CN113557278A

CN113557278A - Multilayer film and laminate comprising same

Info

Publication number: CN113557278A
Application number: CN202180000837.4A
Authority: CN
Inventors: 李康圭; 李扃旻; 玉柄胄; 冰广殷
Original assignee: SKC Hi Tech and Marketing Co Ltd
Current assignee: SK Microworks Solutions Co Ltd
Priority date: 2020-02-19
Filing date: 2021-02-18
Publication date: 2021-10-26
Anticipated expiration: 2041-02-18
Also published as: WO2021167378A1; CN113557278B; KR102142431B1

Abstract

The multi-layered film of the present invention includes a primer layer, an inorganic vapor-deposited layer, and a tie layer having different colors, and thus, a three-dimensional color can be realized by a plurality of colors reflected from the respective layers and their mixed colors. Further, since the multilayer film can be bonded to glass to increase strength, the multilayer film can be applied to various products such as displays, automobiles, and home electric appliances as an anti-scattering film and a decorative film.

Description

Multilayer film and laminate comprising same

Technical Field

The present invention relates to a multilayer film which is suitable for a glass substrate, an electronic device case, and the like, and has an anti-scattering and decorative function.

Background

In the field of electric and electronic devices, display devices have been developed in various forms in consideration of various factors such as use purposes, portability, and convenience, and particularly, consumers have been studying various designs of displays because they pay attention to the design according to the use of the displays. Recently, a design which attracts attention in the electric and electronic fields is a metal (metal) design, and the metal design is widely applied to colors, shapes, and the like of mobile devices, communication electronic devices, and the like which are recently on the market. Although metals are materials that have attracted attention in terms of design because of their inherent luster and excellent brightness, they have disadvantages such as blocking radio waves, heavy weight, and high manufacturing cost.

In order to compensate for the above disadvantages, displays using glass instead of metal have been developed. Compared with metal, glass has the advantages of low preparation cost and light weight. However, glass has a fatal disadvantage of low strength, and therefore, in order to increase the strength of a display made of glass and further improve the design, a method of applying an anti-scattering film that can realize colors is being studied.

As an example, korean laid-open patent No. 2014-0110325 discloses an anti-scattering film including a hard coat layer including a transparent film and an azo (azo) -based dye, and korean laid-open patent No. 2015-0096860 includes a hard coat layer including a colored dye having a maximum absorption rate of 400nm to 700nm and a transparent conductive film including the same. However, the above patent discloses only the physical properties of the film, such as transparency and durability, and does not disclose the design, particularly the color appearance.

Documents of the prior art

Patent document 1: korea laid-open patent No. 2014-0110325

Patent document 2: korean laid-open patent No. 2015-0096860

Disclosure of Invention

Technical problem

Although a general anti-scattering film functions as a protective film for preventing glass from being damaged, colors and designs have recently been introduced into the anti-scattering film, so that products have various colors and decorative functions. However, conventionally, a two-dimensional color is expressed only by a single color or 1 to 2 color gradations, and a three-dimensional color has not been realized.

In contrast, the present inventors have found, after investigation, that a three-dimensional color is realized by a plurality of colors reflected from each layer and a mixed color thereof by a multilayer film including a primer layer, an inorganic vapor-deposited layer, and an adhesive layer to which different colors are imparted.

Accordingly, an object of the present invention is to provide a multilayer film and glass laminate which can realize a more three-dimensional color than conventional ones and which can be bonded to glass with increased strength.

Technical scheme

In accordance with the above object, the present invention provides a multilayer film comprising, in a laminated form: a primer layer having a first color; a substrate layer; an inorganic vapor deposited layer having a second color; and an adhesive layer having a third color, the first color, the second color, and the third color being different colors from each other.

According to another object of the present invention, there is provided a laminate comprising: a glass substrate; and the multilayer film attached so that the adhesive layer of the multilayer film is in contact with at least one surface of the glass substrate.

ADVANTAGEOUS EFFECTS OF INVENTION

The multilayer film of the present invention has a structure in which a primer layer, a base layer, an inorganic deposition layer, and an adhesive layer are laminated, and the primer layer, the inorganic deposition layer, and the adhesive layer are colored differently from each other, so that a three-dimensional color can be realized by a plurality of colors reflected from the respective layers and a mixed color thereof.

