JP5231858B2 - Metallic film - Google Patents

Description

The present invention does not lose specularity even after various high temperature heat treatment processes such as thermoforming processes such as insert molding, thermal laminating processes, overcoat baking processes, etc., and severe conditions such as hot water immersion in a high temperature environment. The present invention relates to a decorative metal-tone film that is useful for giving beautiful decorations that do not cause an appearance abnormality even when left in a rough environment and does not whiten or bulge.

Conventionally, a metallic film is formed by, for example, depositing and laminating a metal layer on a surface resin layer made of a polyester film, an acrylic film, a vinyl chloride film, or the like by a method such as vacuum deposition or sputtering. Etc. are used.

In a metallic film produced using a polyester film as the surface resin layer, the adhesion between the metal layer and the polyester film is generally relatively good. However, the polyester resin itself is not suitable for exterior use because it has poor weather resistance, and the ordinary polyester film is hard, so it has poor curved surface followability and cannot be attached to a curved surface. there were.

In addition, in the metallic film produced using the acrylic film as the surface resin layer, the adhesion to the metal layer is relatively good as in the case of the polyester film. When the properties are improved, the flexibility tends to be lowered, and therefore, it is not possible to impart performance with excellent printability (solvent resistance) and flexibility.

In a metallic film produced using a vinyl chloride film as the surface resin layer, weather resistance, flexibility and solvent resistance are imparted to the film by selecting the type and amount of the vinyl chloride film constituent material. However, in this case, it is generally difficult to obtain close contact with the metal layer. Therefore, there is a problem that the metal layer is peeled off particularly in outdoor use. In addition, when used outdoors, the metal layer may be corroded and deteriorated by hydrochloric acid generated due to deterioration of the vinyl chloride resin, so that a metal film for an exterior having a truly good weather resistance has not been obtained.

Therefore, in order to solve the above disadvantages when using a vinyl chloride film, several measures have been tried, and a metal-tone film in which a first intermediate layer is interposed between the resin layer and the metal layer is proposed. Has been.

For example, in JP-A-1-221238 (Patent Document 1) and JP-A-2-4506 (Patent Document 2), a urethane resin and an acrylic resin are used as the first intermediate layer to suppress corrosion of the metal layer. Further, an example in which the adhesion with the surface resin layer is further improved is disclosed.

In addition, it improves adhesion between the surface resin layer made of vinyl chloride resin and the metal layer, prevents corrosion and deterioration of the metal layer, eliminates the above-mentioned drawbacks, and has sufficient weather resistance. In order to obtain a metallic film, a first intermediate layer is interposed between the vinyl chloride film and the metal layer, and a second intermediate layer is deposited on the metal layer. In addition, it is also proposed to be disposed between the intermediate layer and the second intermediate layer (Japanese Patent Laid-Open No. 2-286328). In this case, from the viewpoint of ensuring adhesion with the vinyl chloride film and securing adhesion with the metal layer, it was a preferred embodiment to use a urethane resin as the first intermediate layer.

In recent years, there has been an increasing demand to attach a metallic film to a resin substrate or the like, which is a member of an automobile, a motorcycle or the like, and decorate the member, but these members are exposed to high temperatures during a plurality of processing steps. There is a case. In this case, in the metal-tone film using the urethane-based resin for the first intermediate layer, the first intermediate layer is deformed at a high temperature, the metal layer is cracked, or the metal-like specularity disappears. A defect occurred.

JP-A-01-212238 Japanese Patent Laid-Open No. 02-4506 Japanese Patent Laid-Open No. 02-286328

The problem to be solved by the present invention is that it is left in a harsh environment such as a high temperature environment or immersion in hot water, even if it undergoes various processing steps exposed to a high temperature without impairing adhesion and weather resistance. It is an object of the present invention to provide a decorative metallic film in which the above-mentioned appearance abnormality does not occur and whitening or swelling does not occur.

The present inventors cross-linked two or more kinds of polyester polyol mixtures having different hydroxyl group contents by isocyanate crosslinking with a polyisocyanate compound having 0.4 to 0.8 equivalents of isocyanate groups with respect to the total hydroxyl groups in the polyester polyol. The said subject was solved by using a polyester-type urethane resin for an intermediate | middle layer, and using the film whose peak value of tan-delta by the dynamic viscoelasticity measurement of this crosslinked polyester-type urethane resin is 80-120 degreeC.

