JP4704107B2 - Decorative film - Google Patents

Description

The present invention relates to a decorative film used for decoration of a signboard or a vehicle, and more particularly to a decorative film used for a member or the like which is attached to a complicated curved surface of an automobile or the like to enhance design properties.

As a method of coloring the surface of the base material to enhance the decorativeness (designability) of the surface, a method of applying a colored decorative film on the surface of the base material, instead of applying a paint having a desired color on the surface Is widely practiced. The decorative film can be easily and uniformly coated on the surface of the base material, and it can be used in a wide range of fields because there is no volatilization of solvents that can be a problem in the case of paints. Has been.

As a decorative film, a film having a structure in which a soft film and an adhesive are laminated is generally used. Conventionally, a vinyl chloride resin has been widely used as a resin for the soft film. The film occupied the majority.

However, since automobiles, motorcycles, and the like are discarded after a predetermined period, processing of decorative films as waste is a big problem. In particular, decorative films using vinyl chloride resin as a base material cannot be incinerated as they are because they generate chlorine-based gas when incinerated when discarded after use. In addition, it is a social problem that harmful chlorine-containing organic compounds are by-produced during the treatment.

Therefore, a decorative film using a resin that does not generate harmful gas even if it is burned at the time of disposal, for example, a decorative film made of an olefin resin such as polypropylene (Japanese Patent Laid-Open No. 2004-307532; Patent Document 1), 2003-225977; Patent Document 2), decorative film made of acrylic resin (Japanese Patent Laid-Open No. 2004-291517; Patent Document 3), decorative film made of urethane resin (Japanese Patent Laid-Open No. 03-45672; Patent Document) Various non-vinyl chloride resin decoration films such as 4), (Japanese Patent Laid-Open No. 2005-97632; Patent Document 5), and (Japanese Patent Laid-Open No. 2003-326629; Patent Document 6) have been proposed.

When accentuating the design with a color different from other parts on the exterior of narrow parts around automobile doors and windows, parts of machinery, etc., finish with a clear and neat appearance Decorative films that can be used are used. For example, a film that produces a high-quality feeling by sticking a black tape-like decorative film different from the body on the door sash portion of an automobile is widely used as a “blackout film” for luxury car decoration.

In addition to basic characteristics such as appearance and strength, the above-mentioned film for automobiles requires gasoline resistance, flexibility of the film to follow a narrow curved surface, and production processability that can be manufactured efficiently at low cost. It is said that.

Conventional non-vinyl chloride resin decorative films are insufficient in gasoline resistance, flexibility and production processability, and there is no film which can be used for this purpose as a single layer. For example, the polypropylene film described in Patent Document 1 and Patent Document 2 is a laminated film in which a urethane resin layer is provided on the surface in order to satisfy gasoline resistance.

Further, the acrylic resin-based decorative film disclosed in Patent Document 3 is brittle and lacks flexibility, and has insufficient gasoline resistance.

Conventionally known polyurethane resin-based decorative films described in Patent Document 4, Patent Document 5, Patent Document 6 and the like satisfy gasoline resistance and flexibility, but the production method of each film is complicated and productivity is high. It was inferior.
JP 2004-307532 A JP 2003-225977 A JP 2004-291517 A Japanese Patent Laid-Open No. 03-45672 JP 2005-97632 A JP 2003-326629 A

An object of the present invention is to provide a non-vinyl chloride resin decorative film excellent in gasoline resistance, flexibility and productivity, which is a basic performance as a decorative film, despite being a single layer film. .

In a decorative film formed from a resin composition in which at least 20 parts by weight of at least two kinds of resin components are blended in 100 parts by weight of the resin composition, the first resin component has a Shore hardness of A 90 to A98. The above-mentioned problems have been solved by a decorative film which is an acrylic resin and / or a urethane resin having a tensile modulus of elasticity of 700 to 1500 MPa at 23 ° C., which is a caprolactan urethane resin or a polycarbonate urethane resin. .

The decorative film of the present invention is a non-vinyl chloride film that does not generate chlorine gas during disposal and does not produce a harmful chlorine-containing organic compound as a by-product, while satisfying the basic characteristics as a decorative film. It is a film excellent in gasoline resistance, flexibility and production processability.

The decorative film of the present invention is formed from a compounded resin of a urethane resin having a specific hardness range (first resin component) and a resin component having a specific tensile strength range (second and subsequent resin components).

The urethane resin that can be used in the present invention is not particularly limited as long as it has a Shore hardness of A85 to A98, preferably A90 to A98. If the Shore hardness is less than A98, a film with good processability can be obtained, and compatibility with the second resin does not deteriorate, and the usable resin is rarely limited. Moreover, if it is A85 or more, it will become a film with a high tensile elasticity modulus and a firmness, and the film which is excellent in sticking property can be obtained. In addition, the hardness said here is the Shore hardness measured based on ISO868.

The urethane resin is composed of an isocyanate component and a polyol component. As the isocyanate component of the urethane resin of the present invention, aliphatic, alicyclic, aromatic, or a mixture thereof generally used in the production of polyurethane. Polyisocyanate compounds of the system can be used as well. Specifically, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 4,4-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate, xylene diisocyanate, transcyclohexane So-called aromatic polyisocyanates such as 1,4-diisocyanate and tetramethylxylene diisocyanate; pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 4,4'-dicyclohexylbutane diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated methylene diphenyl Diisocyanate, hydrogenated xylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecatriiso Aneto, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, trimethylhexamethylene hexose suggested diisocyanate, and the like.

Further, the above-mentioned isocyanate dimers (uretidione), trimers (isocyanurate), carbodiimide modified products, allophanate modified products, biuret modified products, urea modified products, urethane modified products, or blocked isocyanates thereof, etc. These may be used, each of which can be used alone or in combination of two or more.
In particular, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate and the like are preferably used for reasons such as weather resistance and yellowing resistance.