Specifically, when the primer layer, the inorganic deposition layer, and the adhesive layer are given specific colors, various colors can be embodied according to viewing angles to realize three-dimensional colors.

Therefore, the multilayer film can realize a more three-dimensional color than before and can be applied to various products such as displays, automobiles, home appliances, and the like as an anti-scattering film and a decorative film by increasing strength so as to be bonded to glass.

Drawings

Fig. 1 is a cross-sectional view of a multilayer film of an embodiment of the present invention.

Fig. 2 is a cross-sectional view of a multilayer film and a laminate of glass substrates according to an embodiment of the present invention.

Description of reference numerals

100: multilayer film 101: release layer

102: bonding layer 103: inorganic vapor deposition layer

104: organic fixed layer 105: substrate layer

106: primer layer 200: glass substrate

301: mold pattern layer 302: inorganic reflective layer

303: light-shielding printing layer

Detailed Description

The present invention will be described in further detail below with reference to the accompanying drawings. The size, interval, etc. in the drawings may be exaggerated for easy understanding, and may be omitted to show matters obvious to those skilled in the art to which the present invention pertains.

In the following description, it should be understood that when a certain structural element is disposed above or below another structural element, all cases where other structural elements are present or absent between the structural elements are included.

In the present specification, when a certain structural element is "included", it means that other structural elements may be included in addition to the structural element unless otherwise specified.

Multilayer film

Referring to fig. 1, a multilayer film 100 of the present invention comprises in layered form: a primer layer 106 having a first color; a base material layer 105; an inorganic vapor-deposited layer 103 having a second color; and an adhesive layer 102 having a third color, wherein the first color, the second color, and the third color are different colors from each other.

The multilayer film 100 may further include an organic anchor layer 104 containing a binder resin and an inorganic oxide, and the organic anchor layer is located between the base material layer 105 and the inorganic deposition layer 103.

The multilayer film 100 may further include a release layer 101 on the surface of the adhesive layer 102.

Color and reflectance

The multilayer film has a laminated structure including a primer layer, a base layer, an inorganic vapor-deposited layer, and an adhesive layer, and the primer layer, the inorganic vapor-deposited layer, and the adhesive layer are colored differently from each other, so that a three-dimensional color can be realized by a plurality of colors reflected from the respective layers and a mixed color thereof.

According to one example, the first color has a value of L from 40 to 90, -a from 40 to 40 and b from-40 to 40 based on the CIE color system, the second color has a value of L from 25 to 65, -a from 10 to 40 and b from-20 to 40 based on the CIE color system, and the third color may have a value of L from 60 to 90, -a from 30 to 30 and b from-30 to 30 based on the CIE color system. The values of L, a, and b illustrated above may be values of a reflective color or a transmissive color, and more specifically may be values of a transmissive color.

In this case, L, a, and b of the first color, the second color, and the third color may represent different values from each other. First, for the value of L, the first color may be the largest and the second color may be the smallest. And, for the value of a, the second color may be the largest and the first color may be the smallest. And, for the value of b, the second color may be the largest and the first color may be the smallest.

In this case, L, a, and b of the first color, the second color, and the third color may have a difference in a specific range. For example, the colors may have a difference of 1 or more, specifically, may have a difference of 5 or more, and more specifically, may have a difference of 10 or more, respectively. As an example, there may be a difference of 1 to 40, 5 to 30, or 10 to 20 between the colors, respectively. In particular, the value a between the first color and the second color, or between the second color and the third color, may have a difference of 5 to 30 or 10 to 20.

As a specific example, the a value of the second color and the first color and/or the third color based on the CIE color system may have a difference of 5 or more or 10 or more, and specifically, may have a difference of 5 to 30 or 10 to 20.

Thus, the multilayer film may have a color that is a combination of the first color, the second color, and the third color. For example, the multilayer film may have a color L value of 25 to 90, more specifically 65 to 85. And, the color of the above multilayer film may have a value of-40 to 40, more specifically-30 to 30. And, the b value of the color of the above multilayer film may be-40 to 40, more specifically-30 to 30.

As an example, the color of the multilayer film may have a value of L of 25 to 90, a value of 40 to 40, and b value of 40 to 40 based on the CIE color system. As a more specific example, the color of the multilayer film may have a value of L of 50 to 90, a value of a of 40 to 40, and b value of 40 to 40 based on the CIE color system.