That is, the surface resin layer (A) made of a vinyl chloride resin is reacted with a polyisocyanate compound having 0.4 to 0.8 equivalents of isocyanate groups with respect to the total hydroxyl groups in the polyester polyol. It is a metal-like film deposited through an intermediate layer (B) formed of a polyester-based urethane resin, and the peak value of tan δ by dynamic viscoelasticity measurement of the crosslinked polyester-based urethane resin of the intermediate layer is It is a metallic film characterized by being 80 to 120 ° C.,

Preferably, in the intermediate layer (B), a mixture of a polyester polyol (b1) having a hydroxyl group content of 7% or more and a polyester polyol (b2) having a hydroxyl group content of 5% or less is reacted with a polyisocyanate compound. It is a metallic film that is a polyester-based urethane resin,

More preferably, the polyester resin constituting the intermediate layer (B) is made of a resin obtained by mixing the polyester polyol (b1) and the polyester polyol (b2) in a range of 75/25 to 55/45 by weight ratio, The subject matter is solved by a metal film in which the polyisocyanate compound functioning as a crosslinking agent for the mixed resin is an alicyclic polyisocyanate.

The metallic film of the present invention is bonded to an adherend through a surface resin layer (A), an intermediate layer (B), a metal layer (C), and an adhesive layer.

In the present invention, the surface resin layer (A) is formed of a vinyl chloride resin, and the thickness thereof is adjusted to 20 to 200 μm, preferably 25 to 100 μm, more preferably 30 to 70 μm. If the thickness of the surface resin layer is within the above-mentioned preferable range, it is preferable because good adhesion workability can be secured.

The surface resin layer (A) is prepared as a flexible film having a tensile strength at 5% elongation of 20 N / cm or less. If the tensile strength at 5% elongation is 20 N / cm or less, curved surface sticking property can be maintained, which is preferable.

Further, the surface resin layer (A) is adjusted so that the total light transmittance is 30% or more, preferably 40% or more, more preferably 50% or more. A total light transmittance of 30% or more is preferable because the metallic gloss can be maintained.

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. In this resin composition, various additives such as ultraviolet absorbers, various stabilizers, antioxidants, modifier resins, colorants and the like can be included as necessary within the range that satisfies the above conditions. Those having weather resistance are particularly preferable.

In addition, as said resin composition, the thing for semi-rigid vinyl chloride resin shaping | molding which consists of the following composition can be mentioned as a preferable example. That is, (b) 100 parts by weight of a vinyl chloride resin containing 0 to 20% by weight of a copolymer component, (b) a liquid polyester plasticizer having a number average molecular weight (Mn) of 1,500 or more is 1 to 20 parts by weight, and 0 to 10 parts by weight of another plasticizer for vinyl chloride resin, and (c) ethylene / saturated carboxylic acid vinyl ester / carbon monoxide copolymer resin in the main chain
This is a composition comprising an ethylene / vinyl ester-based resin having an amount of 45 to 350% by weight with respect to the total amount of the plasticizer (b) and a yield stress of 9 to 60 MPa.

In the above composition, the vinyl chloride resin (a) is not particularly limited, and any vinyl chloride resin that is usually used for molding can be appropriately selected and used. The vinyl chloride resin may be a copolymer containing up to 20% by weight, preferably 10% by weight, and more preferably up to 6% by weight, in addition to the vinyl chloride homopolymer. Good. As such a copolymer component, any vinyl monomer copolymerizable with a vinyl chloride monomer can be used without particular limitation.

In the above composition, the plasticizer (b) is 1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin (a). Liquid polyester plasticizers and other plasticizers for vinyl chloride resin of 0 to 10 parts by weight.

The number average molecular weight (Mn) of the liquid polyester plasticizer is 1,500 or more, preferably 1,500 to 6,000, more preferably 1,500 to 4,000. Examples of the liquid polyester plasticizer include liquid polyesters derived from a dibasic acid having 4 to 15 carbon atoms and a dihydric alcohol having 2 to 20 carbon atoms. Among them, adipic acid, phthalic acid, Preferred examples include liquid polyesters derived from 1 to 2 types selected from maleic acid and 1 to 3 types selected from propylene glycol, dipropylene glycol, hexanediol, and butanediol. .

Moreover, there is no restriction | limiting in particular as a plasticizer for vinyl chloride resins which can be used together, Normal plasticizers, such as a phthalate ester and an epoxy compound, can be mentioned.

In the composition, the ethylene / vinyl ester-based resin (c) is preferably contained in an amount of 45 to 350% by weight, particularly 50 to 300% by weight, based on the total amount of the plasticizer (b).
Examples of the vinyl ester used for the production of the resin (c) include vinyl acetate and propionate.

