JP2018126938A - Film for metal vapor deposition and metal vapor-deposited film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal vapor-deposited film having excellent adhesion, mirror surface glossiness, and molding properties, and also provide a film for metal vapor deposition for obtaining the metal vapor-deposited film.SOLUTION: A film for metal vapor deposition has a curable resin layer on at least one side of a base film, the curable resin layer being a layer obtained by curing a composition containing a urethane compound having a cyclic skeleton and a reactive inorganic particle.SELECTED DRAWING: None

Description

  The present invention relates to a metal deposition film and a metal deposition film.

  Since a metal vapor deposition film can give properties such as gas barrier properties, light shielding properties, heat ray reflectivity, conductivity, magnetic recording properties, and designability (beauty) by selecting a vapor deposition metal, It is used in various applications such as packaging materials, decorative materials, window glass shielding materials, capacitor materials, display materials, wiring board materials, magnetic recording materials, conductive materials, gas barrier materials, and the like.

  However, the metal vapor deposition film has a problem in adhesion between the base film and the metal vapor deposition film. In order to improve such adhesiveness etc., providing an undercoat layer between a base film and a metal vapor deposition film is proposed (patent documents 1-6).

JP 2007-118479 A JP 2008-179893 A JP 2009-286035 A JP2011-94108A JP 2012-162715 A JP 2014-58154 A

  As described above, the metal vapor deposition film is used for various applications. In addition to the adhesion of the metal vapor deposition film, for example, it has high specular gloss to enhance design and heat ray reflectivity, and a curved surface shape. It is demanded that the moldability to be good.

  However, none of the metal vapor-deposited films described in the above-mentioned patent documents sufficiently satisfy the adhesion, specular gloss, and moldability.

  Therefore, in view of the above problems, an object of the present invention is to provide a metal vapor-deposited film having good adhesion, specular gloss, and moldability. Another object of the present invention is to provide a metal deposition film for obtaining such a metal deposition film.

The above object of the present invention is achieved by the following present invention.
[1] A metal deposition film having a cured resin layer on at least one surface of a base film, wherein the cured resin layer is cured from a composition containing a urethane compound having a cyclic skeleton and reactive inorganic particles. A film for metal vapor deposition, which is a layer.
[2] The film for metal vapor deposition according to [1], wherein the urethane compound having a cyclic skeleton is a urethane (meth) acrylate compound.
[3] The film for metal vapor deposition according to [1] or [2], wherein the reactive inorganic particles are silica particles having an ethylenically unsaturated group.
[4] The metal deposition film according to any one of [1] to [3], wherein the cured resin layer has a surface roughness (Ra) measured by an atomic force microscope (AFM) of less than 2.0 nm. .
[5] The film for metal vapor deposition according to any one of [1] to [4], wherein an indentation hardness measured by a nanoindentation method of the cured resin layer is in a range of 200 to 600 N / mm ² .
[6] The metal deposition film according to any one of [1] to [5], wherein the cured resin layer has a tensile crack elongation of 10% or more.
[7] The metal deposition film according to any one of [1] to [6], wherein the cured resin layer is an active energy ray-curable resin layer.
[8] A metal vapor deposition film obtained by laminating a metal vapor deposition film on the cured resin layer of the metal vapor deposition film according to any one of [1] to [7].
[9] The metal deposited film according to [8], wherein the gloss of the metal deposited film is 100 or more.

  ADVANTAGE OF THE INVENTION According to this invention, the metal vapor deposition film with favorable adhesiveness, specular glossiness, and moldability, and the film for metal vapor deposition for obtaining this metal vapor deposition film can be provided.

  The film for metal vapor deposition of this invention is used in order to obtain a metal vapor deposition film. That is, a metal vapor deposition film is obtained by laminating a metal vapor deposition film on the cured resin layer of the metal vapor deposition film of the present invention.

  The film for metal vapor deposition of the present invention has a cured resin layer on at least one surface of a base film, and the cured resin layer is a layer obtained by curing a composition containing a urethane compound having a cyclic skeleton and reactive inorganic particles. It is characterized by being.

  Hereinafter, each element which comprises the film for metal vapor deposition of this invention is demonstrated in detail.

[Base film]
The base film in the present invention is preferably a plastic film. Examples of the material constituting the base film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, and polymethacrylic. Examples include methyl acid, alicyclic acrylic resin, cycloolefin resin, triacetyl cellulose, and those obtained by mixing and / or copolymerizing these resins. A film obtained by unstretching, uniaxially stretching, or biaxially stretching these resins can be used as a base film.

  Among the above-mentioned base films, polyester films are preferable because they are excellent in dimensional stability, mechanical properties, heat resistance, electrical properties, chemical resistance, etc., and particularly polyethylene terephthalate films (PET films) are preferable. Among these, a biaxially stretched PET film is preferably used.

  The range of 20-300 micrometers is suitable for the thickness of a base film, the range of 30-250 micrometers is preferable, and the range of 50-200 micrometers is more preferable.

  It is preferable that the base film is preliminarily laminated with an easy-adhesion layer as shown below on at least the surface on which the cured resin layer is laminated.

[Easily adhesive layer]
In order to reinforce the adhesion between the base film and the cured resin layer, the base film is preferably provided with an easy adhesion layer on the surface on which the cured resin layer is laminated. Furthermore, it is more preferable that the easy-adhesion layer is laminated on both surfaces of the base film. By laminating the easy-adhesion layer on both surfaces of the base film, even if a cured resin layer having high smoothness is laminated on one surface, good slipperiness and blocking resistance can be ensured.

  The easy adhesion layer is a layer containing a resin as a main component. Here, containing resin as a main component means containing 50 mass% or more of resin with respect to 100 mass% of solid content total amount of an easily bonding layer. Examples of the resin forming the easy adhesion layer include polyester resin, acrylic resin, urethane resin, polycarbonate resin, epoxy resin, alkyd resin, urea resin, and the like. These resins can be used alone or in combination.

  The easy adhesion layer preferably contains at least one selected from the group consisting of a polyester resin, an acrylic resin and a polyurethane resin from the viewpoint of improving the adhesion between the base film and the cured resin layer. In particular, a polyester resin is preferable.

  The content of the resin in the easy adhesion layer is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more with respect to 100% by mass of the total solid content of the easy adhesion layer. Regarding the upper limit, the content of the resin in the easy-adhesion layer is preferably 95% by mass or less, and more preferably 90% by mass or less.

  Further, the easy adhesion layer may be formed in a two-layer structure. In the case of a two-layer structure, it is preferable that the first layer is composed of a polyester resin as a main component and the second layer is composed of an acrylic resin as a main component in order from the base film side. This easy-adhesion layer having a two-layer structure is obtained by applying one coating solution containing a polyester resin and an acrylic resin once, and in the drying process, the first layer containing the polyester resin and the second layer containing the acrylic resin are combined. It can be formed by separating.