The values of L, a, and b illustrated above may be values of a reflective color or a transmissive color, and more specifically, may be values of a transmissive color.

In particular, the above-described multilayer film is visually recognized as different colors according to viewing angles, so that three-dimensional multiple colors can be expressed. For example, when the observation angle of the multilayer film is changed by 5 degrees or more, for example, by 5 degrees to 10 degrees, the change in value a may be 5 or more, specifically 10 or more, more specifically 15 or more. As a specific example, the change in the value of a may be 5 to 40 or 10 to 25. In this case, the observation angle may be an angle based on the plane direction of the multilayer film, and the value a may be a measured value for a transmitted color.

The primer layer and the adhesive layer contain a dye or a pigment, and can realize a color in the visible light region. For example, the primer layer and the tie layer may include a pigment dispersion, and the pigment dispersion may include a pigment and an oligomer compound having one or more of 3 to 8 hydroxyl groups and carbonyl groups.

The pigment is not limited as long as it is commonly used in the art and can realize a color in the visible light region. For example, the primer layer and the adhesive layer may each include at least one of an anthraquinone pigment and a phthalocyanine pigment. For example, the oligomer compound having 3 to 8 of one or more of the above-mentioned hydroxyl groups and carboxyl groups may be N-vinylpyrrolidone, pentaerythritol triacrylate, tricyclodecane dimethanol diacrylate or the like, and specifically may be pentaerythritol triacrylate, tricyclodecane dimethanol diacrylate or the like.

The above pigment may have a maximum absorption rate in a wavelength region of 350nm to 500nm or 400nm to 650 nm. Also, the average particle diameter of the above pigment may be 30nm to 150nm, specifically 30nm to 100 nm.

The multilayer film can have a higher reflectance than before by including an organic anchor layer. For example, the visible light reflectance of the above multilayer film may be 10% to 50%, more specifically, may be 10% to 30%. The visible light reflectance may be an average reflectance in a visible light wavelength range (400nm to 700 nm).

The multilayer film may have a total light transmittance of 70% or more, specifically 85% or more, and a haze of 3% or less, specifically 1% or less.

Substrate layer

The base material layer 105 is a base layer for supporting other functional layers.

The substrate layer may contain a polymer resin, and specifically may contain a transparent polymer resin. For example, the substrate layer may include one or more polymer resins selected from the group consisting of polyethylene terephthalate (PET), Polyimide (PI), cycloolefin polymer (COP), polyethylene naphthalate (PEN), Polyethersulfone (PES), Polycarbonate (PC), and polypropylene. Specifically, the polymer resin of the substrate layer may be one or more selected from the group consisting of polyethylene terephthalate (PET), Polyimide (PI), and cycloolefin polymer (COP).

The substrate layer may have excellent strength so as to prevent the tempered glass of the touch panel from scattering.

Also, the substrate layer may have high transparency so as not to impair optical characteristics. For example, the total light transmittance of the base material layer may be 70% or more, specifically 55% or more.

The thickness of the above base material layer may be 10 μm to 200 μm, specifically 23 μm to 100 μm.

The substrate layer may further include organic particles or inorganic particles on the surface thereof. The organic particles or inorganic particles as described above may function as an anti-blocking agent. The size of the organic particles or inorganic particles may be 0.1 μm or more, for example, 0.1 μm to 5 μm or 0.1 μm to 1 μm.

Inorganic vapor deposition layer

The inorganic deposition layer 103 includes an inorganic deposition material, thereby providing a metallic texture and improving brightness and reflectance.

The inorganic evaporation layer may include one or more selected from the group consisting of inorganic single substances, inorganic composite oxides, and inorganic composite sulfides.

The inorganic single substance may be one or more selected from the group consisting of metals, metalloids, and rare earth metals.

For example, the inorganic single substance may be one or more selected from the group consisting of metals, metalloids, and rare earth metals belonging to periods 3 to 7 of the periodic table. Specifically, the inorganic single substance may be one or more selected from the group consisting of aluminum (Al), silicon (Si), scandium (Sc), titanium (Ti), vanadium (V), chromium (V), manganese (Mn), cobalt (Co), copper (Cu), zinc (Zn), germanium (Ge), rubidium (Rb), niobium (Nb), molybdenum (Mo), indium (In), tin (Sn), and antimony (Sb).