In the composition, the yield stress is 9 to 60 MPa, preferably 9 to 50 MPa, and more preferably 11 to 45 MPa.

When a metal film is prepared using a film made of a composition that satisfies the above-described requirements, it is required as a metal film, such as printability, curved surface stickability, UV absorber retention, weather resistance, etc. It has various characteristics.

In the present invention, the intermediate layer (B) is a crosslinked polyester-based urethane resin obtained by crosslinking a mixture of two types of polyester polyols (b1, b2) with an isocyanate crosslinking agent.
As the polyester polyol, a known polyester polyol can be used, and examples thereof include a polyester polyol obtained by condensation reaction of a low molecular weight diol component and a dibasic acid component. Examples of the low molecular weight diol include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′- Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol , Cyclohexanediol, bisphenol A and the like. Further, glycerin, trimethylolpropane, pentaerythritol and the like may be used in combination with a low molecular weight diol. Examples of the dibasic acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and other aliphatic dibasic acids or aromatic dibasic acids. .
Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones such as poly (ε-caprolactone), poly (β-methyl-γ-valerolactone), and polyvalerolactone can also be used.

In the present invention, the polyester polyol used in the intermediate layer (B) includes a high hydroxyl group polyester polyol (b1) having a hydroxyl group content of 7% or more and a low hydroxyl group polyester polyol (b2) having a hydroxyl group content of 5% or less. However, the formation layer becomes too brittle with only the high hydroxyl group polyester polyol (b1), and the formation layer becomes too soft with only the low hydroxyl group polyester polyol (b2). Therefore, it is preferable to adjust the brittleness.

The high hydroxyl group polyester polyol (b1) here needs to have a hydroxyl group content of 7% or more, preferably 7 to 12%. If the hydroxyl group content of the high hydroxyl group polyester polyol (b1) is 7% or more, a sufficient degree of crosslinking can be obtained, and if it is less than 12%, the formation layer is preferably not too brittle.

The low hydroxyl group polyester polyol (b2) needs to have a hydroxyl group content of less than 5%, and more preferably 0.5 to 5%. If the hydroxyl group content of the low hydroxyl group polyester polyol (b2) is less than 5%, it can be a high molecular weight plasticizer, which is preferable.

The polyester polyol constituting the intermediate layer (B) has a weight ratio of 75/25 to 55/45, preferably 70/30 to 60/40 of the high hydroxyl polyester polyol (b1) and the low hydroxyl polyester polyol (b2). It is a resin mixed in proportion.
In the above blending ratio, if the ratio of the high hydroxyl group polyester polyol is increased, the formed layer can be made brittle, and if the ratio of the low hydroxyl group polyester polyol is increased, the formed layer can be softened. In addition, it can be arbitrarily determined as long as it is within the above preferred range.

In the present invention, the intermediate layer (B) is made of a polyurethane resin obtained by crosslinking a mixture of two kinds of polyester polyols (b1, b2) with a polyisocyanate compound.
As the polyisocyanate compound, known aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate and the like can be used.
Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4. '-Toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, Examples include 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane Etc.
Moreover, the adduct type modified body, burette type modified body, and isocyanurate type modified body of the polyisocyanate mentioned above may be sufficient.

Among the polyisocyanate compounds described above, alicyclic polyisocyanates are preferable from the viewpoint of ensuring excellent heat resistance, and IPDI and modified products thereof are particularly preferable.

The polyisocyanate compound is preferably added in an amount of 0.4 to 0.8 equivalent of an isocyanate component based on the total hydroxyl groups of the polyester polyol mixture.
The crosslinked polyester urethane resin used for the intermediate layer (B) of the present invention crosslinks a part of the hydroxyl groups of the polyester polyol. By leaving a specific amount of hydroxyl groups, the surface resin layer (A) and the metal layer Excellent adhesion to both layers is ensured.

The thickness of the intermediate layer (B) is adjusted to 0.5 to 50 μ, preferably 1 to 30 μ, and more preferably 2 to 20 μ. If the thickness of the intermediate layer (B) is set within the above preferred range, the metal layer is stably fixed, and further, the metal layer is protected from hydrochloric acid and the like due to deterioration of the vinyl chloride resin, Moreover, it is preferable because migration of the compounding agent and the like from the vinyl chloride film can be effectively prevented.

