitive adhesive or an adhesive. -Considering the presence or absence of the jing time, a pressure-sensitive adhesive is preferable. Such an adhesive layer is
Although not particularly limited, an acrylic resin is preferred in terms of weather resistance, transparency, yellowing resistance, and the like.

The main component of the monomer in the acrylic resin is preferably an alkyl (meth) acrylate having 4 to 14 carbon atoms in the alkyl group. If the number of carbon atoms deviates from the range of 4 to 14, the resin layer may be hard and may have poor flexibility. Further, it is preferable that the main component of the monomer in the acrylic copolymer is 50 mol% or more. If the proportion is less than 50 mol%, the acrylic resin becomes hard and may have poor flexibility.

Examples of the alkyl (meth) acrylate include n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methylpentyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. ) Acrylate, lauryl (meth) acrylate and the like can be mentioned.

Examples of monomers of other components copolymerized with the acrylic resin include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, and styrene. Can be.

The functional groups of monomers that can be introduced into these resins include carboxyl groups such as (meth) acrylic acid and itaconic acid, hydroxy (meth) acrylate, n-
Examples thereof include a hydroxyl group such as methylol acrylamide and an epoxy group such as glycidyl (meth) acrylate. In the present invention, a urethane crosslinking method in which a general polyisocyanate crosslinking agent is combined is employed. Preferably, in this case, a carboxyl group and a hydroxyl group are preferred.

Examples of the solvent used for copolymerizing these monomers include, for example, benzene, toluene,
Conventionally known solvents such as xylene, methyl cellosolve, ethyl cellosolve, ethyl acetate, and methanol can be used alone or as a mixture of two or more thereof. Examples of the polymerization initiator include azobisisobutyrate. An azo initiator such as lonitrile and a peroxide initiator such as di-t-butyl peroxide can be used.

The weight average molecular weight (M
w) is preferably 200,000 to 1,000,000, more preferably 400,000 to 800,000. Such a molecular weight can be adjusted by the amount of the polymerization initiator or by adding a chain transfer agent.

Incidentally, additives such as a tackifier, an ultraviolet absorber, a light stabilizer and an antioxidant can be added to the acrylic resin as required. As a crosslinking agent for the acrylic resin thus obtained, polyisocyanate
By adding 0.1 to 1 gram equivalent, preferably 0.3 to 0.7 gram equivalent to the functional group, the adhesive force to the adherend can be strengthened. At the time of this crosslinking reaction, a reaction accelerator can be added as necessary.

Thus, the composite marking sheet of the present invention is obtained by attaching a metal plate such as stainless steel, aluminum, iron, or alloy, preferably a metal plate such as stainless steel, aluminum, particularly stainless steel, to the outer wall material, Building materials such as inner wall materials, roof materials, ceiling materials, stainless steel sashes, tunnel inner wall materials,
It can be suitably used when decorating the surface of molded articles such as civil engineering materials such as road side wall materials, household goods such as refrigerators, air conditioners, resin hoods, bath units, and toilets.

Therefore, in each of the above molded articles decorated with the composite marking sheet of the present invention, the colored resin layer is protected by the transparent resin layer, so that it is excellent in weather resistance and abrasion resistance. -Irradiation light transmitted through the base is reflected from the underground, and the colored resin layer without color unevenness is expressed as glossy color in combination with the metallic luster of the base of the molded product, the surface is beautiful and the design is excellent It becomes something.

[0097]

The present invention will be specifically described below with reference to the following examples. It goes without saying that the present invention is not limited to the following examples.

In this embodiment, a composite marking sheet shown in FIG. 1 was prepared. This composite marking sheet 10
As shown in FIG. 1, a transparent resin layer 11, a colored resin layer 12,
It has an adhesive layer 13 and a release sheet layer 14. Then, the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in the present composite marking sheet 10 were formed using resin solutions prepared as follows.