The inorganic composite oxide and the inorganic composite sulfide may be those in which an inorganic component is bonded to oxygen (O) or sulfur (S) by ionic bonding, covalent bonding, or the like. The inorganic composite oxide and the inorganic composite sulfide may have one or more lattice structures selected from the group consisting of simple cubic, face-centered cubic, and body-centered cubic.

The above inorganic composite oxide may contain a metal, a nonmetal, a metalloid, a rare earth metal, etc. as an inorganic component. Specifically, the inorganic composite oxide may include one or more inorganic components selected from the group consisting of lithium (Li), aluminum, potassium (K), titanium, vanadium, chromium, manganese, cobalt, zinc, strontium (Sr), niobium, molybdenum, indium, silicon, tin, antimony, and cesium. More specifically, the inorganic composite oxide may include one or more inorganic components selected from the group consisting of lithium, potassium, strontium, niobium, silicon, and cesium.

The above inorganic complex sulfide may contain an inorganic component belonging to groups 3 to 12 of the periodic table. Specifically, the inorganic complex sulfide may include one or more inorganic components selected from the group consisting of titanium, vanadium, chromium, manganese, cobalt, zinc, niobium, and molybdenum.

The inorganic vapor-deposited layer can be formed by a physical vapor deposition method such as sputtering or electron beam evaporation. As a specific example, the inorganic deposition layer may be formed by non-conductive vacuum plating (NCVM).

The thickness of the inorganic deposition layer may be 10nm to 500nm, and specifically, the inorganic deposition layer may have a thickness of 30nm to 70 nm. When within the above range, it is advantageous to maintain the adhesiveness between layers and to have a suitable level of brightness and metallic texture.

In the step of forming the inorganic vapor deposition layer, the vapor deposition of the inorganic substance may be performed under heating. For example, the temperature at the time of evaporating the above inorganic substance may be 40 ℃ to 200 ℃, more specifically 60 ℃ to 150 ℃.

Primer layer

The primer layer 106 is formed on the surface of the base material layer 105. The primer layer can realize a color in the visible light region, or can improve the bonding force with other layers.

The primer layer may include one or more selected from a thermosetting resin, an Ultraviolet (UV) curable resin, and specifically, may include a urethane resin, an acrylic resin, and the like.

The primer layer may realize a color in a visible light region by including a dye or a pigment. Specifically, the above-mentioned primer layer may contain a pigment dispersion, in which case the kind of the pigment or pigment dispersion used is as described above.

The above pigment dispersion may be contained in an amount of 1 to 30 weight percent, 5 to 20 weight percent, 0.1 to 10 weight percent, or 0.2 to 8 weight percent, relative to the total weight of the above primer layer or the primer layer composition for preparing the same. When within the above range, it is advantageous to realize colors in the entire visible light region.

The primer layer may be formed by a micro gravure coating method, a slit coating method, or the like.

The thickness of the above primer layer may be 2 μm to 10 μm, and specifically, may have a thickness of 3 μm to 6 μm. When within the above range, it is advantageous to realize a color in the visible light region.

Adhesive layer

The adhesive layer 102 is formed on the surface of the inorganic deposition layer 103. When the adhesive layer is attached to the surface of a product such as glass, the adhesive layer imparts an adhesive force to improve visibility and improve heat insulation by eliminating an air layer.

The adhesive layer may include a binder resin and a curing agent. The binder resin is not particularly limited as long as it is a resin that does not yellow due to ultraviolet rays and has excellent dispersibility of the ultraviolet absorber. For example, the binder resin may be a polyester resin, an acrylic resin, an alkyd resin, an amino resin, or the like. The binder resin may be used alone, or two or more kinds of copolymers or mixtures thereof may be used. Among them, acrylic resins having excellent optical properties, weather resistance, adhesion to substrates, and the like are preferably used.

The curing agent is not particularly limited as long as it can cure the binder resin. Specifically, it may be one or more selected from the group consisting of an isocyanate curing agent, an epoxy curing agent and an aziridine curing agent which do not yellow by ultraviolet rays. Also, the curing agent may be included in an amount of 0.2 to 0.5 weight percent, 0.3 to 0.45 weight percent, or 0.35 to 0.45 weight percent, relative to the total weight of the tie layer. When the content is within the above range, it is advantageous to prevent the decrease in adhesion or the decrease in durability in a heat-resistant and moisture-resistant environment.