  It is preferable that an easily bonding layer contains particle | grains from a viewpoint of ensuring appropriate slipperiness and winding-up property in the manufacturing process of the film for metal vapor deposition.

  The particles contained in the easy adhesion layer are not particularly limited, but inorganic particles such as silica particles, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, zeolite particles, acrylic particles, silicone particles, polyimide particles, Teflon (registered) (Trademark) particles, crosslinked polyester particles, crosslinked polystyrene particles, and core-shell particles. Among these, silica particles are preferable, and colloidal silica is particularly preferable.

  The particles contained in the easy adhesion layer preferably have an arithmetic average particle size larger than the thickness of the easy adhesion layer. Specifically, the arithmetic average particle diameter is preferably 1.3 times or more, more preferably 1.5 times or more, and particularly preferably 2.0 times or more the thickness of the easy adhesion layer. The upper limit is preferably 20 times or less, more preferably 15 times or less, and particularly preferably 10 times or less.

  The arithmetic average particle size of the particles contained in the easy-adhesion layer is appropriately selected according to the thickness design of the easy-adhesion layer. Specifically, the arithmetic average particle size is preferably in the range of 0.02 to 1 μm. The range of 0.05 to 0.7 μm is more preferable, and the range of 0.1 to 0.5 μm is particularly preferable. If the arithmetic average particle size is less than 0.02 μm, the slipperiness may be lowered. When the arithmetic average particle diameter exceeds 1 μm, the particles may fall off, the transparency may deteriorate, or the appearance may deteriorate.

  The thickness of the easy adhesion layer is preferably in the range of 0.005 to 0.3 μm. When the thickness of an easily bonding layer is less than 0.005 micrometer, the adhesiveness of a base film and a cured resin layer may fall. Moreover, when the thickness of an easily bonding layer becomes larger than 0.3 micrometer, the blocking resistance after laminating | stacking a cured resin layer may fall. In addition, when the easily bonding layer is comprised with multiple layers, let the total thickness of multiple layers be the thickness of an easily bonding layer.

  From the above viewpoint, the thickness of the easy adhesion layer is preferably 0.010 μm or more, more preferably 0.015 μm or more, and particularly preferably 0.020 μm or more. Regarding the upper limit, the thickness of the easy adhesion layer is preferably 0.25 μm or less, preferably 0.20 μm or less, and particularly preferably 0.15 μm or less.

  The content of the particles in the easy-adhesion layer is preferably in the range of 0.05 to 10% by mass, more preferably in the range of 0.1 to 8% by mass, particularly 0% with respect to 100% by mass of the total solid content of the easy-adhesion layer. The range of 5-5 mass% is preferable. When the content of the particles in the easy-adhesion layer is less than 0.05% by mass, good slipperiness may not be obtained, and when the content of the particles exceeds 10% by mass, the transparency may be lowered, The applicability of the cured resin layer may deteriorate, or the smoothness of the cured resin layer may decrease.

  The easy-adhesion layer preferably further contains a crosslinking agent. The easy adhesion layer is preferably a thermosetting layer containing the above-described resin and a crosslinking agent. By making the easy-adhesion layer into such a thermosetting layer, the adhesion between the base film and the cured resin layer can be further improved. The conditions (heating temperature, time) for thermosetting the easy-adhesion layer are not particularly limited, but the heating temperature is preferably 70 ° C or higher, more preferably 100 ° C or higher, particularly preferably 150 ° C or higher, and most preferably 200 ° C or higher. preferable. Regarding the upper limit, the heating temperature is preferably 300 ° C. or lower. The range of the heating time is preferably from 5 to 300 seconds, more preferably from 10 to 200 seconds.

  Examples of the crosslinking agent include melamine crosslinking agent, oxazoline crosslinking agent, carbodiimide crosslinking agent, isocyanate crosslinking agent, aziridine crosslinking agent, epoxy crosslinking agent, methylolated or alkylolized urea crosslinking agent, acrylamide Examples thereof include system crosslinking agents, polyamide resins, amide epoxy compounds, various silane coupling agents, and various titanate coupling agents. Among these, melamine-based crosslinking agents, oxazoline-based crosslinking agents, carbodiimide-based crosslinking agents, isocyanate-based crosslinking agents, and aziridine-based crosslinking agents are preferable, and melamine-based crosslinking agents are particularly preferable.

  Examples of the melamine-based crosslinking agent include imino group type methylated melamine resin, methylol group type melamine resin, methylol group type methylated melamine resin, and fully alkyl type methylated melamine resin. Among these, imino group type melamine resins and methylolated melamine resins are preferably used.

  The content of the crosslinking agent in the easy-adhesion layer is preferably in the range of 0.5 to 40% by mass, more preferably in the range of 1 to 30% by mass with respect to 100% by mass of the total solid content of the easy-adhesion layer. A range of 20% by weight is preferred.

[Hardened resin layer]
The cured resin layer in the present invention is a layer obtained by curing a composition containing a urethane compound having a cyclic skeleton and reactive inorganic particles.

  The cured resin layer in the present invention is preferably a thermosetting resin layer or an active energy ray curable resin layer, and particularly preferably an active energy ray curable resin layer.

  The thermosetting resin layer heats a coating film containing, for example, a crosslinking agent (for example, a melamine crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, or an epoxy crosslinking agent). It is obtained by doing.

  The active energy ray cured resin layer is a cured resin layer cured by irradiating the coating film with active energy rays such as ultraviolet rays and electron beams. Details of the active energy ray-curable resin layer will be described later.

[Urethane compound having a cyclic skeleton]
A urethane compound having a cyclic skeleton has a cyclic skeleton in the molecule. Here, examples of the cyclic skeleton include an aromatic ring, an alicyclic ring, a heterocyclic ring, and a composite ring thereof.

  Examples of the aromatic ring include benzene, naphthalene, anthracene, and fluorene.

  Examples of the alicyclic ring include cycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, tricyclodecane, cyclopentene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, and the like. Of the cycloalkene.

  Examples of the heterocyclic ring include thiophene, furan, pyrrole, tetrahydrothiophene, tetrahydrofuran, pyridine, tetrahydrothiopian, tetrahydropyran, piperidine, pyridine, imidazole, oxazole, thiazole, pyrazine, morpholine, thiazine, purine, and pteridine. .

  Examples of the complex ring include indole, benzimidazole, quinoline, chromene, and isochromene.

  Among the cyclic skeletons described above, an aromatic ring is particularly preferable.