On the other hand, the polyol component can also be a monomeric or polymeric polyol that has been conventionally used in the production of polyurethane. For example, ethylene glycol, propylene glycol, butanediol, hexanediol, cyclohexanedimethanol, Monomer diols such as diethylene glycol, dipropylene glycol, bisphenol, bishydroxyethoxybenzene, neopentyl glycol, triethylene glycol, hydrogenated bisphenol A; polyester polyol, polycaprolactone polyol, polyether polyol, polycarbonate polyol, acrylic polyol, butadiene polyol, Polymer polyols such as phenolic polyol and epoxy polyol, etc. Specific examples of the remer polyol include, for example, polyether diol, 1,6-hexanediol, phosgene, ethylene carbonate produced using water, propylene glycol, ethylene glycol, potassium hydroxide, or alkylene oxide as an initiator. And polyethylene adipate produced by dehydration condensation of adipic acid and ethylene glycol.

In addition to such a bifunctional alcohol, for example, polyfunctional alcohols such as trimethylolethane, trimethylolpropane, pentaerythritol, glycerin, and diglycerin can be used. Furthermore, using a polyol having an ethylenically unsaturated bond, for example, a polyester diol synthesized using a polycarboxylic acid having an ethylenically unsaturated bond, such as maleic acid, itaconic acid, etc. as part of the carboxylic acid component, You may make it make the polyurethane resin containing an ethylenically unsaturated bond.

Among them, the polyol component that can be suitably used in the present invention includes polycaprolactone polyol and polycarbonate polyol, which are excellent in oil resistance and heat resistance,
In particular, a caprolactan-based urethane resin containing a polycaprolactone polyol as a polyol component, which is less likely to cause production processability such as calendar moldability and physical properties of the calendar molded product, is particularly preferably used.

The polyurethane resin comprising the isocyanate component and the polyol component described above can be produced by a method known per se.

Furthermore, in this invention, the urethane resin manufactured by preparing an isocyanate terminal prepolymer previously from the said isocyanate component and a polyol component, and making this prepolymer react with a chain extension agent can also be used. Examples of chain extenders that can be used here include polyhydric alcohols such as ethylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, and hydroquinone diethylol ether; ethylenediamine, propylenediamine, hexamethylenediamine, piperazine, Isophoronediamine, cyclohexylmethanediamine, 3,3′-dichloro4,4′-diaminodiphenylmethane, diphenylmethanediamine, m-phenylenediamine and other diamines; tolylene diisocyanate dimers, isocyanate modified products such as urea modified products; Etc. Here, a trifunctional or higher functional compound also serves as a crosslinking agent.

Thus, for the production of polyurethane resins, monoalcohols such as methanol, ethanol, and propanol; monoamines such as diethylamine, dipropylamine, and dibutylamine; monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, and the like, as necessary. It is also possible to adjust the molecular weight by using the alkanolamine as a chain elongation terminator.

Furthermore, the urethane resin layer may be modified by graft polymerization of at least one vinyl monomer. Examples of vinyl monomers that can be graft-polymerized include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and (meth) acrylic. C1-C12 alkyl esters of (meth) acrylic acid such as hexyl acid, heptyl (meth) acrylate, octyl (meth) acrylate, and nonyl (meth) acrylate; N-C1 such as methylolacrylamide and butyrolacrylamide ~ C6 alkyl (meth) acrylamide; C2-C6 hydroxyacrylic ester of (meth) acrylic acid such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate or a caprolactone modified product thereof [for example, Daicel Chemical Industries, Ltd. "Plaxel FM series"]; Polyalkylene ether glycol (mono) methacrylate having a degree of polymerization of 2 to 50, such as ethylene glycol acrylate, diethylene glycol acrylate, propylene glycol acrylate, hydroxy polyalkylene ether glycol (mono) methacrylate; acrylic acid, methacrylic acid, malee Ethylenically unsaturated carboxylic acids such as acid, itaconic acid and crotonic acid; oxyalkyl (meth) acrylates such as ethylene oxide phosphoric acid (meth) acrylate and propylene oxide phosphoric acid (meth) acrylate; dicyclopentenyl (meth) Acrylate, N-vinyl pyrrolidone, acrylonitrile, acrylamide, styrene, vinyl toluene, vinyl acetate, etc. These can be used alone or in combination of two or more.

The graft amount of the vinyl monomer can be changed according to the type of vinyl monomer, the characteristics required for the modified urethane resin to be obtained, etc., but generally, up to 100% by weight based on the weight of the polyurethane resin to be grafted, It is preferably within the range of 70 to 2% by weight, more preferably 60 to 5% by weight.
As urethane resin used for this invention, it is possible to use the said urethane resin 1 type or in mixture of 2 or more types.

As the second resin of the present invention, a resin that does not contain chlorine, is compatible with the urethane resin, and has a tensile modulus of 500 to 2000 MPa, preferably 600 to 1800 MPa, and particularly preferably 700 to 1500 MPa, For example, acrylic resin, polyester resin, urethane resin, and the like can be given. In addition, the tensile elasticity modulus said here is calculated | required by the method based on JISK7113.

The second resin can be used alone or in combination of two or more as required, and it is particularly preferable to use a urethane resin or an acrylic resin excellent in compatibility with the first resin.

The acrylic resin used as the second resin is a resin whose main component is a resin produced by polymerization of an acrylic monomer. The main component is a resin containing 50% or more of an acrylic resin as a resin component. For example, acrylic ester, methyl acrylate, propyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate And a resin obtained by polymerizing ethylene glycol dimethacrylate as a monomer.