The adhesive layer contains a dye or a pigment, and can realize a color in a visible light region. Specifically, the above-mentioned adhesive layer may contain a pigment dispersion, and the kind of the pigment or the pigment dispersion used herein is as described above. The content of the above pigment dispersion may be 1 to 30 weight percent, 5 to 20 weight percent, 0.1 to 10 weight percent, or 0.2 to 5 weight percent, relative to the total weight of the above tie layer or the tie layer composition used to prepare the same. When within the above range, it is advantageous to realize colors in the entire visible light region.

In addition, the adhesive layer may further include additives such as an antioxidant, a light stabilizer, a photoinitiator, and the like. For example, the photoinitiator may be one or more selected from the group consisting of benzophenones (benzophenones), thioxanthones (thioxanthones), α -hydroxyketones (α -hydroxy ketones), ketones (ketones), phenylglyoxalates (phenylglyoxalates), and acrylophosphineoxides (acryl phosphine oxides).

In order to prevent the glass from scattering due to damage, the adhesive layer may have an adhesive force of 10N/inch or more, specifically, 10N/inch to 30N/inch. When the amount is within the above range, it is advantageous to obtain a sufficient scattering prevention effect, and in the case of a defective process, it is possible to facilitate the execution of the re-processing for recycling the glass.

In order to suppress the extrudability caused by the process and the foreign matter, the adhesive layer has a glass transition temperature of-40 ℃ or higher, and specifically, may have a glass transition temperature of-40 ℃ to-15 ℃ or-30 ℃ to-15 ℃.

The thickness of the above adhesive layer may be 10 μm to 30 μm, 15 μm to 25 μm, 15 μm to 20 μm, or 15 μm to 17 μm. When the content is within the above range, it is advantageous to prevent the occurrence of defects due to pressing and maintain the adhesion.

Release layer

The release layer can protect the surface of the adhesive layer, and the multilayer film can be removed after being applied to a product.

For example, the release layer may be made of epoxy, epoxy-melamine, amino alkyd, acrylic, melamine, silicone, fluorine, cellulose, urea-formaldehyde resin, polyolefin, paraffin, or the like.

Organic fixed layer

The organic anchor layer 104 is formed between the base material layer 105 and the inorganic deposition layer 103, and includes a binder resin and an inorganic oxide.

In the conventional process of preparing a scattering preventive film, if an inorganic vapor-deposited layer is directly vapor-deposited on a base material layer in order to impart a metallic texture, the surface of the base material layer is damaged by heat applied during the vapor-deposition process, which may result in a blurred product appearance and a reduced color visibility. However, when the inorganic deposition layer is formed over the organic fixing layer formed on the surface of the base material layer, impact due to heat applied to the base material layer can be eliminated, and thus the appearance characteristics and color visibility of the product can be further improved.

In addition, the organic fixed layer functions as an optical layer having a different refractive index between the conventional base layer and the inorganic deposition layer, and thus the reflectivity can be improved by optical compensation of the product.

The organic fixing can improve interlayer bonding strength by the inorganic oxide.

Furthermore, the organic fixed layer can improve optical characteristics by reducing the surface roughness of the multilayer film of the present invention. Specifically, the surface roughness of the inorganic deposition layer or the like is increased on the surface of the base material layer by the organic particles or the inorganic particles usually contained as the anti-blocking agent, and thus, although the optical characteristics may be impaired, the organic anchor layer is interposed between the base material layer and the inorganic deposition layer and functions as a buffer layer, and thus, the increase in the surface roughness can be suppressed.

The binder resin of the organic fixing layer may include one or more selected from a thermosetting resin and an ultraviolet curable resin, and specifically, the binder resin may include one or more selected from an acrylic resin and a urethane resin. When the binder component is contained, it is advantageous to ensure optical transparency and to stably form an inorganic deposition layer.

The acrylic resin may be polymerized from one or more acrylic monomers and carboxyl group-containing unsaturated monomers, respectively. Specifically, the acrylic monomer may be, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, methyl α -hydroxymethylacrylate, ethyl α -hydroxymethylacrylate, propyl α -hydroxymethylacrylate, butyl α -hydroxymethylacrylate, 2-methoxyethyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and the like, 3-methoxybutyl (meth) acrylate, ethoxydiglycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1, 1, 1, 3, 3, 3-hexafluoroisopropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and mixtures thereof. More specifically, the acrylic monomer may be, for example, methyl (meth) acrylate, butyl (meth) acrylate, or a mixture thereof.