  The urethane compound can be obtained, for example, by polymerizing a polyol compound and a polyisocyanate compound. The urethane compound having a cyclic skeleton in the present invention can be synthesized by using a compound having a cyclic skeleton in one or both of a polyol compound and a polyisocyanate compound.

  The urethane compound having a cyclic skeleton in the present invention is preferably synthesized using a polyol compound having a cyclic skeleton. The polyisocyanate compound used for this synthesis may or may not have a cyclic skeleton.

[Polyol compound having a cyclic skeleton]
Examples of the polyol compound having a cyclic skeleton include the following compounds (a1) to (a4).
(A1) Epoxy (meth) acrylate compound obtained by reacting a diepoxy compound having a cyclic skeleton in the molecule with (meth) acrylic acid. Here, (meth) acrylic acid means “acrylic acid” and “ It is a generic term including “methacrylic acid”, and “... (Meth) acrylate” is a generic term for “acrylate” and “methacrylate”, and the same applies in the following description.

As a diepoxy compound having a cyclic skeleton in the molecule,
For example, diepoxy compounds of aromatic glycols such as bisphenol A type, hydrogenated bisphenol A type, bisphenol F type, hydrogenated bisphenol F type, resorcin, hydroquinone, and their alkylene oxide adducts,
Cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, norbornanediol, norbornanedimethanol, norbornanediethanol, decalindiol, decalindimethanol, decalindiethanol, etc. Compound,
Diepoxy compounds such as phthalic acid, isophthalic acid, terephthalic acid,
Fats such as 3,4-epoxycyclohexylmethylcarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro 3,4-epoxy) cyclohexane-metadioxane, bis (3,4-epoxycyclohexyl) adipate Cyclic epoxy compounds, etc.
Is mentioned.
(A2) Alicyclic polyhydric alcohol For example, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated dimer diol, cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, norbornane Diol, norbornane dimethanol, norbornane diethanol, decalin diol, decalin dimethanol, decalin diethanol, bis (hydroxy) cyclohexane, bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) cyclohexane, bis (hydroxypropyl) cyclohexane, bis (hydroxymethoxy) ) Cyclohexane, bis (hydroxyethoxy) cyclohexane, bis (hydroxymethoxy) Rohexyl) propane, bis (hydroxyethoxycyclohexyl) propane, bis (hydroxycyclohexyl) methane, bis (hydroxycyclohexyl) propane, bis (hydroxymethyl) cyclopropane, bis (hydroxymethyl) cyclobutane, bis (hydroxymethyl) cyclopentane, bis (Hydroxymethyl) cycloheptane, bis (hydroxymethyl) cyclooctane, bis (hydroxymethyl) cyclononane, bis (hydroxymethyl) cyclodecane, bis (hydroxymethyl) cycloundecane, bis (hydroxymethyl) cyclododecane, bis (hydroxymethyl) Bicyclobutane, bis (hydroxymethyl) bicyclopentane, bis (hydroxymethyl) bicyclohexane, bis (hydroxymethyl) bicyclo Butane, bis (hydroxymethyl) bicyclooctane, bis (hydroxymethyl) bicyclononane, bis (hydroxymethyl) bicyclodecane, bis (hydroxymethyl) bicycloundecane, bis (hydroxymethyl) bicyclododecane, bis (hydroxymethyl) tricycloheptane, Bis (hydroxymethyl) tricyclooctane, bis (hydroxymethyl) tricyclononane, bis (hydroxymethyl) tricycloundecane, bis (hydroxymethyl) tricyclododecane, bis (hydroxymethyl) spirooctane, bis (hydroxymethyl) spirononan Bis (hydroxymethyl) spirodecane, bis (hydroxymethyl) spirodecane, bis (hydroxymethyl) spirododecane, bis (hydroxymethyl) cyclo Down chest pyro cyclobutane, bis (hydroxymethyl) cyclohexane spiro cyclopentane and the like.
(A3) Aromatic polyol For example, aromatic glycols such as bisphenol A type, bisphenol F type, resorcin, hydroquinone, and their alkylene oxide adducts, or polyethylene terephthalate diol, polyethylene isophthalate diol, polyhexamethylene isophthalate adipate Examples thereof include aromatic polyester polyols such as diols, and alkylene oxide adducts thereof.
(A4) Polyester polyol having an alicyclic skeleton For example, a) a polycondensation product of a polyhydric alcohol having an alicyclic skeleton and a polycarboxylic acid, and b) a polyvalent carboxylic having a polyhydric alcohol and an alicyclic skeleton. Examples thereof include condensation polymerization products with acids.

  Here, as the polyhydric alcohol having an alicyclic skeleton, the alicyclic polyhydric alcohol (a2) can be used.

  Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, and 2-methyl-1,3-trimethylene. Diol, 1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, glycerin, Examples include trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A and bisphenol F), and sugar alcohols (such as xylitol and sorbitol). It is.

  Examples of the polyvalent carboxylic acid having a cyclic skeleton include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, Examples include aromatic dicarboxylic acids such as trimellitic acid.

  Among the above-described compounds (a1) to (a4), a compound having an aromatic ring as a cyclic skeleton is preferable, and an epoxy (meth) acrylate compound having an aromatic ring is particularly preferable.

[Polyisocyanate compound]
Examples of the polyisocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylene diisocyanate, and 1,4-xylene. Diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methyl Cyclohexylene diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-to Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like.

  Among the polyisocyanate compounds described above, alicyclic polyisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, and methylcyclohexylene diisocyanate are preferred from the viewpoint of film physical properties to be described later of the cured resin layer.

[Urethane (meth) acrylate compound having a cyclic skeleton]
The urethane compound having a cyclic skeleton in the present invention is preferably a urethane (meth) acrylate compound having a cyclic skeleton. By forming the cured resin layer with a urethane (meth) acrylate compound having a cyclic skeleton, film physical properties described later can be easily obtained.

  The urethane (meth) acrylate compound having a cyclic skeleton is, for example, a method for synthesizing the above-described urethane compound having a cyclic skeleton, for example, synthesis using a compound having a cyclic skeleton in one or both of a polyol compound and a polyisocyanate compound. In the method, it can be obtained by reacting a (meth) acrylate compound having a hydroxyl group in the molecule.

  Examples of the (meth) acrylate compound having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclopentanediol mono (meth) acrylate, cyclopentanedimethanol mono (meth) acrylate, cyclopentanedimethanol mono (meth) acrylate, cyclohexane Diol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, cyclohexanediethanol mono (meth) acrylate, norbornanediol (Meth) acrylate, norbornane dimethanol mono (meth) acrylate, norbornane diethanol mono (meth) acrylate, decalindiol mono (meth) acrylate, decalin dimethanol mono (meth) acrylate, decalin diethanol mono (meth) acrylate, hydrogenated bisphenol A mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, isocyanuric Examples include acid di (meth) acrylate.