(I) Preparation of transparent resin solution for transparent resin layer

(1) Preparation of transparent resin solution a 30 parts by weight of methyl acrylate, butyl acrylate 3
9 parts by weight, 1 part by weight of acrylic acid, 30 parts by weight of 2-hydroxyethyl acrylate having a weight average molecular weight of 1500
0 (converted to styrene by GPC method), number average molecular weight is 7
200 parts by weight of 200 polymer, ultraviolet absorber
4 parts by weight of Sorb 704 (manufactured by Shiroishi Calcium Co., Ltd.), 3 parts by weight of Tinuvin 234 (manufactured by Ciba Geigy), 3 parts by weight of light stabilizer Sanol LS-765 (manufactured by Sankyo Co., Ltd.), silicone System additive L-7500 (manufactured by Union Carbide) 0.0
4 parts by weight, 90 parts by weight of toluene and 75 parts by weight of a crosslinking agent Colonate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added to prepare a uniform transparent resin solution a.

(2) Preparation of Transparent Resin Solution b Polycarbonate urethane resin solution Resamine LU-4
187 (manufactured by Dainichi Seika Co., Ltd.), 100 parts by weight, 2 parts by weight of ultraviolet absorber Tinuvin 213 (benzotriazole-based ultraviolet absorber: manufactured by Ciba Geigy), and Seesorb 704
1 part by weight (manufactured by Shiraishi Calcium Co., Ltd.), 1 part by weight of light stabilizer Tinuvin 622LD (manufactured by Ciba Geigy), and 5 parts by weight of cross-linking agent Coronate HL (manufactured by Nippon Polyurethane Industry Co., Ltd.) are added, and the mixture is uniformly transparent. Resin solution b was prepared.

(3) Preparation of Transparent Resin Solution c 100 parts by weight of an acrylic polyol-based resin solution Arotan P-116 (manufactured by Nippon Shokubai Chemical Industry Co., Ltd.) was added to an ultraviolet absorber tinuvin 327 (benzotriazole-based ultraviolet light). (Absorbent: Ciba-Geigy) 1.5 parts by weight, Seesorb 704
1.5 parts by weight (manufactured by Shiraishi Calcium Co., Ltd.), light stabilizer
1 part by weight of LA-63 (manufactured by Adeka Argus), 20 parts by weight of xylene, and 40 parts by weight of a crosslinking agent Colonate HL (manufactured by Nippon Polyurethane Industry Co., Ltd.) were added to obtain a uniform transparent resin solution c. Prepared.

(4) Preparation of Transparent Resin Solution d 2 parts by weight of ultraviolet absorber Tinuvin 213 (manufactured by Ciba Geigy) and 100 parts by weight of acrylic resin-based resin solution ST-100 (manufactured by Nikka Polymer Co., Ltd.), and tinuvin 238
1 part by weight (manufactured by Ciba Geigy), light stabilizer mark LA-6
1 (manufactured by Asahi Denka Co., Ltd.), 18 parts by weight of melamine-based cross-linking agent Nikarac MS-11 (manufactured by Sanwa Chemical Co., Ltd.), and catalyst Beckamine P-198 (manufactured by Dainippon Ink Co., Ltd.) 2
A uniform transparent resin solution d was prepared by adding parts by weight.

(5) Preparation of Transparent Resin Solution e UV absorber Tinuvin 21 in the transparent resin solution b
3. The transparent resin solution e was prepared by removing the sheath 704.

(6) Preparation of Transparent Resin Solution f Crosslinking agent Niclac MS-1 in the above transparent resin solution d
1 was prepared as a transparent resin solution f.

(II) Preparation of Base Resin Solution for Colored Resin Layer (1) Preparation of Base Resin Solution A 100 parts by weight of vinyl chloride resin Nicavinyl SG-1100N (manufactured by Nippon Carbide Industrial Co., Ltd.) Parts, 25 parts by weight of ethylene-vinyl ester resin Elvaloy 742 (manufactured by Mitsui Dupont Chemical Co., Ltd.), polyester plasticizer NS-3
700 (manufactured by Dainichi Seika Co., Ltd.), 6 parts by weight, UV absorber Ubinal N-539 (manufactured by BASF)

1 part by weight of Tinuvin 328 (manufactured by Ciba Geigy) and light stabilizer Mark LA-63 (ADEKA A
Gas) 1 part by weight, antioxidant Irganox 1010
0.5 parts by weight (manufactured by Ciba Geigy), heat stabilizer TM-18
0J (Katsuta Kako Co., Ltd.) 1 part by weight, 1.2 parts by weight of coloring agent A, 2.3 parts by weight of coloring agent B, 0.9 parts by weight of coloring agent C
The mixture was placed in a closed container together with 540 parts by weight of HF and stirred and dissolved at 100 ° C. for 1 hour to prepare a base resin solution A of a vinyl chloride resin.