The inorganic oxide contains one or more inorganic components, and for example, may contain a silicon (Si) oxide. More specifically, the inorganic oxide may include silicon monoxide (SiO) and silicon dioxide (SiO)₂) At least one of (1).

The content of the inorganic oxide may be 10 to 50 wt%, more specifically 20 to 40 wt%, based on the weight of the organic fixed layer. When the content is within the above range, the bonding force between the organic anchor layer and the inorganic evaporation layer can be improved, and reworking (reworking) at the time of peeling after the adhesive layer is attached to glass can be facilitated.

The inorganic oxide may have a particle form. For example, the average particle diameter of the above inorganic oxide may be 20nm to 100nm, more specifically, 50nm to 80 nm. When the particle diameter is within the above range, a sufficient bonding force with the inorganic anchor layer can be exhibited, and the optical transmittance of the multilayer film can be further improved while reducing the surface roughness.

The organic fixing layer may further include a curing agent, for example, a thermal curing agent and/or a photo-curing agent.

The organic fixing layer may be formed by wet coating (wet coating). For example, a binder resin and an inorganic oxide are applied by a wet method using a coating composition prepared from an additive such as a curing agent and a solvent. As an example, the coating method that can perform the wet process includes spin coating, gap coating, roll coating, screen printing, and applicator coating. For example, after a wet coating layer having a thickness of 2 to 25 μm is formed using the above coating method, the organic fixing layer may be formed by drying at a temperature of 50 to 150 ℃ for 1 to 10 minutes.

Subsequently, the organic fixing layer can be cured, for example, by irradiation with active light of 200nm to 450 nm. As a light source for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon laser, or the like can be used, and X-rays, electron beams, or the like can be used in some cases. Although the exposure amount varies depending on the structure and thickness of the organic fixed layer, in the case of using a high-pressure mercury lamp, the exposure amount may be 100mJ/cm in a wavelength of 365nm²The following.

The thickness of the above organic fixing layer may be 0.15 μm to 3 μm, and more specifically, may be 0.5 μm to 1.5 μm. Preferably, the organic fixing layer may have a thickness of 0.5 μm to 1 μm. When within the above thickness range, the coating film of the inorganic deposition layer can be further stably formed on the organic fixing layer, and an effect of suppressing an increase in surface roughness is advantageously exerted.

Preferred examples

The multilayer film of the preferred embodiment comprises in layered form: a primer layer having a first color; a substrate layer; an inorganic vapor deposited layer having a second color; and an adhesive layer having a third color, wherein the first color, the second color, and the third color are different colors from each other, a value difference between the second color and the first color or the third color based on the CIE color system is 5 or more, and when an observation angle of the multilayer film is changed by 5 to 10 degrees, a value change of a transmitted color based on the CIE color system is 10 or more.

Effect and use

Specifically, when the primer layer, the inorganic deposition layer, and the adhesive layer are given specific colors, various colors can be realized according to viewing angles to realize three-dimensional colors.

Also, the multilayer film of the present invention has low surface roughness and thus can have excellent optical characteristics. For example. The Ra surface roughness of the above multilayer film or the Ra surface roughness of the above inorganic deposition layer may be 0 μm to 1 μm or 0 μm to 0.1 μm.

In particular, the multilayer film can realize a more three-dimensional color than before and can be used as an anti-scattering film and a decorative film having a metallic texture by increasing strength so as to be bonded to glass.

Laminated body

Referring to fig. 2, the laminate of the present invention includes: a glass substrate 200; and the multilayer film 100 of the above-described example, which is attached such that the adhesive layer 102 of the multilayer film is in contact with at least one surface of the glass substrate.

The multilayer film 100 has the same structure and characteristics as those of the multilayer film described in the above example.

The glass substrate 200 is not particularly limited as long as it is a glass substrate generally used in displays, automobiles, household appliances, and the like, and for example, tempered glass may be used, and may have a thickness of 50 μm to 700 μm.

The laminate may further include a functional layer. For example, the laminate may further include at least one of a mold pattern layer 301, an inorganic reflective layer 302, and a light-shielding printed layer 303 on the primer layer 106 of the multilayer film.