The ratio of the urethane resin component and the other resin components in the compounded resin needs to be 20 parts by weight or more in 100 parts by weight of the compounded resin. The ratio of (urethane resin component) / (other resin component) is 20 parts by weight / 80 parts by weight to 70 parts by weight / 30 parts by weight, preferably 30 parts by weight / 70 parts by weight to 65 parts by weight / 35 parts by weight. Particularly preferably, the content is 40 parts by weight / 60 parts by weight to 60 parts by weight / 40 parts by weight. If the urethane resin is 20 parts by weight or more, a film having excellent gasoline resistance can be obtained, and if it is 70 parts by weight or less, the processing temperature during film formation does not increase and a film having good processability is obtained. be able to.

Further, as a processing aid for selecting a wider calendar processing temperature range, a system in which polycaprolactone having a weight average molecular weight of 100,000 or less is used in combination with the compounded resin is particularly preferable.

Polycaprolactone used as a processing aid acts as a plasticizer for compounded resins and has the effect of increasing the fluidity of the resin over a wide temperature range and widening the gelation temperature range during calendar processing.

The ratio of polycaprolactone as a processing aid is 0.1 to 15 parts by weight, preferably 0.5 to 12 parts by weight, particularly preferably 100 parts by weight of the sum of urethane resin and other resins. Is preferably 1.0 to 10 parts by weight. Even if polycaprolactone is added in an amount of more than 15 parts by weight, the gelation temperature range does not increase, and if it is 0.1 parts by weight or less, the addition effect does not appear.

The compounded resin of the present invention may contain a colorant in order to improve design properties. In particular, when used as a decorative film for automobiles such as a blackout film, a black or dark pigment is often used among the pigments described later.

When obtaining a colored decorative film by coloring the compounded resin, the addition ratio of the colorant to the colored resin layer may be selected in a suitable range depending on the desired color and the type of the colorant, but is generally 0. The colorant should be contained in an amount of 01 to 200% by weight, preferably 0.05 to 100% by weight, more preferably 0.1 to 50% by weight. If the added amount of the colorant is less than 0.01% by weight, the colorability of the colored resin layer is inferior, and the significance of the coloration is less preferred, and if it exceeds 200% by weight, the physical properties of the colored resin layer are inferior. There is a possibility that the decorativeness, flexibility, moldability, etc. may be adversely affected.

The colorant that can be used is preferably a weathering colorant that can be used for a long period of time. Specifically, Color Index 3rd published by The Society of Dyers and Colorists, Inc.
You can choose from the colorants listed in Edition (1971) and Supplements (1975). The colorant names shown below are the Color Index defined in the same document.
According to Generic Name. For example, Y-1 means CIPigment Yellow 1, O is orange, R is red, V is purple, B is blue, C is green, Br Represents brown, Bk represents black, and W represents 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 preferable colorant is specifically illustrated.
Examples of preferable yellow colorants include azo, condensed polycyclic, metal complex, and inorganic pigments.

Preferred azo pigments include, for example, Y-97, Y-116, Y-120, Y-151, Y-154 for insoluble monoazo pigments, Y-81, Y-83, Y-155 for disazo pigments, condensation Examples of the azo pigment include Y-93, Y-94, Y-95, and Y-128, and preferred condensed polycyclic pigments include
For example, Y-24, Y-108, Y-147, Y-123, Y-99 for anthraquinone pigments, Y-109, Y-110, Y-173 for isoindolinone pigments, Y-139 for isoindoline pigments, Examples of quinophthalone pigments include Y-138, and examples of preferable metal complex salt pigments include Y-117 and Y-129 for the azomethine pigment, Y-153 for the nickel nitroso pigment, and G- for the nickel azo pigment. 10 can be mentioned. Further, examples of preferable inorganic pigments include Y-42 for iron oxide yellow and Y-53 for titanium-antimony-nickel oxide.

Examples of preferred orange pigments include azo pigments and condensed polycyclic pigments.
Preferred azo pigments include, for example, O-36, O-5, O-38, O-60, O-62 for insoluble monoazo pigments, O-34 for disazo pigments, and O-34 for condensed azo pigments. In addition, examples of preferred condensed polycyclic pigments include O-43 for perylene pigments, O-40 and O-51 for anthraquinone pigments, and O-42 for isoindolinone pigments. Examples of quinacridone pigments include O-48 and O-49.

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

Preferred examples of the azo pigment include R-2, R-6, R-7, R-9, R-10, R-12, R-14, R-112, and R-146 for insoluble monoazo pigments. , R-147, R-170, R-171, R-175, R-185, R-187, R-188, R-208, R-52: 2, R-115, R for azo lake pigments -151, R-243, R-144, R-166, R-214, R-220, R-221, R-242 for condensed azo pigments, R-38, R-37 for disazo pigments Can

Preferred examples of the condensed polycyclic pigment include R-168, R-177, and R-216 for anthraquinone pigments, R-88 for thioindigo pigments, R-194 for perinone pigments, and perylene pigments. For R-123, R-149, R-178, R-179, R-190, R-224 and quinacridone pigments, V-19, R-122, R-202, R-207, R-209, R- 206)

In addition, as a new pigment, diketopyrrolopyrrole pigments may include Ciba Geiger Irgadine DPP Red BO, and preferred inorganic pigments include red iron oxide R-101 for Bengala and R for zinc / iron oxide. -225 etc. can be mentioned.

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

Examples of preferable azo pigments include V-50 for monoazo pigments, and examples of preferable condensed polycyclic pigments include V-29 for perylene pigments and V-29 for anthraquinone pigments. 31, V-33, V-38, V-36 for thioindigo pigments, V-19 for quinacridone pigments, V-23, V-37 for dioxazine pigments, and inorganic preferred Examples of the pigment include V-14: 1 for the cobalt phosphate type, V-18 for the ferrolite violet pigment, and V-47 for the cobalt / lithium / vanadium phosphate pigment.