  Among the above compounds, compounds having one hydroxyl group and one or more functional groups ((meth) acrylate groups) in the molecule are preferable, and in particular, one hydroxyl group and 2 to 6 groups in the molecule. A compound having a functional group is preferred. For example, pentaerythritol tri (meth) acrylate and dipentaerythritol pentaacrylate are preferable.

  Among the urethane (meth) acrylate compounds having a cyclic skeleton described above, an epoxy (meth) acrylate compound obtained by reacting the aforementioned (a1) diepoxy compound having a cyclic skeleton in the molecule with (meth) acrylic acid, A urethane (meth) acrylate compound having a cyclic skeleton obtained by reacting the above-described polyisocyanate compound and the (meth) acrylate compound having a hydroxyl group in the molecule is preferable.

  Moreover, in order to increase the urethane bond amount of the urethane (meth) acrylate compound having a cyclic skeleton, it is preferable to further react a compound having two hydroxyl groups in the molecule in the synthesis method described above.

  As the compound having two hydroxyl groups in the molecule, an aliphatic diol compound is preferably used. Examples of the aliphatic diol compound include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 2, 3-butanediol, 1,2-butanediol, 3-methyl-1,2-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentane Diol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylene glycol, tetramethylene glycol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1, 3-pentanediol, 1,6-hexanedio 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, polyethylene glycol , Polypropylene glycol, polybutylene glycol and the like.

  The content of the urethane compound having a cyclic skeleton in the cured resin layer is preferably in the range of 20 to 90% by mass with respect to 100% by mass of the total solid content of the cured resin layer, from the viewpoint of adhesion and moldability. The range of -85 mass% is more preferable, and the range of 40-80 mass% is especially preferable.

[Reactive inorganic particles]
The reactive inorganic particle in the present invention is an inorganic particle that reacts by heating or irradiation with active energy rays. For example, the surface of the particle has an activity such as an epoxy group or a thermally reactive group such as melamine or an ethylenically unsaturated group. It is a particle having a reactive group by energy beam irradiation.

  The reactive inorganic particles in the present invention are particularly preferably inorganic particles having an ethylenically unsaturated group on the particle surface. Here, examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, and a methacryloyloxy group.

  Particles having an ethylenically unsaturated group on the particle surface can be obtained by surface modification with a compound having an ethylenically unsaturated group. As the compound having an ethylenically unsaturated group, a silane coupling agent having an ethylenically unsaturated group is preferably used.

  Examples of the silane coupling agent having an ethylenically unsaturated group include 3- (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, and 3- (meth) acryloyloxypropyltriethoxy. Silane, 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, vinylphenylenetrimethoxysilane, vinylphenylenetriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc. These compounds can be used alone or in combination of two or more.

  Among the above compounds, a compound selected from 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane is obtained by irradiation with active energy rays. It is particularly preferable in terms of excellent polymerization activity.

  Examples of the method of modifying the surface of the inorganic particles with the silane coupling agent include a wet method in which the inorganic particles are dispersed in a solvent and then the silane coupling agent is added and reacted.

  Examples of the inorganic particles include metal oxide particles such as silica particles, alumina particles, zirconia particles, titania particles, and zinc oxide particles. Among these inorganic particles, silica particles are used from the viewpoint of increasing the film strength of the cured resin layer. And alumina particles are preferable, and silica particles are particularly preferable. Examples of the silica particles include colloidal silica, fumed silica (dry silica), and precipitated silica. Among these, colloidal silica is preferably used.

  Silica particles generally have a silanol group on the surface, and reactive inorganic particles can be made relatively easily by reacting this silanol group with the aforementioned silane coupling agent having an ethylenically unsaturated group. Can be obtained.

  Examples of the shape of the inorganic particles include a sphere, an ellipsoid, a polyhedron, a scale shape, and an indeterminate shape. The shape of the inorganic particles is preferably uniform and sized. A spherical shape is particularly preferable.

  The arithmetic average particle diameter of the inorganic particles is preferably in the range of 3 to 300 nm, more preferably in the range of 5 to 150 nm, from the viewpoint of improving the moldability of the metal deposition film and the surface smoothness of the cured resin layer. The range of 7 to 100 nm is preferable, and the range of 10 to 50 nm is particularly preferable.

  Further, from the viewpoint of the surface smoothness of the cured resin layer, the ratio (r / d) between the arithmetic average particle diameter (r: μm) of the inorganic particles and the film thickness (d: μm) of the cured resin layer is 0.5. The following is preferable, 0.1 or less is more preferable, and 0.05 or less is particularly preferable. The lower limit is about 0.001.

  The content of the reactive inorganic particles in the cured resin layer is preferably 1% by mass or more with respect to 100% by mass of the total solid content of the cured resin layer, from the viewpoint of improving the moldability of the metal vapor deposition film. More preferably, it is more preferably 3% by mass or more. Since the surface smoothness of the cured resin layer may decrease if the content of the reactive inorganic fine particles is excessive, the upper limit content is 30% by mass with respect to 100% by mass of the total solid content of the cured resin layer. The following is preferable, 20% by mass or less is more preferable, and 15% by mass or less is particularly preferable.

[Active energy ray cured resin layer]
The cured resin layer in the present invention is preferably an active energy ray curable resin layer. The active energy ray cured resin layer is a cured resin layer cured by irradiating the coating film with active energy rays such as ultraviolet rays and electron beams.

  When the cured resin layer is an active energy ray cured resin layer, it is preferable to contain a urethane (meth) acrylate compound as the urethane compound. Furthermore, in order to increase the film strength of the cured resin layer, it is preferable to contain a compound having two or more ethylenically unsaturated groups. The compound having two or more ethylenically unsaturated groups does not include a urethane (meth) acrylate compound.

  Examples of the compound having two or more ethylenically unsaturated groups include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditri Tyrolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Examples include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tri (meth) acrylate, and tripentaerythritol hexa (meth) acrylate.

  The content of the compound having two or more ethylenically unsaturated groups is preferably in the range of 3 to 45% by mass with respect to 100% by mass of the total solid content of the cured resin layer (active energy ray curable resin layer). The range of 40% by mass is more preferable, and the range of 7 to 35% by mass is particularly preferable.

  Moreover, the content ratio (mass ratio) of the urethane compound having a cyclic skeleton and the compound having two or more ethylenically unsaturated groups is within the range described below for the indentation hardness measured by the nanoindentation method of the cured resin layer. From the viewpoint of adjustment, a range of 95: 5 to 30:70 is preferable, a range of 90:10 to 40:60 is more preferable, and a range of 85:15 to 50:50 is particularly preferable.