Pattern layer of mold

The mold pattern layer 301 is a layer for realizing a pattern (design) desired by a user.

For example, after a raw material is injection molded in one side of the primer layer 106, the mold pattern layer 301 may be patterned by ultraviolet curing.

The material of the mold pattern layer may contain urethane acrylate oligomer, amine monomer, carboxyl monomer, and the like as main components.

The thickness of the above mold pattern layer may be 10 μm to 20 μm, and specifically may be 10 μm to 17 μm or 15 μm to 17 μm.

Inorganic reflective layer

The inorganic reflective layer 302 reflects incident light through the glass substrate 200 and imparts a metallic luster thereto.

The inorganic reflective layer may be formed by sputtering a non-conductive inorganic substance. Specifically, the inorganic reflective layer may be formed by non-conductive vacuum plating (NCVM).

The non-conductive inorganic substance may be one or more selected from the group consisting of niobium, silicon, and titanium, and specifically may be niobium or silicon.

The thickness of the inorganic reflective layer may be 0.01 to 0.1. mu.m, specifically 0.02 to 0.05. mu.m. When within the above range, it is advantageous to maintain the adhesion between layers and provide a suitable level of metallic luster.

Light-shielding printing layer

The light-shielding printed layer 303 can further improve the reflection effect by blocking light.

The light-shielding printed layer can comprise expected pictures, patterns, various colors, lines and the like according to the taste.

Specifically, the light-shielding printed layer may include Black ink, for example, Black ink (product name: Black) of HS chemical company.

The thickness of the light-shielding printed layer may be 10 μm to 50 μm, and may specifically be 15 μm to 20 μm.

Modes for carrying out the invention

The present invention will be described in further detail below with reference to examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1: preparation of multilayer films

To prepare the primer layer composition, 80 parts by weight of urethane acrylate oligomer (UV1700B, NIPP) was mixedON GOHSEI), 15 parts by weight of pentaerythritol triacrylate (M340, MIWEN) and 5 parts by weight of a photoinitiator (1-184, Ciba) and methyl ethyl ketone were added to make the solid content 20 weight percent, and then 4 parts by weight of a pigment was added with respect to 100 parts by weight of the solid content. In this case, 3 parts by weight of pigment 1(BV231, iridos) and 1 part by weight of pigment 2(BO260, iridos) were used as pigments. The primer layer composition was applied to one surface of a substrate layer (PET film) having a thickness of 100 μm in a thickness of 3 μm using a Macler Bar (Mayer bar), dried at 80 ℃ for 2 minutes, and then cured by ultraviolet rays (light amount 0.4J/cm)²) And forming a color primer layer.

Next, to prepare an organic anchor layer composition, 60 parts by weight of urethane acrylate oligomer (UV1700B, NIPPON GOHSEI), 15 parts by weight of pentaerythritol triacrylate (M340, MIWEN), 20 parts by weight of silicon-based nanoparticles (MAC2000, TOYOINK) and 5 parts by weight of photoinitiator (1-184, Ciba) were mixed and methyl ethyl ketone was added to make the solid content 20 weight%. The organic anchor layer composition was applied to the other surface of the substrate layer in a thickness of 1 μm using a Macler rod, dried at 80 ℃ for 2 minutes, and then cured by ultraviolet rays (light amount 0.4J/cm)²) An organic fixing layer is formed.

A color inorganic deposition layer is formed by sputtering and depositing niobium (Nb) and silicon (Si) on the surface of the organic fixed layer.

And, to prepare an adhesive layer composition, 35 parts by weight of a pressure sensitive adhesive (305S, Saiden corporation) and 65 parts by weight of Methyl Ethyl Ketone (MEK) were mixed, to which 0.02 parts by weight, 0.03 parts by weight, or 0.05 parts by weight of a red dye (RD-01, iridos corporation) was added, respectively. The above adhesive layer composition was applied on the surface of the colored inorganic vapor-deposited layer using a gap coater (gap coater), and dried and cured to form a colored adhesive layer having a thickness of 25 μm. Subsequently, a release film is attached to the surface of the color adhesive layer to form a multilayer film.