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

Preferable phthalocyanine pigments include, for example, B-15: 1 and B-15: 2 for α-type copper phthalocyanine-based pigments, B-15: 3, B-15: 4 and ε-type for β-type copper phthalocyanine pigments Examples of phthalocyanine pigments include B-15: 6, and metal-free phthalocyanine pigments include B-16. Preferred condensed polycyclic pigments include, for example, B-60 and B-21 for indatron pigments. , B-22, B-64,

Examples of preferable inorganic pigments include B-27 for amber, B-29 for ultramarine blue, B-28 for cobalt-aluminum oxide pigments, B-36 for cobalt-chromium-aluminum oxide pigments, etc. Can be mentioned.

Further, examples of preferable green pigments include phthalocyanine pigments, condensed polycyclic pigments, and inorganic pigments.

Preferred phthalocyanine pigments include, for example, G-37 for medium chlorinated copper phthalocyanine pigments, G-7 for high salt bromide copper phthalocyanine pigments, G-36 for high salt brominated copper phthalocyanine pigments, etc. Examples of preferable condensed polycyclic pigments include G-47 for violant long lean, and preferable inorganic pigments include, for example, G- for chromium oxide pigments. 17, G-19 for cobalt-titanium-nickel-zinc oxide pigments, G-50 for cobalt-titanium pigments, and the like.

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

Examples of preferred azo pigments include Br-25 and Br-32 for monoazo pigments, Br-5 and Br-2 for metal complex azo pigments, and Br-23 for condensed azo pigments. Examples of preferred condensed polycyclic pigments include Br-28 for anthraquinone pigments and Br-26 for perylene pigments.

Examples of preferable inorganic pigments include Br-6 for iron oxide pigments, Br-29 for iron-chromium oxide pigments, and Br-31 for zinc-iron oxide pigments.

Examples of preferable black pigments include organic pigments and inorganic pigments. Examples of preferable organic pigments include Bk-1 for aniline black and Bk-31 for perylene black.
Examples of preferable inorganic pigments include Bk-31, Bk-7, and Bk-9 for carbon black, Bk-11 for iron black, and Bk-13 for cobalt oxide pigments. it can.

In addition, as a preferred white pigment, an inorganic pigment is preferable, for example, W-4 for zinc white, W-7 for zinc sulfide, W-6 for titanium dioxide, W-18 for calcium carbonate, W-19, barium sulfate W-21, alumina white W-24, silica W-27, muscovite W-20, tank W-26, etc.

Other preferable pigments include, for example, titanium dioxide-coated mica known as a par pigment, and those having a particle size of 2 to 200 μm are preferable, more preferably 4 to 150 μm, and particularly preferably. Is 5 to 100 μm. Moreover, it is preferable that the titanium oxide of a coating layer is a rutile type from a point of a weather resistance.

Furthermore, it may be colored with a colorant such as iron oxide, may exhibit an interference color, or may have a silvery or milky color.

Commercially available products include those made by Merck, Iriojimall, and highlights.
In addition to the pigment, the colored resin layer can contain mica and aluminum powder as long as the transparency and weather resistance are not affected.

Furthermore, it is preferable to add additives such as an ultraviolet absorber, a light stabilizer, and an antioxidant to the compounded resin in order to improve the weather resistance and the like of the decorative film.

Considering the ultraviolet absorbing ability of the ultraviolet absorbent and compatibility with the synthetic resin to be used, it can be appropriately selected from a wide range of one or several kinds. For example, the following can be used: Can be mentioned.
Hydroquinone; hydroquinone, hydroquinone disalicylate salicylic acid; phenyl salicylate, paraoctylphenyl salicylate

Benzophenone series; 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,4-hydroxybenzo Phenone, 2,2'-hydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2-hydroxy- 4-methoxy-5-sulfonebenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-hydroxy-4,4′-dimethoxy-5-sodium sulfobenzophenone, 4, -Dotesyloxy-2-hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone

Benzotriazole type; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfonebenzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy- 5'-amylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5 ' -Dimethylphenyl) -5-methoxybenzotriazole, 2- (2'-methyl-4'-hydroxyphenyl) benzotriazole, 2- (2'-stearyloxy-3 ', 5'-dimethylphenol Enyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-hydroxy-3'-methyl-5'-third Butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazo 2- (2'-hydroxy-5'-phenylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-cyclohexylphenyl) benzo Riazole, 2- (2'-hydroxy-4 ', 5'-dimethylphenyl) -5-carboxylic acid benzotriazole butyl ester, 2- (2'-hydroxy-3', 5'-dichlorophenyl) ) Benzotriazole, 2- (2'-hydroxy-4 ', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dimethylphenyl) -5-ethylsulfone Benzotriazole, 2- (2'-hydroxy-5'-phenylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy -5'-methoxyphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid ester benzotriazole, 2- (2'- Setokishi 5'-methylphenyl) benzotriazole - le, 2- (2'-hydroxy-3', 5'-di Tashiya butylphenyl) -5-chlorobenzotriazole azo - le.

Of these ultraviolet absorbers, those based on benzophenone and benzotriazole are suitable for improving the weather resistance. Among them, 2,3′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole in benzotriazole system 2- (2′-hydroxy-5-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2-hydroxy-5′-tert-butylphenyl) benzotriazole,

2- (2′-hydroxy-3′-methyl-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′ditert-butylphenyl) -5-chloro-benzotriazole and 2- (2'-hydroxy-5'-phenylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-ditertiarybutylphenyl) -5-chlorobenzotriazo- And 2- (2'-hydroxy-5'-octoxyphenyl) benzotriazole and the like are particularly effective.