(2) Preparation of base resin solution B Instead of colorants A to C in base resin solution A, 0.2 parts by weight of colorant A, 0.5 parts by weight of colorant D, -5 parts by weight of a pigment, Iriodin IIIWII (Merck),
Otherwise, base resin solution B was prepared in the same manner as base resin solution A.

Preparation of Colorant (a) Colorant A Fluororesin solution Lumiflon LF-554 (Asahi Glass Co., Ltd.)
100 parts by weight of carbon black-based black pigment,
After adding 20 parts by weight of Gull 330R (manufactured by Cabot), kneading well with a three-roll mill, diluting with toluene so that the solid content becomes 40% by weight, and further dispersing with a colloid mill,
Colorant A was prepared.

(B) Colorant B In place of legal 330R in colorant A, a copper azomethine-based yellow pigment, Palioto-Louiero-L-1070
Colorant B in the same manner as Colorant A using (manufactured by BASF)
Was prepared.

(C) Colorant C In place of the legal 330R in the colorant A, a perylene red pigment Paliogen Red L-3885 (BASF
) Was prepared in the same manner as Colorant A.

(D) Colorant D The colorant D was prepared in the same manner as the colorant A using an indanthrone-based blue pigment Chromophthal-A3R (manufactured by Ciba Geigy) instead of the legal 330R in the colorant A. Prepared.

(III) Preparation of Adhesive Solution for Adhesive Layer (1) Preparation of Adhesive Solution A 100 parts by weight of acrylate-based adhesive PE-121 (manufactured by Nippon Carbide Industry Co., Ltd.) , Crosslinking agent CK-4
01 (manufactured by Nippon Carbide Industrial Co., Ltd.), 4 parts by weight, ultraviolet absorber Tinuvin 327 (manufactured by Ciba Geigy), 1.4 parts by weight,
An adhesive solution A was prepared by mixing 0.7 parts by weight of the light stabilizer LA-63 (manufactured by Adair Agas) and 40 parts by weight of toluene.

(2) Preparation of Adhesive Solution B Acrylic ester adhesive KP-1384 (Nippon Kagaku Co., Ltd.)
100 parts by weight of Bide Industry Co., Ltd.) and the crosslinking agent CK-
Adhesive solution B was prepared by mixing 4 parts by weight of 401 (manufactured by Nippon Carbide Industry Co., Ltd.) and 40 parts by weight of toluene.

(IV) Preparation of Composite Marking Sheet (1) Product 1 of the Present Invention A transparent resin solution a was cast on a polyester film which had been subjected to a peeling treatment in advance, and was then heated at 80 ° C. for 5 minutes, then at 140 ° C. For 5 minutes to form a transparent resin layer 11, then cast a base resin solution A on the transparent resin layer 11 and dry it again at 140 ° C. for 10 minutes to form a colored resin layer 12 A layer was formed on the layer 11.

On the other hand, the adhesive solution A was cast on a 50 μm-thick release polyester base sheet 14 and dried at 100 ° C. for 4 minutes to form an adhesive layer 13. After bonding, the polyester film was peeled from the transparent resin layer 11 to prepare the product 1 of the present invention.

The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in the product 1 of the present invention is 20 μm.
m, 40 μm, and 30 μm. The above transparent resin layer 11
Of 550 nm wavelength light is 92%, 360 nm
Was less than 1%.

(2) Inventive product 2 A base resin solution B was cast on a polyester film which had been subjected to a peeling treatment in advance, and dried at 140 ° C. for 10 minutes to form a colored resin layer 12. Next, after bonding the colored resin layer 12 to the adhesive layer 13 obtained in the above (1), the polyester film is peeled from the colored resin layer 12, and the transparent resin solution b is cast on the colored resin layer 12. 1 at 140 ° C
After drying for 0 minutes, the product 2 of the present invention was obtained.