  The active energy ray-curable resin layer preferably further contains a photopolymerization initiator. Specific examples of such photopolymerization initiators include, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoylformate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, teto Sulfur compounds such as lamethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone can be used. These photopolymerization initiators may be used alone or in combination of two or more.

  Moreover, generally the photoinitiator is marketed and they can be used. For example, Irgacure (registered trademark) 184, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870, Irgacure OXEDA, manufactured by Ciba Specialty Chemicals Co., Ltd. (Registered trademark) TPO, DAROCUR1173, etc., Speedcure (registered trademark) MBB, Speedcure PBZ, SpeedcureITX, SpeedcureCTX, SpeedcureEDB, Esacure (registered trademark) ONE ) KAYACURE (registered trademark) DE X-S, KAYACURE CTX, KAYACURE BMS, KAYACURE DMBI, and the like.

  The content of the photopolymerization initiator is preferably in the range of 0.1 to 10% by mass, and 0.5 to 8% by mass with respect to 100% by mass of the total solid content of the cured resin layer (active energy ray curable resin layer). The range of is more preferable.

  Examples of the active energy ray for curing the active energy ray-curable resin layer include ultraviolet rays, visible rays, infrared rays, electron beams, rays, β rays, and γ rays. Among these active energy rays, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferably used.

  Although it does not specifically limit as a light source for irradiating an ultraviolet-ray, For example, an ultraviolet fluorescent lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp etc. can be used. . An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are preferably used. In addition, when irradiating with ultraviolet rays, it is preferable to perform irradiation in an atmosphere having a low oxygen concentration, for example, an atmosphere having an oxygen concentration of 500 ppm or less because it can be cured efficiently.

Irradiation light amount of the ultraviolet rays is preferably from 50 mJ / cm ² or more, 100 mJ / cm ² or more, and particularly 150 mJ / cm ² or more. The upper limit is preferably 2000 mJ / cm ² or less, and more preferably 1000 mJ / cm ² or less.

  The cured resin layer is preferably applied on the base film by a wet coating method, for example, reverse coating method, spray coating method, bar coating method, gravure coating method, rod coating method, die coating method, spin coating method, A coating method such as an extrusion coating method can be used.

[Preferred characteristics / physical properties of cured resin layer]
The thickness of the cured resin layer is preferably 0.5 μm or more, more preferably 0.75 μm or more, and particularly preferably 1.0 μm or more from the viewpoint of increasing the film strength. On the other hand, from the viewpoint of obtaining good moldability, it is preferably 7 μm or less, more preferably 6 μm or less, and particularly preferably 5 μm or less.

  The surface of the cured resin layer is preferably smooth. When laminating a metal vapor-deposited film on the cured resin layer, if the surface smoothness of the cured resin layer is low, pinholes and cracks may occur in the metal vapor-deposited film, or the mirror glossiness of the metal vapor-deposited film may be reduced. There is.

  From the above viewpoint, the surface roughness (Ra) measured with an atomic force microscope (AFM) on the surface of the cured resin layer is preferably less than 2.0 nm, more preferably less than 1.5 nm, and particularly preferably less than 1.0 nm. . The lower limit is not particularly limited, but is practically about 0.1 nm.

  The surface roughness (Ra) of the surface of the cured resin layer is, for example, adjusted by adjusting the arithmetic average particle diameter of the inorganic particles constituting the reactive inorganic particles contained in the cured resin layer to the range described above, or inorganic. It can be obtained by adjusting the ratio (r / d) of the arithmetic average particle diameter (r: μm) of the particles and the thickness (d: μm) of the cured resin layer to the above-mentioned range.

The cured resin layer preferably has an appropriate hardness from the viewpoint of obtaining good adhesion and moldability. In view of the above, indentation hardness measured by nanoindentation method of the cured resin layer is preferably in the range of 200~600N / mm ^2, more preferably in the range of 250~550N / mm ^2, in particular 300~500N / mm A range of ² is preferred.

  From the viewpoint of obtaining good moldability, the cured resin layer preferably has a tensile crack elongation of 10% or more, more preferably 13% or more, and particularly preferably 15% or more. The upper limit is about 200%.

  Here, the tensile crack elongation is the elongation when a crack is generated in the cured resin layer when one side of the metal vapor deposition film is fixed and the metal vapor deposition film is pulled at a tensile speed of 50 mm / min. .

  The tensile crack elongation is, for example, 1-30 mass for the cured resin layer containing a urethane compound having a cyclic skeleton, and the content of reactive inorganic particles with respect to 100 mass% of the solid content of the cured resin layer. % Can be obtained by adjusting in the range of%.

[Metal vapor deposition film]
A metal vapor deposition film can be obtained by laminating a metal vapor deposition film on the cured resin layer of the metal vapor deposition film of the present invention. The metal vapor deposition film is preferably laminated directly on the cured resin layer.

  Examples of the metal of the metal vapor deposition film in the metal vapor deposition film include aluminum, magnesium, palladium, zinc, nickel, silver, copper, gold, platinum, indium, tin, stainless steel, chromium, titanium and the like. Alternatively, two or more kinds can be mixed and used. Of the metals described above, aluminum is most preferred. The above metals include metal oxides, sulfides, nitrides, and carbides. Moreover, the metal of the metal vapor deposition film in the present invention does not include silicon which is a semimetal and compounds containing silicon (compounds such as oxides, nitrides and carbides).

  As a vapor deposition method, a conventionally known method such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a plasma CVD method can be used.

  The thickness of the metal vapor deposition film is preferably in the range of 3 to 300 nm, more preferably in the range of 5 to 200 nm, and particularly preferably in the range of 10 to 100 nm. When the film thickness is less than 3 nm, the specular gloss may decrease. On the other hand, when the film thickness exceeds 300 nm, the flexibility (flexibility) of the deposited film may decrease and the molding processability may decrease.

  In order to impart good design properties and heat ray reflectivity to the metal vapor-deposited film, the gloss of the metal vapor-deposited film is preferably 100 or more, more preferably 110 or more, and particularly preferably 120 or more. . The upper limit is not particularly limited, but is practically about 500.

Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the following examples.
[Evaluation method]
First, an evaluation method in each example and comparative example will be described. The number of evaluation n was n = 5 unless otherwise specified, and the arithmetic average value was obtained.
(1) Measurement of surface roughness (Ra) measured with an atomic force microscope The surface roughness (Ra) of a cured resin layer is measured using an atomic force microscope “AFM5100N” manufactured by Hitachi High-Tech Science under the following conditions. did.
・ Scanning mode: DFM
・ Scanning range: 5μm × 5μm
-Number of data: 256 x 256
Measurement environment: 25 ° C. in the atmosphere.
(2) Measurement of indentation hardness by nanoindentation method It measured using the nanoindenter "ENT-2100" made from Elionix. Fix the opposite side of the metal vapor deposition film measurement surface (cured resin layer surface) to a special sample fixing base via an adhesive ("Aron Alpha" (registered trademark)) manufactured by Toagosei Co., Ltd. The indentation hardness (H _IT (N / mm ² )) of the layer was measured using a triangular pyramid diamond indenter (Berkovich indenter) with a ridge angle of 115 ° under the following conditions. It processed with the exclusive analysis software (version 6.18).
<Measurement conditions>
・ Measurement mode: Load-unloading test ・ Maximum load: 100 mN
-Holding time when maximum load is reached: 1 second-Loading speed, unloading speed: 10 mN / sec
Indentation depth: 1/10 of the film thickness.
(3) Tensile crack elongation of the cured resin layer After the metal deposition film was stored at room temperature for 1 day, it was cut into a short shape having a length of 110 mm and a width of 20 mm to prepare a test sample. Using a tensile tester (“Autograph AGS-500NX” manufactured by Shimadzu Corporation), a tensile test was performed while visually confirming the cracked state of the cured resin layer at a chuck distance of 50 mm and a tensile speed of 50 mm / min. It was. The elongation at the time when the crack occurred was obtained by the following calculation formula and was defined as the tensile crack elongation. The environment at the time of measurement is 23 ° C. ± 2 ° C. and relative humidity 55% ± 5%.

<Calculation formula of tensile crack elongation>
(L ₁ -L ₀ ) / L ₀ × 100
In the above formula, L ₀ represents a dimension before pulling, and L ₁ represents a dimension when a crack occurs in the cured resin layer.
(4) Put 100 crosscut of 1 mm ² on the surface of the metallized film adhesion test metallized film (aluminum film), affixed Nichiban Co., Ltd. manufactured cellophane tape (registered trademark) thereon, the finger After pressing strongly with, it peeled rapidly in the direction of 90 degrees, and the adhesion was evaluated according to the following criteria based on the number remaining.
A: 90/100 (remaining number / measured number) or more B: 80 to 89/100 (remaining number / measured number)
C: Less than 80/100 (remaining number / measured number).
(5) Glossiness The glossiness of the metal-deposited film surface of the metal-deposited film was measured at 85 ° using a gloss meter (Gloss Mobile “GM-1”) of Suga Test Instruments Co., Ltd.
(6) Thickness of each layer About the metal vapor deposition film and the metal vapor deposition film, samples for cross-sectional observation of the cured resin layer and the metal vapor deposition film are obtained by the FIB method using a microsampling system (Hitachi FB-2000A) (specifically Was prepared on the basis of the method described in “Polymer Surface Processing” (by Satoshi Iwamori), pages 118-119). With a transmission electron microscope (Hitachi H-9000UHRII), the cross section of the cross section observation sample was observed at an acceleration voltage of 300 kV, and the thicknesses of the cured resin layer and the metal vapor deposition film were measured.
(7) Measurement of the arithmetic average particle diameter of particles contained in the cured resin layer The cross section of the cured resin layer was observed with a TEM (transmission electron microscope) (approximately 10,000 to 300,000 times), and from the cross-sectional photograph. Thirty particles were randomly selected, the maximum length was measured, and the arithmetic average of these values was taken as the arithmetic average particle size of the particles.
(8) Molding workability A metal deposition film was placed on a vacuum molding machine (Forming 300 model manufactured by Seiko Sangyo Co., Ltd.), and the metal deposition film was heated to 100 ° C. with a ceramic heater. Then, using the metal mold | die with a shaping ratio of 1.1 times, the metal mold | die was pressed against the film for metal vapor deposition, and it shape | molded by attracting | sucking in a vacuum from the metal mold | die side.

  An aluminum film (film thickness 40 nm) is laminated on the surface of the cured resin layer of the metal vapor deposition film molded as described above in the same manner as in Example 11 below, and the adhesion and glossiness of the aluminum film are as described above (4 ) And (5). The smaller the change in the adhesion and glossiness of the aluminum film before and after the molding process, the better the molding processability.

[Materials used in Examples and Comparative Examples]
≪Synthesis of urethane compound having cyclic skeleton≫
<UA-1; urethane (meth) acrylate compound having a cyclic skeleton (aromatic ring)>
In a four-necked flask, 3180 parts by mass of bisphenol F type diepoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Epototo YDF-8170C, epoxy equivalent: 159), 1440 parts by mass of acrylic acid, and hydroquinone monomethyl as a polymerization inhibitor 4.6 parts by mass of ether and 23 parts by mass of dimethylaminoethyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: acrylate ester DM) as a synthesis catalyst were added and the temperature was raised to 95 ° C. while stirring, The reaction was continued for 14 hours while being held. When the acid value became 1 mgKOH / g or less, the internal temperature was cooled to 60 ° C. to obtain an epoxy (meth) acrylate compound.

  Next, 298 parts by mass of the epoxy (meth) acrylate compound and 711.3 parts by mass of ethyl acetate were placed in a four-necked flask and heated to an internal temperature of 60 ° C. 0.21 part by mass of di-n-butyltin dilaurate was added as a synthesis catalyst, and 199 parts by mass of methylcyclohexylene diisocyanate (Mitsui Chemical Polyurethane Co., Ltd., trade name: Takenate 600) was stirred for 1 hour while stirring. And dripped. The reaction was continued for 2 hours after completion of the dropping, and then 27.3 parts by mass of diethylene glycol (a reagent manufactured by Wako Pure Chemical Industries, Ltd., trade name: diethylene glycol, molecular weight 106) and pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd.) , Trade name: Aronix M-306) A mixture of 187 parts by mass was added dropwise over 1 hour. Reaction was continued for 5 hours after dripping, and the urethane (meth) acrylate compound (UA-1) of the mass mean molecular weight 19800 was obtained.

<UA-2; urethane (meth) acrylate compound having a cyclic skeleton>
In the synthesis of UA-1, 3462 parts by mass of bisphenol A diepoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Epototo YD-8125, epoxy equivalent: 173.1) was used instead of bisphenol F diepoxy resin. The urethane (meth) acrylate compound (UA-2) was obtained in the same manner as UA-1, except that hydroquinone monomethyl ether was changed to 4.9 parts by mass and dimethylaminoethyl methacrylate was changed to 24 parts by mass. .