The ultraviolet absorber is preferably added in an amount of 0.05 to 3.0% by weight. If the UV absorber is added within this range, the UV cut rate (at 380 nm) is 90% or more, and even when exposed outdoors, 1 to 2 years (equivalent to 1,000 hours of sunshine weatherometer) 90% The above can be held. When the amount is more than this range, the film tends to be whitened, blown out to the film surface, etc., which is not preferable.

As the light stabilizer, bis (2,2,6,6, -tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6, -pentamethyl-4-piperidyl) sebacate, 1- [2 -[3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Hindered amine light stabilizers such as -2,2,6,6, -tetramethylpiperidine and 4-benzoyloxy-2,2,6,6, -tetramethylpiperidine, and quenchers such as organic nickel can be used.

The method for producing the decorative film of the present invention is not particularly limited, and the compounded resin may be formed by a known film production method such as a calendar molding method or a T-die extrusion molding method.

The compounded resin of the present invention does not use a solvent, and can be continuously molded in a large amount, is easy to be molded in a calendar molding method that is excellent in productivity and environmental pollution, and a decorative film obtained by molding is sufficient. Having the necessary characteristics is the biggest feature.

In the compounded resin, a lubricant containing a long-chain fatty acid ester, a glycerin ester or the like as a main component for the purpose of improving processability when forming the compounded resin into a film, if necessary, particularly improving moldability during calendering, Additives such as processing aids such as calcium carbonate and heat stabilizers can also be added.

When adhering the decorative film of the present invention to a substrate via an adhesive layer, an adhesive layer is provided on the surface opposite to the surface.
The adhesive layer has a thickness of 20 to 100 μm, preferably 30 to 70 μm, more preferably 30 to 50 μm. When the film thickness is less than 20 μm, the film is peeled off from the adherend and the workability such as bending of the adherend deteriorates, which is not preferable, and when the film thickness exceeds 100 μm, the initial adhesive strength becomes too high. There exists a possibility that it may be inferior to sticking suitability and cost may become high.

Further, the adhesive strength of the adhesive layer is that when the composite film having a width of 25.4 mm is bonded to the adherend and left for 24 hours and then folded back by 180 ° in a peel test with a Tensilon tensile tester. The measured value is preferably 1.0 kg / 25.4 mm or more. When the adhesive strength is less than 1.0 kg / 25.4 mm, there is a possibility that the film is peeled off from the adherend when the adherend to which the composite decorative film is attached is bent.

The material for forming the adhesive layer is preferably an acrylic resin from the viewpoints of weather resistance, transparency, yellowing resistance and the like.

The main component of the monomer in the acrylic resin is preferably a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 14 carbon atoms. When the number of carbon atoms deviates from the range of 4 to 14, the resin layer becomes hard and may have poor flexibility. The main component of the monomer in the acrylic copolymer is preferably contained in an amount of 50 mol% or more. When the ratio is less than 50 mol%, the acrylic resin becomes hard and may have poor flexibility.

Examples of the (meth) acrylic acid alkyl ester include n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methylpentyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. And lauryl (meth) acrylate.

Examples of the other component monomer copolymerized with the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, and styrene.

The functional groups of monomers that can be introduced into these resins include carboxyl groups such as (meth) acrylic acid and itaconic acid, hydroxyl groups such as hydroxy (meth) acrylate and n-methylolacrylamide, glycidyl ( In the present invention, it is preferable to employ a urethane crosslinking method in combination with a general polyisocyanate crosslinking agent. In this case, a carboxyl group, Hydroxyl groups are preferred.

Examples of the solvent used when copolymerizing these monomers include conventionally known solvents such as benzene, toluene, xylene, methyl cellosolve, ethyl cellosolve, ethyl acetate, and methanol. Two or more kinds can be mixed and used. Examples of the polymerization initiator include azo initiators such as azobisisobutyronitrile and peroxide initiators such as di-t-butyl peroxide. Can be used.

The acrylic resin preferably has a weight average molecular weight (Mw) of 200,000 to 1,000,000, more preferably 400,000 to 800,000. The molecular weight can be adjusted by the amount of the polymerization initiator or by adding a chain transfer agent.

In addition, additives, such as a tackifier, an ultraviolet absorber, a light stabilizer, and an antioxidant, can be added to the acrylic resin as necessary. The acrylic resin thus obtained is added to the adherend by adding 0.1 to 1 equivalent, preferably 0.3 to 0.7 equivalent, of polyisocyanate as a crosslinking agent to the functional group. The adhesive strength of can be strengthened. In addition, a reaction accelerator can be added as necessary during the crosslinking reaction.

The decorative film of the present invention is a single-layer film that can be produced at low cost and in large quantities by a calendering method, and in particular, an automotive decorative film that is applied to a narrow part around the door or window of an automobile. Suitable for decorating member curved surfaces such as (blackout film).

In addition, the decorative film of the present invention does not generate harmful chlorine compounds at the time of disposal, and can be produced inexpensively and in large quantities by a calendering method, while having basic characteristics, gasoline resistance, and weather resistance. Therefore, it can be effectively used for conventional decorative films such as signboards.

In order to describe the present invention in more detail, examples will be described below, but the present invention is not limited thereto. In addition, the measuring method in an Example is as follows.

Moreover, about the test piece used for (2) gasoline resistance test, (3) heat resistance test, (4) moisture resistance test, (5) hot water resistance test, and (8) weather resistance test, the film surface is as follows. Use the one with the adhesive layer on the opposite side.
A release paper (Lintec Co., Ltd. E) was prepared by mixing and stirring 1.5 parts by weight of an isocyanate crosslinking agent (Nihon Polyurethane Coronate L) with 100 parts by weight of an acrylic pressure-sensitive adhesive (KP-2279, manufactured by Nippon Carbide Industries Co., Ltd.) -KB) is coated and dried to a dry thickness of 35 μm, and this pressure-sensitive adhesive surface is bonded to the surface opposite to the film surface.