The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in the product 2 of the present invention is 20 μm.
m, 40 μm, and 30 μm.

The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in the product 1 of the present invention is 20 μm.
m, 40 μm, and 30 μm. The above transparent resin layer 11
Of 550 nm wavelength light is 93%, 360 nm
Was less than 1%.

(3) Product 3 of the Present Invention According to the same method as Product 2 of the present invention, base resin solution A,
Inventive product 3 was prepared using the transparent resin solution c.

The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in the product 3 of the present invention is 15 μm.
m, 40 μm and 35 μm. The above transparent resin layer 11
Of 550 nm wavelength light is 92%, 360 nm
Was less than 1%.

(4) Product 4 of the Present Invention A transparent resin solution d was cast on a polyester film which had been subjected to a peeling treatment in advance, and dried at 80 ° C. for 5 minutes and then at 140 ° C. for 10 minutes to form a transparent resin layer 11. Then, the base resin solution B was cast on the transparent resin layer 11 and dried again at 140 ° C. for 12 minutes to form a colorant layer 12 on the transparent resin layer 11.

On the other hand, the adhesive solution B was cast on a sheet 14 of a 38 μm-thick release polyester base material,
After the adhesive layer 13 is formed by drying the adhesive layer 13 on the colored resin layer 12, the transparent resin layer 11 is formed.
The polyester film of the present invention was peeled off to prepare the product 4 of the present invention. The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in the product 4 of the present invention is 30 μm, 25
μm and 25 μm. The transmittance of light having a wavelength of 550 nm in the transparent resin layer 11 was 92%, and the transmittance of light having a wavelength of 360 nm was less than 1%.

(5) Inventive product 5 Marking film, Hyescal 5040 comprising an in-pay black PVC colored resin layer and an acrylic adhesive layer
The transparent resin solution b was cast on a product (manufactured by Nippon Carbide Industry Co., Ltd.) and dried at 80 ° C. for 5 minutes and subsequently at 100 ° C. for 15 minutes to prepare a product 5 of the present invention. The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in the product 5 of the present invention was 20 μm, 50 μm, and 30 μm.

(6) Comparative product 1 A comparative product 1 was prepared in the same manner as the inventive product 2 using the transparent resin solution e. The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in Comparative Example 1 was 20 μm, 40 μm, and 30 μm.

The transmittance of light having a wavelength of 550 nm in the transparent resin layer 11 was 93%, and the transmittance of light having a wavelength of 360 nm was 85%.

(7) Comparative product 2 Comparative product 2 was prepared in the same manner as in the present invention product 4, using the transparent resin solution f. The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in the comparative product 2 was 30 μm, 25 μm, and 25 μm. The transmittance of light having a wavelength of 550 nm in the transparent resin layer 11 is 92%.
%, The transmittance of light having a wavelength of 360 nm was 87%.

(8) Comparative product 3 A comparative product 3 was prepared in the same manner as the inventive product 5 using the transparent resin solution e. The thickness of each of the transparent resin layer 11, the colored resin layer 12, and the adhesive layer 13 in Comparative Product 3 was 20 μm, 50 μm, and 30 μm.

(V) Test of the product of the present invention and evaluation thereof (1) Measurement of transmittance Using a spectrophotometer UV-365 (manufactured by Shimadzu Corporation), the transparent resin layer 11 of the composite marking sheet was applied. 290
Irradiation at ~ 800 nm, the transmittance in that range was measured and recorded.

(2) Interlayer adhesion test and its evaluation A composite marking sheet attached to a stainless steel (SUS-304) plate was subjected to an accelerated exposure tester WOM (Suga tester ( After the exposure test was performed to obtain a test sample, an adhesion test was performed using a cellophane (manufactured by Nichiban Co., Ltd.).
The results are shown in Table 1 below. In Table 1 below, the mark x indicates that the transparent resin layer 11 was peeled off together with the cellophane, and the mark ○ indicates that the cellophane alone was peeled off and no abnormality was observed in the sample.