Further, the total light transmittance of the first intermediate layer (B) is adjusted to 30% or more. A total light transmittance of 30% or more is preferable because the metallic luster is not lost.

Furthermore, various compounding agents can be added to the first intermediate layer (B) as long as the above conditions such as light transmittance are satisfied. Examples of the compounding agent include colorants such as general pigments, pearl pigments and metal foils, ultraviolet absorbers, various stabilizers, coupling agents, antioxidants, modifiers and the like.

Among them, it is a preferable embodiment to add a silane coupling agent as a coupling agent used for further improving the adhesion with the metal layer (C).

Examples of silane coupling agents include mercapto group-containing silane compounds, alicyclic epoxy group-containing silane compounds, epoxy group-containing silane compounds, carboxyl group-containing silane compounds, amino group-containing silane compounds, hydroxyl group-containing silane compounds, and amide group-containing silanes. A compound, an isocyanate group-containing silane compound, or the like can be used.

Among these silane compounds, for example, methyltri (glycidyl) silane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Use of an epoxy group-containing silane compound typified by glycidoxypropyltriethoxysilane is preferred.

The silane coupling agent is used in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the polyester urethane resin. If the amount used is within a suitable range, it is preferable because inconveniences such as peeling of the metal layer hardly occur.

In the present invention, the metal layer (C) can be formed of the following metal, and the thickness thereof varies depending on the metal used, but is 100 to 2,000 mm, preferably 300 to 1,500 mm. If the thickness of the metal layer (C) is set within the above preferred range, the metal layer (C) maintains a sufficient concealing property, and the metal layer (C) does not crack due to deformation of the sheet. Therefore, it is preferable.

In the present invention, the metal layer (C) is deposited and laminated by a vapor deposition method, a sputtering method, a plasma method or the like. The metal that forms the metal layer (C) of the present invention is not particularly limited, and examples thereof include metals such as aluminum, gold, silver, copper, tin, chromium, and indium. In view of the properties and the like, aluminum, tin, indium, and chromium are preferable, and it is particularly preferable to use aluminum, tin, and indium excellent in corrosiveness. In addition, you may form the said metal layer (C) with the alloy which consists of 2 or more types of metals.

Furthermore, in this invention, you may form a protective layer (D) in the surface on the opposite side to the said intermediate | middle layer (B) of a metal layer (C).

The metallic film of the present invention is used as a laminate in which a pressure-sensitive adhesive layer or an adhesive layer is provided on the metal layer (C) surface or the protective layer (D) surface, and a release paper is further laminated. Alternatively, it can be attached to a desired adherend through an adhesive layer. Although there is no restriction | limiting in the structure of the said adhesive layer or an adhesive bond layer, It is preferable to form with an acrylic adhesive or adhesive with good water resistance.

In the metallic film of the present invention, the peak value of tan δ by dynamic viscoelasticity measurement of the crosslinked polyester urethane resin forming the intermediate layer (B) of the laminated film is 80 to 120 ° C, preferably 90 to 110 ° C. It is characterized by. When the peak value of tan δ is within the above preferred range, excellent heat resistance and excellent workability can be ensured.

Here, tan δ by dynamic tensile viscoelasticity measurement is a value measured according to, for example, JIS K-7244-4.

Next, one aspect of a production method suitable for producing the metallic film of the present invention will be described. The metallic film of the present invention can be easily and reliably produced by the following method.

That is, first, a support film is prepared, and a surface resin layer (A) is deposited on one surface of the support film. The support film is not particularly limited as long as it is a film or paper made of a material that can withstand manufacturing conditions such as tension, heat, and solvent in each manufacturing process and processing process, and is generally called a process film or a process paper. However, a polyester film is preferably used in terms of surface smoothness and thickness accuracy.

Further, the method for forming the surface layer (A) is not particularly limited, and examples thereof include a spray method, a printing method, a coating method, etc. Among them, there is a solution coating method that is excellent in workability and thickness accuracy. Is preferred.

Next, an intermediate layer (B) made of a crosslinked polyester urethane resin is deposited on the surface layer (A) formed on the support film. The method for forming the intermediate layer (B) is not particularly limited, and a spray method, a printing method, a coating method, or the like can be adopted as in the case of the surface resin layer (A). Can also adopt a heat laminating method.

Further, a metal layer (C) is deposited on the intermediate layer (B) formed on the surface layer (A). As the method for forming the metal layer (C), as described above, a vacuum deposition method, a sputtering method, or a plasma method is employed.