(1) Film elongation, yield point elongation, yield point stress, elastic modulus Samples were cut into 10mm width tapes with No. 1 dumbbell (10mm width), using a tensile tester, gripping interval 50mm, tensile speed A tensile test was performed at 200 mm / min, and film elongation, yield point elongation, yield point stress, and elastic modulus were measured at 23 ° C.

(2) Gasoline resistance test A 2.5 cm square sample is affixed to an alkyd melamine coated plate (manufactured by Nippon Test Panel Co., Ltd.) washed with IPA and dried, and left at room temperature for 24 hours to prepare a test piece. This test piece is immersed in JIS No. 1 gasoline at room temperature for 30 minutes and then taken out to check the appearance.
○: No change in appearance is observed in the sample.
Δ: A slight change in appearance is observed in the sample.
X: A clear appearance abnormality occurs in the sample.

(3) Heat resistance test A test piece is prepared in the same manner as the gasoline resistance test. The test piece is left in a dryer at 80 ° C. for 168 hours and then removed to check the appearance.
○: No change in appearance is observed in the sample.
Δ: A slight change in appearance is observed in the sample.
X: A clear appearance abnormality occurs in the sample.

(4) Moisture resistance test A test piece is prepared in the same manner as the gasoline resistance test. The specimen is left in a constant temperature and humidity chamber at 50 ° C. and 98% for 168 hours and then taken out to check the appearance.
○: No change in appearance is observed in the sample.
Δ: A slight change in appearance is observed in the sample.
X: A clear appearance abnormality occurs in the sample.

(5) Hot water resistance test A test piece is prepared in the same manner as the gasoline resistance test. The test piece is left in a 40 ° C. water bath for 168 hours and then removed to check the appearance.
○: No change in appearance is observed in the sample.
Δ: A slight change in appearance is observed in the sample.
X: A clear appearance abnormality occurs in the sample.

(6) Scratch resistance test Using a Gakushin type tester, the surface of the film and the colored state of kanakin are checked after reciprocating the surface of the film 1000 times with a load of 500 g using cotton cloth No.3.
○: The film surface is not damaged. Δ: The film surface is slightly scratched, but the cotton cloth Kanakin No. 3 has no transition of the resin layer film color (black).
X: The resin layer film color is scratched, and the cotton fabric Kanakin No. 3 has a color transition of the resin layer film color (black).

(7) Dimensional stability test A film sample prepared to a 10 cm square is taken out after being left in a dryer at 80 ° C. for 0.5 hour, and the shrinkage rate is measured.
○: 0.5% or less ×: 0.5% or more

(8) Weather resistance test A test piece is prepared in the same manner as the gasoline resistance test. This test piece is irradiated with a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd., black panel temperature 63 ° C.) for 3000 hours, and then the appearance is confirmed.
○: No change in appearance is observed in the sample.
Δ: A slight change in appearance is observed in the sample.
X: A clear appearance abnormality occurs in the sample.

(9) Calendar workability As a processing temperature range test device, a mixing roll (roll size φ200 mm × L500 mm manufactured by Nippon Roll Manufacturing Co., Ltd.) is used, the roll rotation speed is 14 rpm / 11 rpm, and the roll gap is 100 μm. The sheet was melt kneaded while winding the compound around a roll, and the sheet kneaded after 5 minutes was sampled. At the time of sampling, the temperature at which the molten resin adheres to the roll and cannot be peeled is the upper limit temperature for calendering, and the temperature at which the sheet surface is not smooth and the surface transfer state becomes defective The lower limit temperature was set. The range between the upper limit temperature and the lower limit temperature of this calendering is ΔT, and if this ΔT is 10 ° C. or higher, it is judged that it is suitable for calendering.

Visually confirm the surface condition of the finished film.
○: The sheet surface is smooth and has a mirror surface state △: A small part of the flow mark is observed on the sheet surface.

Example 1
50 parts by weight of a polycaprolactone-based urethane resin having a Shore hardness of A97 (Resamine P-4597 manufactured by Dainichi Seika Kogyo Co., Ltd.), 50 parts by weight of an acrylic resin having a tensile elastic modulus of 1220 MPa (Parapet GR-F manufactured by Kuraray Co., Ltd.), and a molecular weight of 50 5 parts by weight of polycaprolactone (Placcel H5 manufactured by Daicel Chemical Co., Ltd.), 5 parts by weight of acrylic resin (Mettablen P551 manufactured by Mitsubishi Rayon Co., Ltd.) as a processing aid, and UV absorber (Ciba Specialty Chemicals) Co., Ltd. Tinuvin 234) 0.3 parts by weight, light stabilizer (Ciba Specialty Chemicals Co., Ltd. Tinuvin 144) 0.3 parts by weight, antioxidant (Ciba Specialty Chemicals Co., Ltd. IRGANOX 1010) 0 .4 parts by weight, lubricant (kura Ant Japan Co., Ltd. Licowax
E) 0.3 part by weight, 5.0 parts by weight of a coloring agent (W-8012-G3 manufactured by Nihongo Bix Co., Ltd.), and 5.0 parts by weight of calcium carbonate (WS-100 manufactured by Takehara Chemical Co., Ltd.) as a filler. Dry blending was performed with a Henschel mixer to prepare a compound. The calendering temperature range of this compound was 188 to 213 ° C., and ΔT was 25 ° C. Next, this compound is heated and gelled with a mixing roll at 195 ° C. for 5 minutes, and colored with a thickness of 100 μm using a 200 ° C. calender roll (200 × 700 type 6 calender manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. As shown in the following table, the obtained film was excellent in film appearance, scratch resistance, gasoline resistance, and weather resistance.