Sample exposure test conditions Black panel temperature: 63 ° C. Spray cycle: 18 minutes / 180 minutes Exposure time: 2000 hours

(3) Weather Resistance Test and Evaluation Thereof The WOM-exposed sample and the sample before exposure, which were tested under the same conditions as those described in the section of the adhesion test, were respectively subjected to a spectrophotometer Macbeth MS- 2020 (manufactured by Macbeth), the color difference (ΔE) between the two was determined, and the weather resistance was evaluated based on the ΔE. The results are shown in Table 1 below.

ΔE = less than 5 ○ ΔE = 5-10 ΔΔE = 10 or more ×

(5) Blocking resistance test and evaluation The composite marking sheet was cut into 100 mm × 100 mm, 20 sheets were stacked, and left at 38 ° C. for 72 hours. 20 more
After leaving at 30 ° C. for 3 hours, the degree of adhesion of the 20 composite marking sheets to each other was evaluated.

Smoothly peeled ○ Transparent resin adhering lightly to each other but not remaining on the surface of layer 11 Adhering strongly to each other, × or remaining

(6) Solvent resistance test and evaluation 5 ml of toluene was dropped on the surface of the composite marking sheet with a pipette, left at room temperature for 2 minutes, and then wiped off with a gauze.
The change in surface appearance was observed and the solvent resistance was evaluated.

No change in appearance observed ○ Change in gloss observed △ Dissolution or swelling of surface layer ×

(7) Stain resistance test and its evaluation Oily magic (black) was applied to the surface of the composite marking sheet, and after one day, the surface was wiped off with a cloth soaked with isopropyl alcohol, and the surface contamination was observed. ,evaluated.

[0140] Almost no contamination was observed. ○ Slight contamination remains. △ Remarkably contamination remains. ×

(8) Workability test and its evaluation The composite marking sheet was made of a 0.5 mm thick stainless steel plate (S
US304), a test sample is prepared, and left for about 3 hours, and then the test sample is applied to a coating film bending tester (manufactured by Toyo Seiki Seisaku-Sho, Ltd.) in accordance with JIS K-5400 8.1. ) Was bent about 180 ° using a 2 mmφ rod, and the presence or absence of whitening (due to many minute cracks) at that time was observed and evaluated.

Not whitened at all ○ Slightly whitened △ Notably whitened ×

(9) Measurement of Gel Fraction The transparent resin layer 11 formed on the polyester film was peeled off, cut to about 25 mm × 25 mm, weighed about 2 g, precisely weighed, and equipped with a cooling tube with balls. Put into a 300 ml round bottom flask, add 100 ml of toluene and add 2 ml at 70 ° C.
Heat for 4 hours. After cooling to room temperature, the contents of the flask were filtered off on a filter paper of known weight, dried at 60 ° C. for 60 minutes, and weighed.

The gel fraction was calculated according to the following equation. Gel fraction = [(weight of filter paper after filtration and drying−weight of filter paper before filtration) / (weight of transparent resin layer before extraction with toluene)] × 100

Table 1 shows the test results.

[0146]

[Table 1]

[0147]

The composite marking sheet of the present invention has excellent weather resistance and abrasion resistance, and imparts a glossy color to the surface without unevenness of the color by utilizing the gloss of the metal surface. It can be finished to.

[Brief description of the drawings]

FIG. 1 is an enlarged sectional view showing one embodiment of a composite marking sheet of the present invention.

FIG. 2 is a cross-sectional view showing a state where the composite marking sheet shown in FIG. 1 is bent in a workability test.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Composite marking sheet 11 Transparent resin layer 12 Colored resin layer 13 Adhesive layer 14 Base material 20 Base material

Claims (2)

(57) [Claims] 1. A gel fraction having a thickness of 5 to 100 .mu.m and transmitting 90 to 95% of light having a wavelength of 550 nm and substantially blocking light in a wavelength range of at least 360 nm and below.
A cross-linkable acrylic or cross-linkable urethane-based resin layer having a thickness of at least 70%,
0.01 relative to the resin of the colorant resin layer colorant μm
A composite marking sheet for use, comprising: a colored resin layer containing 200% by weight; and an adhesive layer applied to the colored resin layer and having a thickness of 20 to 100 μm. 2. The method according to claim 1, wherein the content of the colorant is in the resin of the colorant resin layer.
Composite marking sheet according to claim 1, wherein a 3-150 wt% against