After forming the metal layer (C) as described above, a protective layer (D) made of an acrylic resin may be deposited on the other surface of the metal layer (C). The deposition can be performed in the same manner as in the case of the intermediate layer (B), for example. Then, the metallic film of this invention is formed by peeling the said support film from a surface layer (A).

In addition, for example, it is needless to say that various treatments may be performed without peeling the metal-like film from the support film until the step of laminating the pressure-sensitive adhesive and the adhesive on the metal-like film and further laminating the release paper. Absent.

According to the manufacturing method described above, since the support film functions as a carrier for fixing each layer of the metal tone film in each step, and also functions as a protective layer for the surface resin layer, the metal tone film can be easily and reliably formed. In addition, it is possible to effectively prevent the surface from being damaged by an external factor in each step.
In the above manufacturing method, a step of forming another layer such as a surface coat layer may be added as necessary.

Hereinafter, the metallic film of the present invention will be described in more detail with reference to Examples and Examples. First, test methods performed in Reference Examples, Examples, and Comparative Examples described later will be described.

Total light transmittance
The laminated film before vapor deposition of the present invention was used as a measurement sample.
In addition, the measurement used NDH2000 (made by Nippon Denshoku Industries Co., Ltd.) as an apparatus, and measured the total light transmittance based on JIS K-7361-1.

Measurement of tan δ Each resin compounding solution shown in Table 1 was coated and dried on PL75GS (manufactured by Lintec), which is a PET film treated with silicone, to form an intermediate layer (B) of about 30 μm.
Thereafter, the sample was cut into a strip shape having a width of 10 mm and a length of 20 mm to obtain a measurement sample.
In addition, the measurement used DMS6100 (made by Seiko Instruments) as an apparatus, measured dynamic viscoelasticity, and computed tan (delta) based on JISK-7244-4.
Detailed measurement conditions are shown below.
Distance between clamps = 10 mm, frequency = 1 Hz, measurement temperature range = 25 to 140 ° C., heating rate = 3 ° C./min

The heat-resistant metal-like film was cut into 50 mm × 50 mm, and the release paper was peeled off, and then attached on a glass plate using a squeegee. Next, this was allowed to stand at room temperature for 24 hours, and then gently left for 40 minutes in a hot-air circulating dryer adjusted to 140 ° C. for heat treatment. After completion of the heat treatment, the panel was taken out, the state of cracks in the metal layer was visually observed, and the heat resistance of the metallic film was evaluated in three stages of ○, Δ, and × according to the following evaluation method.

◯: The metal layer has no cracks and has a mirror surface property.
Δ: Cracks are observed in a part of the metal layer.
X: The metal layer has cracks and the specularity is lost.

Adhesive of the intermediate layer (B) with respect to the surface layer (A) is laminated on the film in the stage before vapor deposition, and this is attached to an aluminum plate, immersed in 80 ° C. hot water for 4 hours, and then taken out. After leaving at room temperature for 24 hours, an attempt was made to separate the surface layer and the intermediate layer using a feather blade, and the adhesion between the surface layer (A) and the intermediate layer (B) was evaluated according to the following evaluation method. Was evaluated with ○ and ×.

○: The surface layer and the intermediate layer cannot be separated.
X: The surface layer and the intermediate layer can be separated.

Adhesion of metal layer (C)
The cellophane tape is pressure-bonded to the metal layer side of the test piece in the stage before the pressure-sensitive adhesive layer (or adhesive layer) is laminated, and the peeling state of the metal layer when the cellophane tape is peeled off is visually observed. Observed, the adhesion between the metal layer (C) and the intermediate layer (B) was evaluated by ○ and × according to the following evaluation method.
○: The metal layer does not peel off.
X: The metal layer peels even at a part.

The film prior to 40 ° C. warm water metal layer deposition was immersed in warm water at 40 ° C. for 168 hours, and the degree of whitening of the film at that time was visually observed, and the warm water resistance of the film was evaluated according to the following evaluation method. , Δ, and x were evaluated in three stages.
○: No whitening occurred.
Δ: Extremely thin whitening occurs on the entire surface or a part of the film.
X: Whitening occurs on the entire surface of the film.

The film before deposition of the boiling-resistant aqueous metal layer was immersed in boiling water for 5 minutes, and the degree of whitening of the film at that time was visually observed and evaluated according to the same criteria as in the previous section.