Comparative example 1: preparation of multilayer film suitable for transparent adhesive layer

In the embodiment of example 1, the color primer layer was formed on one surface of the base layer (PET film), and the organic anchor layer was formed on the other surface. Subsequently, a color inorganic deposition layer was formed by sputtering and depositing niobium (Nb) on the surface of the organic fixed layer, and finally, an optically transparent adhesive (OCA, SKC HT & M) was applied to the surface of the inorganic deposition layer to obtain a multilayer film.

Comparative example 2: preparation of multilayer film without organic fixed layer and inorganic deposition layer

A color primer layer was formed on one surface of the base material layer (PET film) in the manner of example 1 described above. Subsequently, an optically clear adhesive (OCA, SKC HT & M) was laminated on the other surface of the base layer to obtain a multilayer film.

Test example: transmitted color coordinates

The release film was removed from each of the multilayer films prepared by the above examples and comparative examples, and the transmission color was measured using a color measuring apparatus (UV Spectrometer U4100, Hitachi corporation). The transmitted color of the same portion was measured according to the angle. The results are collated in Table 1 below.

TABLE 1

As shown in the results of table 1, the multilayer film of example 1 exhibited a large difference in transmission color depending on the angle, as compared to the multilayer films of comparative examples 1 and 2, and thus it was confirmed that a plurality of colors could be expressed at each angle.

Claims

1. A multilayer film, comprising in layered form:

a primer layer having a first color;

a substrate layer;

an inorganic vapor deposited layer having a second color; and

an adhesive layer having a third color,

the first color, the second color, and the third color are different colors from each other.

2. The multilayer film of claim 1,

said first color having a value of L from 40 to 90, -a from 40 to 40 and b from-40 to 40 based on the CIE color system,

said second color having a value of L from 25 to 65, -a from 10 to 40 and b from-20 to 40 based on the CIE color system,

the third color has a value of L of 60 to 90, -a of 30 to 30 and b of-30 to 30 based on the CIE color system.

3. The multilayer film of claim 2, wherein the multilayer film has a color having a value L of 25 to 90, a value a of 40 to 40, and b value b of 40 to 40 based on the CIE color system.

4. The multilayer film of claim 2, wherein the difference in a values based on the CIE color system between the second color and the first color or the third color is greater than 5.

5. The multilayer film according to claim 1, wherein when the observation angle of the multilayer film is changed by 5 degrees or more, the a value of the transmitted color by the CIE color system is changed to 10 or more.

6. The multilayer film according to claim 1, wherein the primer layer and the tie layer each comprise at least one of an anthraquinone-based pigment and a phthalocyanine-based pigment.

7. The multilayer film of claim 1, wherein said inorganic vapor deposited layer has a thickness of 10nm to 500 nm.

8. The multilayer film according to claim 1, wherein the inorganic deposition layer is formed by sputtering or electron beam evaporation.

9. The multilayer film according to claim 1, wherein the inorganic vapor deposition layer contains one or more selected from the group consisting of inorganic single substances, inorganic complex oxides, and inorganic complex sulfides.

10. The multilayer film according to claim 9, wherein the inorganic single substance is one or more selected from the group consisting of metals, metalloids and rare earth metals,

the inorganic composite oxide contains one or more inorganic components selected from the group consisting of lithium, aluminum, potassium, titanium, vanadium, chromium, manganese, cobalt, zinc, strontium, niobium, molybdenum, indium, silicon, tin, antimony, and cesium,

the inorganic complex sulfide includes one or more inorganic components selected from the group consisting of titanium, vanadium, chromium, manganese, cobalt, zinc, niobium, and molybdenum.

11. The multilayer film according to claim 1, further comprising an organic anchor layer comprising a binder resin and an inorganic oxide, wherein the organic anchor layer is located between the substrate layer and the inorganic vapor deposition layer.

12. The multilayer film according to claim 11, wherein the binder resin of the organic anchor layer comprises one or more of an acrylic resin and a urethane resin.

13. The multilayer film according to claim 11, wherein the inorganic oxide contains an oxide of silicon and has an average particle diameter of 20nm to 100 nm.

14. The multilayer film of claim 1, wherein the multilayer film is used as an anti-scatter film and a decorative film having a metallic texture.

15. A laminate, comprising:

a glass substrate; and

the multilayer film according to claim 1, wherein the adhesive layer of the multilayer film is attached so as to be in contact with at least one surface of the glass substrate.