<UA-3; urethane compound having a cyclic skeleton (aromatic ring)>
In a four-necked flask, 300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (trade name: Epoxy ester 3000A) and 710 parts by mass of ethyl acetate are added and heated to an internal temperature of 60 ° C. did. As a synthesis catalyst, 0.2 part by mass of di-n-butyltin dilaurate was added, and 200 parts by mass of dicyclohexylmethane 4,4′-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. Reaction was continued for 2 hours after completion | finish of dripping, and 25 mass parts of diethylene glycol (made by Wako Pure Chemical Industries Ltd.) was dripped over 1 hour continuously. The reaction was continued for 5 hours after the dropwise addition to obtain a urethane compound (UA-3) having a cyclic skeleton having a mass average molecular weight of 20,000. In addition, this urethane compound (UA-3) does not have an ethylenically unsaturated group.

<UA-4; urethane (meth) acrylate compound having a cyclic skeleton (alicyclic ring)>
A four-necked flask was charged with 75 parts by mass of hexamethylene diisocyanate and 100 parts by mass of n-butyl acetate, and the internal temperature was adjusted to 50 ° C. Then, a cyclohexanedicarboxylic acid polyester polyol (P-1041 manufactured by Kuraray Co., Ltd .; molecular weight) A mixed liquid of 1002, 220 parts by mass of a hydroxyl value of 111.7 mgKOH / g) and 100 ppm of dibutyltin dilaurate (addition amount to the obtained urethane (meth) acrylate) was dropped over 2 hours. After further aging reaction for 4 hours and confirming that the NCO concentration no longer changed, the internal temperature was raised to 70 ° C., then 54 parts by mass of hydroxyethyl acrylate, 50 parts by mass of n-butyl acetate, and 800 ppm of hydroquinone monomethyl ether (obtained) (Addition amount with respect to urethane (meth) acrylate) was added dropwise over 1 hour and further reacted for 4 hours. After confirming that the NCO concentration was 0.1% by mass or less, the reaction was terminated to obtain a urethane (meth) acrylate compound (UA-4).

≪Silica particles≫
<Reactive silica (Si-1)>
To 150 parts by mass of colloidal silica (organosilica sol “MEK-ST” manufactured by Nissan Chemical Industries, Ltd., solid content 30% by mass, methyl ethyl ketone 70% by mass), 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicon Co., Ltd., product) Name: KBM-503) 13.7 parts by weight and 1.7 parts by weight of a 10% by weight formic acid aqueous solution were mixed and stirred at 70 ° C. for 1 hour to obtain reactive silica particles (Si-1).

<Reactive silica (Si-2)>
In a four-necked flask, 2,000 parts by mass of colloidal silica (“IPA-ST” manufactured by Nissan Chemical Industries, Ltd., solid content 30% by mass, isopropyl alcohol 70% by mass), and 3-methacryloyloxypropyltrimethoxysilane 382 parts by mass (trade name: KBM-503, manufactured by Shin-Etsu Silicon Co., Ltd.) were added. Next, the temperature in the flask is raised while stirring, and 150 parts by mass of pure water are gradually added dropwise so as to maintain the reflux temperature at the same time as the reflux of the volatile components starts. After completion of the addition, the mixture is stirred for 2 hours under reflux. Hydrolysis was performed. At the end of hydrolysis, volatile components such as alcohol and water are distilled off at normal pressure. When the solid concentration is about 60% by mass, 600 parts by mass of toluene is added, and alcohol, water, etc. are used together with toluene. Distilled to the boil. Furthermore, 1,500 parts by mass of toluene was added, and the solvent was completely replaced with a toluene dispersion. The solid content concentration at this time was about 40% by mass. Further, the reaction was carried out at 110 ° C. for 4 hours while distilling toluene, so that the solid content concentration was about 60% by mass.

<Non-reactive silica (Si-3)>
Colloidal silica (organosilica sol “MEK-ST” manufactured by Nissan Chemical Industries, Ltd., solid content 30 mass%, methyl ethyl ketone 70 mass%) 150 mass parts, tetramethoxysilane 13.7 mass parts and 10 mass% formic acid aqueous solution 1.7 parts by mass were mixed and stirred at 70 ° C. for 1 hour to obtain silica particles whose surface was modified with a silane coupling agent. The surface-modified silica particles are non-reactive.

<Non-reactive silica (Si-4)>
Colloidal silica; Organo silica sol “MEK-ST” manufactured by Nissan Chemical Industries, Ltd., solid content 30% by mass, methyl ethyl ketone 70% by mass)
[Example 1]
A metal deposition film was prepared in the following manner.

<Preparation of easy adhesion layer laminated polyethylene terephthalate (PET) film>
PET pellets (intrinsic viscosity 0.63 dl / g) substantially free of externally added particles are sufficiently vacuum-dried, then supplied to an extruder, melted at 285 ° C., extruded from a T-shaped die into a sheet shape, It was wound around a mirror-casting drum having a surface temperature of 25 ° C. using an electric application casting method and cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film. After performing corona discharge treatment in air on both surfaces of this uniaxially stretched film, the following easy-adhesion layer coating solutions were respectively applied to both surfaces of the uniaxially stretched film.

  Next, after gripping the uniaxially stretched film coated with the easy-adhesion layer coating solution with a clip, it is guided to the preheating zone, dried at an ambient temperature of 75 ° C., raised to 110 ° C. using a radiation heater, and dried again at 90 ° C. Subsequently, it was continuously stretched 3.5 times in the width direction in a heating zone at 120 ° C., followed by heat treatment for 20 seconds in a heating zone at 220 ° C. to produce a biaxially stretched PET film in which crystal orientation was completed.

  The thickness of the easy adhesion layer laminated PET film thus obtained was 125 μm, and the thickness of the easy adhesion layer laminated on both surfaces was 0.09 μm.

<Easily adhesive layer coating solution>
An aqueous dispersion coating solution was prepared by mixing 26% by mass of polyester resin a, 54% by mass of polyester resin b, 18% by mass of melamine-based crosslinking agent, and 2% by mass of particles in terms of solid content by mass.
Polyester resin a; polyester resin obtained by copolymerizing 43 mol% of 2,6-naphthalenedicarboxylic acid, 7 mol% of 5-sodium sulfoisophthalic acid, and 50 mol% of a diol component containing ethylene glycol; polyester resin b; Polyester resin and melamine-based crosslinking agent obtained by copolymerization of 38 mol% terephthalic acid, 12 mol% trimellitic acid, and 50 mol% diol component containing ethylene glycol; "Nikarac MW12LF" manufactured by Sanwa Chemical Co., Ltd.
Particles: colloidal silica having an arithmetic average particle size of 0.19 μm.

<Lamination of cured resin layer>
The following coating resin a1 for cured resin layer is applied to one surface of the easy-adhesion layer-laminated PET film prepared above with a gravure coater, dried at 90 ° C., and then cured by irradiation with ultraviolet rays of 400 mJ / cm ^2. A resin layer was formed. The thickness of this cured resin layer was 3 μm.