Reference Example 1 Preparation of Crosslinked Polyester-Based Urethane Resin Solution Desmophen 651MPA / X (66.5% solution made by Sumika Bayer Urethane: 5.4% as hydroxyl content) 70 parts by weight as high hydroxyl polyester polyol, desmophene as low hydroxyl polyester polyol 670BA (80.3% solution made by Sumika Bayer Urethane: 3.4% as hydroxyl content), Desmodur Z4470BA (made by Sumika Bayer Urethane: isocyanate group content) which is an alicyclic polyisocyanate as a crosslinking agent 11.7%) 50.7 parts by weight, 0.07 part by weight of Silaace S510 (manufactured by Chisso), which is an epoxy group-containing silane compound as an adhesion improver with the metal layer, and dibutyltin dilaurate (IV) (IV) as a crosslinking accelerator Wako Pure Chemical Industries) 0.022 parts by weight To prepare a cross-linked polyester urethane resin solution A shown in Table 1 were mixed by stirring 92 parts by weight of methyl isobutyl ketone (MIBK) (manufactured by Yamaichi Chemical Industries) as a solution viscosity modifier.

Reference Example 2 to Reference Example 4, Comparative Reference Example 1 to Comparative Reference Example 4
The cross-linked polyester-based urethane resin solutions B to H shown in Table 1 were prepared in the same manner as in Reference Example 1 except that the blending ratio of the polyester polyol and the amount of polyisocyanate added were changed as shown in Table 1.

Example 1
A resin solution A is applied to a vinyl chloride resin (PVC) film substrate (N-15, manufactured by Nippon Carbide Industries) using an applicator, and 90 ° C. × 2.5 minutes + 140 ° C. using a hot air circulation dryer. The resin solution A was dried under conditions of × 10 minutes, and an intermediate layer having a thickness of 10 μm was laminated.
Next, aluminum is vapor-deposited on the intermediate layer using a vacuum deposition apparatus (manufactured by BMC-500 SYNCHRON) so that the thickness is about 1,000 mm, and a laminate of PVC film substrate / intermediate layer / metal layer (1) Obtained.

Formation of Adhesive Layer On PL75GS (manufactured by Lintec), which is a PET film treated with silicone, 100 parts by weight of PE-121L (manufactured by Nippon Carbide Industries) and 0.3 part by weight of a crosslinking agent CK-117 (manufactured by Nippon Carbide Industries), viscosity An acrylic pressure-sensitive adhesive solution prepared by mixing and stirring 20 parts by weight of tertiary butanol (t-BuOH) (manufactured by Wako Pure Chemical Industries, Ltd.) serving as a regulator is coated and dried, and an adhesive layer of about 30 μm and a laminate ( The laminated body concerning this invention was obtained by bonding together the metal layer of 1). Various physical properties of the laminate are shown in Table 2.

Example 2 to Example 4
Each laminate was obtained in the same manner as in Example 1 except that the resin solution A was changed to the resin solutions B to D. Table 2 shows various physical property values of the obtained laminate.

Comparative Examples 1 to 4
Each laminated body was obtained like Example 1 except having changed the resin solution A into resin solution EH. Table 2 shows various physical property values of the obtained laminate.

Claims (6)

The surface resin layer (A) made of vinyl chloride resin was reacted with a polyisocyanate compound in which the metal layer (C) had 0.4 to 0.8 equivalents of isocyanate groups with respect to the total hydroxyl groups in the polyester polyol. A decorative metallic-tone film formed through an intermediate layer (B) formed of a polyester-based urethane resin, wherein the peak value of tan δ by dynamic viscoelasticity measurement of the polyester-based urethane resin is 80 to 120 A decorative metallic film characterized by a temperature of ° C. The polyester system in which the intermediate layer (B) is crosslinked by reacting a mixture of a polyester polyol (b1) having a hydroxyl group content of 7% or more and a polyester polyol (b2) having a hydroxyl group content of 5% or less with an isocyanate compound. The decorative metal-tone film according to claim 1, which is a urethane resin. The polyester resin constituting the intermediate layer (B) is a resin in which the polyester polyol (b1) and the polyester polyol (b2) are mixed in a weight ratio of 75/25 to 55/45. Item 3. A decorative metallic film according to any one of Items 2 to 3. The decorative polytone film according to any one of claims 1 to 3, wherein the polyisocyanate compound is an alicyclic polyisocyanate compound. The decorative metal-tone film according to any one of claims 1 to 4 , further comprising a silane coupling agent in the intermediate layer (B). The decorative metallic film according to claim 1, wherein a protective layer (D) is formed on the surface of the metal layer (C) opposite to the intermediate layer (B).