Example 2 to Example 6
Table 1 shows the number of parts of a polycaprolactone-based urethane resin having a Shore hardness of A97 (Resamine P-4597 manufactured by Dainichi Seika Kogyo Co., Ltd.) and an acrylic resin having a tensile elastic modulus of 1220 MPa (Parapet GR-F manufactured by Kuraray Co., Ltd.). Otherwise, a film was obtained in the same manner as in Example 1. As shown in the following table, the obtained film was excellent in film appearance, scratch resistance, gasoline resistance, and weather resistance.

Example 7
A compound was prepared in the same manner as in Example 1 except that polycaprolactone having a molecular weight of 50,000 was removed. The calendering temperature range of this compound was 193 to 211 ° C., and ΔT was 18 ° C. Next, this compound is heated and gelled with a 200 ° C. mixing roll for 5 minutes, and colored with a thickness of 100 μm using a 205 ° C. calendar roll (200 × 700 6 calendars manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. As shown in the following table, the obtained film was excellent in film appearance, scratch resistance, gasoline resistance, and weather resistance.

Example 8
As a processing aid, 60 parts by weight of a polycaprolactone-based urethane resin having a Shore hardness of A95 (Milactolan E-995, manufactured by Nippon Milactolan Co., Ltd.), 40 parts by weight of an acrylic resin having a tensile modulus of 1220 MPa (Parapet GR-F, manufactured by Kuraray Co., Ltd.) 5 parts by weight of polycaprolactone having a molecular weight of 50,000 (Placcel H5 manufactured by Daicel Chemical Co., Ltd.), 0.3 parts by weight of an ultraviolet absorber (Cinubin 234 manufactured by Ciba Specialty Chemicals Co., Ltd.), a light stabilizer (Ciba 0.3 parts by weight of Tinuvin 144 manufactured by Specialty Chemicals Co., Ltd., 0.4 parts by weight of antioxidant (IRGANOX 1010 manufactured by Ciba Specialty Chemicals Co., Ltd.), W-8012- manufactured by Nihongo Bix Co., Ltd. G3) 5.0 parts by weight of Henschel Miki Dry blending with a sir produced a compound. The calendering temperature range of this compound was 190 to 210 ° C., and ΔT was 20 ° C. Next, this compound is heated and gelled with a mixing roll at 195 ° C. for 5 minutes, and colored with a thickness of 100 μm using a 200 ° C. calender roll (200 × 700 type 6 calender manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. The obtained film was excellent in film appearance, scratch resistance, gasoline resistance, and weather resistance as shown in the following table.

Example 9
30 parts by weight of a polycaprolactone-based urethane resin having a Shore hardness of A97 (Resamine P-4597 manufactured by Dainichi Seika Kogyo Co., Ltd.) and 70 parts by weight of a urethane resin having a tensile elastic modulus of 730 MPa (Rezamin P-4230 manufactured by Dainichi Seika Kogyo Co., Ltd.) 5 parts by weight of polycaprolactone (Placcel H5 manufactured by Daicel Chemical Co., Ltd.) having a molecular weight of 50,000 as a processing aid, 5 parts by weight of an acrylic resin (Metabrene P551 manufactured by Mitsubishi Rayon Co., Ltd.), and a UV absorber (Cipro Kasei Co., Ltd. Sea Sorb 103) 0.7 parts by weight, light stabilizer (Asahi Denka Co., Ltd. LA-63P) 0.7 parts by weight, antioxidant (Ciba Specialty Chemicals Co., Ltd. IRGANOX 1010) 0 .4 parts by weight, colorant (manufactured by Nihongo Bix Corporation W-8012 G3) 5.0 parts by weight of calcium carbonate as a filler (Takehara Chemical Co., Ltd. WS-100) were dry-blended 5.0 parts by weight of a Henschel mixer to prepare a compound. The calendering temperature range of this compound was 201 to 215 ° C., and ΔT was 14 ° C. Next, this compound was heated and gelled with a 205 ° C. mixing roll for 5 minutes, and colored with a thickness of 100 μm using a 210 ° C. calendar roll (200 × 700 6 calendars manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. The obtained film was excellent in film appearance, scratch resistance, gasoline resistance, and weather resistance as shown in the following table.

Example 10
A compound was produced in the same manner as in Example 1 except that the urethane resin was changed to a polycarbonate urethane resin having a Shore hardness of A90 (Resamine P890 manufactured by Dainichi Seika Kogyo Co., Ltd.). The calendering temperature range of this compound was 173 to 188 ° C., and ΔT was 15 ° C. Next, this compound was heated and gelled with a 180 ° C. mixing roll for 5 minutes, and colored with a thickness of 100 μm using a 183 ° C. calendar roll (200 × 700 6 calendars manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. The obtained film was excellent in film appearance, scratch resistance, gasoline resistance, and weather resistance as shown in the following table.

Example 12
40 parts by weight of a polycaprolactone urethane resin having a Shore hardness of A97 (Resamine P-4597 manufactured by Dainichi Seika Kogyo Co., Ltd.), 40 parts by weight of an acrylic resin having a tensile elastic modulus of 1220 MPa (Parapet GR-F manufactured by Kuraray Co., Ltd.), and tensile elasticity 20 parts by weight of urethane resin with a rate of 730 MPa (Resamine P-4230 manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 parts by weight of polycaprolactone (Placcel H5 manufactured by Daicel Chemical Co., Ltd.) having a molecular weight of 50,000 as a processing aid, and further processing aids As acrylic resin (Mittabrene P551, manufactured by Mitsubishi Rayon Co., Ltd.) 5 parts by weight, and further UV absorber (Ciba Specialty Chemicals Co., Ltd., chinubin 234) 0.3 parts by weight, light stabilizer (Ciba Specialty Chemicals Co., Ltd.) Tinuvin 144 manufactured by company) 0.3 parts by weight Antioxidant (Ciba Specialty Chemicals Co., Ltd. IRGANOX1010) 0.4 parts by weight, a lubricant (Clariant Japan KK Licowax
E) 0.3 part by weight, 5.0 parts by weight of a coloring agent (W-8012-G3 manufactured by Nihongo Bix Co., Ltd.), and 5.0 parts by weight of calcium carbonate (WS-100 manufactured by Takehara Chemical Co., Ltd.) as a filler. Dry blending was performed with a Henschel mixer to prepare a compound. The calendering temperature range of this compound was 197 to 218 ° C., and ΔT was 21 ° C. Next, this compound was heated and gelled with a 205 ° C. mixing roll for 5 minutes, and colored with a thickness of 100 μm using a 210 ° C. calendar roll (200 × 700 6 calendars manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. The obtained film was excellent in film appearance, scratch resistance, gasoline resistance, and weather resistance as shown in the following table.