<Coating liquid a1 for cured resin layer>
140 parts by mass of urethane (meth) acrylate compound (UA-1) having an aromatic ring, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate DPE-6A), photopolymerization initiator ("Irgacure" (registered trademark) 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass and reactive silica (Si-1) in a solid content mass ratio (ratio to the total solid content of the coating solution) of 5 The mass% was mixed and diluted with an organic solvent (methyl ethyl ketone) to prepare a solid content concentration of 20 mass%.

[Example 2]
A metal vapor deposition film was produced in the same manner as in Example 1 except that the cured resin layer coating solution a2 was changed to the following.

<Coating liquid a2 for cured resin layer>
140 parts by mass of urethane (meth) acrylate compound (UA-2) having an aromatic ring, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate DPE-6A), photopolymerization initiator 5 parts by mass (“Irgacure” (registered trademark) 907 manufactured by Ciba Specialty Chemicals Co., Ltd.) and 5 parts by weight of the reactive silica (Si-2) (the ratio of the coating liquid to the total solids) The mass% was mixed and diluted with an organic solvent (methyl ethyl ketone) to prepare a solid content concentration of 20 mass%.

[Example 3]
A metal vapor deposition film was produced in the same manner as in Example 1 except that the cured resin layer coating solution a3 was changed to the following.

<Coating liquid a3 for cured resin layer>
100 parts by mass of urethane compound (UA-3) having an aromatic ring, 40 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), photopolymerization initiator (Ciba Specialty) -5 parts by mass of "Irgacure" (registered trademark) 184) manufactured by Chemicals Co., Ltd. and 5% by mass of reactive silica (Si-1) in a solid mass ratio (ratio to the total solid content of the coating solution) Then, it was diluted with an organic solvent (methyl ethyl ketone) to prepare a solid content concentration of 20% by mass.

[Example 4]
A metal vapor deposition film was produced in the same manner as in Example 1 except that the coating liquid a4 for the cured resin layer was changed to the following.

<Coating liquid a4 for cured resin layer>
150 parts by mass of urethane (meth) acrylate compound (UA-4) having an alicyclic ring, 30 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), photopolymerization started Agent (“Irgacure” (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 5 parts by mass, and reactive silica (Si-1) in solid content mass ratio (ratio to the total solid content of the coating solution) 5% by mass was mixed and diluted with an organic solvent (methyl ethyl ketone) to prepare a solid concentration of 20% by mass.

[Comparative Example 1]
A metal vapor deposition film was produced in the same manner as in Example 1 except that the cured resin layer coating solution a5 was changed to the following.

<Coating liquid a5 for cured resin layer>
70 parts by mass of an aliphatic polyfunctional urethane (meth) acrylate compound ("KRM8452" from Daicel Cytec Co., Ltd.) and 30 dipentaerythritol hexaacrylate (trade name: Light Acrylate DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) 5 parts by mass, 5 parts by mass of photopolymerization initiator (“Irgacure” (registered trademark) 184 manufactured by Ciba Specialty Chemicals Co., Ltd.), and solid content mass ratio of reactive silica (Si-1) (total amount of the coating solution) 5% by mass in a ratio to the solid content) and mixed in an organic solvent (methyl ethyl ketone) to prepare a composition having a solid content concentration of 30% by mass.

[Comparative Example 2]
A metal vapor deposition film was produced in the same manner as in Example 1 except that the cured resin layer coating solution a6 was changed to the following.

<Coating liquid a6 for cured resin layer>
100 parts by mass of urethane compound (UA-3) having an aromatic ring, 40 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), photopolymerization initiator (Ciba Specialty) -5 parts by mass of “Irgacure” (registered trademark) 184) manufactured by Chemicals Co., Ltd. and 5% by mass of non-reactive silica (Si-3) in solid mass ratio (ratio to the total solid content of the coating solution) It mixed and diluted with the organic solvent (methyl ethyl ketone), and it prepared so that solid content concentration might be 20 mass%.

[Comparative Example 3]
A metal vapor deposition film was produced in the same manner as in Example 1 except that the cured resin layer coating solution a7 was changed to the following.

<Coating liquid a7 for cured resin layer>
150 parts by mass of urethane (meth) acrylate compound (UA-4) having an alicyclic ring, 30 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Acrylate DPE-6A), photopolymerization started 5 parts by weight of the agent (“Irgacure” (registered trademark) 184) manufactured by Ciba Specialty Chemicals Co., Ltd., and 3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Silicon Co., Ltd.) The non-reactive silica (Si-4) is mixed at a solid content mass ratio (ratio to the total solid content of the coating solution) of 5 mass%, diluted with an organic solvent (methyl ethyl ketone), and the solid content concentration is 20 mass. %.

[Examples 11-14 and Comparative Examples 11-13]
On the surface of the cured resin layer of the film for metal vapor deposition produced in Examples 1 to 4 and Comparative Examples 1 to 3, an aluminum film was formed using a bell jar type vacuum vapor deposition machine EBH-6 (manufactured by ULVAC, Inc.). Was deposited to be 80 nm to obtain metal deposited films of Examples 11 to 14 and Comparative Examples 11 to 13.

[Evaluation]
About the metal vapor deposition film obtained in said Examples 1-4 and Comparative Examples 1-3, and the metal vapor deposition film obtained in Examples 11-14 and Comparative Examples 11-13, the above-mentioned measurement and evaluation were performed. It was. The results are shown in Table 1.

Claims (9)

  A metal deposition film having a cured resin layer on at least one surface of a base film, wherein the cured resin layer is a layer obtained by curing a composition containing a urethane compound having a cyclic skeleton and reactive inorganic particles. A metal deposition film characterized by the above.   The metal deposition film according to claim 1, wherein the urethane compound having a cyclic skeleton is a urethane (meth) acrylate compound.   The film for metal vapor deposition of Claim 1 or 2 whose said reactive inorganic particle is a silica particle which has an ethylenically unsaturated group.   The film for metal vapor deposition in any one of Claims 1-3 whose surface roughness (Ra) measured with the atomic force microscope (AFM) of the said cured resin layer is less than 2.0 nm. The film for metal vapor deposition in any one of Claims 1-4 whose indentation hardness measured by the nanoindentation method of the said cured resin layer is the range of 200-600 N / mm < ² >.   The film for metal vapor deposition in any one of Claims 1-5 whose tensile crack elongation of the said cured resin layer is 10% or more.   The film for metal vapor deposition in any one of Claims 1-6 whose said cured resin layer is an active energy ray cured resin layer.   The metal vapor deposition film by which a metal vapor deposition film is laminated | stacked on the cured resin layer of the film for metal vapor deposition in any one of Claims 1-7.   The metal vapor deposition film of Claim 8 whose glossiness of the said metal vapor deposition film is 100 or more.