Comparative Example 1
In Example 1, a compound was produced in the same manner except that the ratio of urethane resin / acrylic resin was changed from 50 parts by weight to 50 parts by weight to 10 parts by weight / 90 parts by weight. The calendering temperature range of this compound was 180 to 195 ° C., and ΔT was 15 ° C. Next, this compound was heated and gelled with a mixing roll at 185 ° C. for 5 minutes, and colored with a thickness of 100 μm using a calendar roll at 185 ° C. (200 × 700 6 calendars manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. As shown in the following table, the obtained film was excellent in film appearance, but was inferior in scratch resistance and gasoline resistance.

Comparative Example 2
A compound was prepared in the same manner as in Example 1 except that the ratio of urethane resin / acrylic resin was changed from 50 parts by weight to 50 parts by weight to 100 parts by weight / 0 parts by weight. This compound had a calendering temperature range of 193 to 203 ° C. and ΔT of 10 ° C. Next, this compound was heated and gelled with a 197 ° C. mixing roll for 5 minutes, and colored with a thickness of 100 μm using a 200 ° C. calender roll (200 × 700 6 calendars manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. As shown in the table below, the obtained film was excellent in film appearance, scratch resistance and gasoline resistance, but had a low tensile elastic modulus and inferior processability.

Comparative Example 3
A compound was prepared with the same composition as in Example 1 except that a lactone urethane resin having a Shore hardness of D75 (T-5070, manufactured by DIC Bayer Polymer Co., Ltd.) was used as the urethane resin. The processing temperature range of this compound was 207 to 215 ° C., and ΔT was 8 ° C. Next, this compound was heated and gelled with a 210 ° C. mixing roll for 5 minutes, and colored with a thickness of 100 μm using a 212 ° C. calender roll (200 × 700 6 calendars manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. The obtained film had a flow mark and had a very poor appearance.

Comparative Example 4
A compound was produced with the same composition as in Example 1 except that Shore hardness A80 (Daijin Seika Kogyo Co., Ltd. Rezamin P880) was used as the urethane resin. The calendering temperature range of this compound was 167 to 183 ° C., and ΔT was 16 ° C. Next, this compound was heated and gelled with a 180 ° C. mixing roll for 5 minutes, and colored with a thickness of 100 μm using a 175 ° C. calendar roll (200 × 700 6 calendars manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. As shown in the following table, the obtained film was excellent in film appearance and scratch resistance, but was inferior in gasoline resistance.

Comparative Example 5
A compound was prepared with the same composition as in Example 1 except that an acrylic resin having a tensile modulus of 8 MPa (RF-040 manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the acrylic resin. The calendering temperature range of this compound was 188 to 205 ° C., and ΔT was 17 ° C. Next, this compound is heated and gelled with a mixing roll at 195 ° C. for 5 minutes, and colored with a thickness of 100 μm using a 200 ° C. calender roll (200 × 700 type 6 calender manufactured by Nippon Roll Manufacturing Co., Ltd.). A film was obtained. As shown in the table below, the obtained film was excellent in film appearance and scratch resistance, but was inferior in gasoline resistance, in low tensile elastic modulus and inferior in workability.

Comparative Example 6
A compound was produced with the same composition as in Example 1 except that a polyester resin having a tensile modulus of 2610 MPa (Byron 245 manufactured by Toyobo Co., Ltd.) was used instead of the acrylic resin. An attempt was made to gel this compound with a mixing roll, but it did not melt uniformly and could not be sampled.

Claims (7)

In a decorative film formed from a resin composition in which at least 20 parts by weight of at least two kinds of resin components are blended in 100 parts by weight of the resin composition, the first resin component has a Shore hardness of A 90 to A98. of a caprolactam-based urethane resin or polycarbonate-based urethane resin, decorative film resin component other than it tensile modulus at 23 ° C. is an acrylic resin and / or urethane resins 500～2000MPa. 2. The decorative film according to claim 1, wherein the tensile modulus of elasticity of other resin components at 23 ° C. is 700 to 1500 MPa. 2. The decorative film according to claim 1, wherein the Shore hardness of the first resin component is A90 to A97, and the tensile modulus of elasticity of the other resin components at 23 ° C. is 730 to 1220 MPa. The decorative film according to any one of claims 1 to 3, wherein a blending ratio of the urethane resin as the first resin component is 20 to 70 parts by weight in 100 parts by weight of the resin blend. The decoration according to any one of claims 1 to 4 , wherein the decoration is formed from a resin blend in which 0.1 to 15 parts by weight of polycaprolactone having a weight average molecular weight of 100,000 or less is further blended with 100 parts by weight of the resin blend. Film. The decorative film according to any one of claims 1 to 5, which has a tensile elastic modulus at 23 ° C of 150 to 1000 MPa and an elongation at break of 80 to 450%. The decorative film according to any one of claims 1 to 6, wherein a film forming method is a calendar method.