CN113557278B

CN113557278B - Multilayer film and laminate comprising same

Info

Publication number: CN113557278B
Application number: CN202180000837.4A
Authority: CN
Inventors: 李康圭; 李扃旻; 玉柄胄; 冰广殷
Original assignee: Escape Mcavo Solutions Co ltd
Current assignee: Escape Mcavo Solutions Co ltd
Priority date: 2020-02-19
Filing date: 2021-02-18
Publication date: 2023-07-04
Anticipated expiration: 2041-02-18
Also published as: WO2021167378A1; CN113557278A; KR102142431B1

Abstract

The multilayer film of the present invention includes a primer layer, an inorganic vapor layer, and an adhesive layer having different colors, and thus, stereoscopic colors can be realized by a plurality of colors reflected from each layer and their mixed colors. Further, since the multilayer film can be bonded to glass to increase strength, it is useful as a scattering preventing film and a decorative film for various products such as a display, an automobile, and a household electrical appliance.

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 a scattering prevention and decorative function.

Background

In the fields of electric and electronic appliances, display devices are developed in various forms in consideration of various factors such as use purpose, portability, convenience, etc., and in particular, various designs of displays are being studied because consumers pay attention to their designs according to the use of the displays. Recently, a metal (metal) design is attracting attention in the fields of electric appliances and electronics, and is widely applied to colors, shapes, and the like of mobile devices, communication electronic devices, and the like which are recently marketed. Although metals are attractive materials in terms of design because they have a luster inherent to metals and excellent brightness, they have drawbacks such as radio wave blocking, heavy weight, and high manufacturing cost.

In order to remedy the above-mentioned drawbacks, displays using glass instead of metal are being 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 thus, in order to increase the strength of a display manufactured from glass and further improve the design, a method of applying a scattering preventing film that can realize a color is being studied.

As an example, korean laid-open patent No. 2014-0110225 discloses a scattering preventing film comprising a hard coat layer comprising a transparent film and an azo (azo) type dye, korean laid-open patent No. 2015-0096860 discloses a hard coat layer comprising a colored dye having a maximum absorptivity at 400nm to 700nm, and a transparent conductive film comprising the same. However, the above patent discloses only physical properties related to transparency, durability, and the like of the film, and does not disclose matters related to design, in particular, matters related to color development.

Prior art literature

Patent document 1: korean laid-open patent No. 2014-0110225

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, recently, colors and designs have been introduced into the anti-scattering film so that the product has various colors and decorative functions. However, conventionally, a two-dimensional color is represented only by a single color or a gradation of 1 to 2 colors, and a stereoscopic color cannot be realized.

In contrast, the present inventors have found after studies that a multilayer film including a primer layer, an inorganic deposition layer, and an adhesive layer to which different colors are applied realizes a three-dimensional color from a plurality of colors reflected from each layer and their mixed colors.

Accordingly, an object of the present invention is to provide a multilayer film and a laminate of the multilayer film and glass, which can achieve a more three-dimensional color than before and can be bonded to glass to increase strength.

Technical proposal

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 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.

According to another object of the present invention, there is provided a laminate comprising: a glass substrate; and the multilayer film is attached such that an adhesive layer of the multilayer film contacts 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 material layer, an inorganic deposition layer, and an adhesive layer are laminated, and the primer layer, the inorganic deposition layer, and the adhesive layer are provided with mutually different colors, whereby a three-dimensional color can be realized by a plurality of colors reflected from the respective layers and their mixed colors.

Specifically, when the primer layer, the inorganic vapor layer, and the adhesive layer are given specific colors, a plurality of colors can be expressed according to the viewing angle to realize a stereoscopic color.

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

Drawings

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

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

Description of the reference numerals

100: multilayer film 101: release layer

102: adhesive layer 103: inorganic vapor deposition layer

104: organic fixing layer 105: substrate layer

106: primer layer 200: glass substrate

301: mold pattern layer 302: inorganic reflective layer

303: shading printing layer

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings. The dimensions or intervals, etc. in the drawings may be enlarged for ease of understanding, and contents apparent to those of ordinary skill in the art to which the present invention pertains may be omitted.

In the following description, it should be understood that when a certain structural element is disposed above or below another structural element, all cases in which other structural elements are or are not present between these structural elements are included.

In this specification, when a certain component is "included", unless the context clearly indicates otherwise, it means that other components may be included in addition to the above components.

Multilayer film

Referring to fig. 1, the multilayer film 100 of the present invention includes, in a laminated form: a primer layer 106 having a first color; a base material layer 105; an inorganic deposition 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 fixing layer 104 including a binder resin and an inorganic oxide, and disposed between the base 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 material layer, an inorganic deposition layer, and an adhesive layer, and the primer layer, the inorganic deposition layer, and the adhesive layer are provided with mutually different colors, whereby a three-dimensional color can be realized by a plurality of colors reflected from the respective layers and a mixed color thereof.

According to an example, the first color has an L value of 40 to 90, -an a value of 40 to 40, and a b value of-40 to 40 based on the CIE color system, the second color has an L value of 25 to 65, -an a value of 10 to 40, and a b value of-20 to 40 based on the CIE color system, and the third color may have an L value of 60 to 90, -an a value of 30 to 30, and a b value of-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, second, and third colors 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. For the value of a, the second color may be the largest and the first color may be the smallest. 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, second, and third colors may have a difference value in a specific range. For example, these colors may each 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. As an example, these colors may have a difference between 1 to 40, 5 to 30, or 10 to 20, respectively. In particular, the value of 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 second color and the first color and/or the third color may have a difference of 5 or more or 10 or more, specifically, a difference of 5 to 30 or 10 to 20 based on a value of a of the CIE color system.

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 L-value of the color of the above multilayer film may be 25 to 90, more specifically 65 to 85. And, the color of the 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 an L value of 25 to 90, -an a value of 40 to 40, and a 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 an L value of 50 to 90, -an a value of 40 to 40, and a 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, and thus may exhibit a plurality of colors in a stereoscopic manner. For example, when the observation angle of the above-described multilayer film is changed by 5 degrees or more, for example, by 5 degrees to 10 degrees, the change in a' value may be 5 or more, specifically 10 or more, and more specifically 15 or more. As a specific example, the change in the a value 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 a value may be a measured value for the transmitted color.

The primer layer and the adhesive layer contain dyes or pigments, and can realize colors in the visible light range. For example, the primer layer and the adhesive 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 general 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. The oligomer compound having 3 to 8 hydroxyl groups and/or carboxyl groups may be, for example, N-vinylpyrrolidone, pentaerythritol triacrylate, tricyclodecane dimethanol diacrylate or the like, and specifically pentaerythritol triacrylate, tricyclodecane dimethanol diacrylate or the like.

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

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

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

Substrate layer

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

The base material layer may include a polymer resin, and specifically, may include a transparent polymer resin. For example, the base material layer may include one or more polymer resins selected from the group consisting of polyethylene terephthalate (PET), polyimide (PI), cyclic Olefin Polymer (COP), polyethylene naphthalate (PEN), polyether sulfone (PES), polycarbonate (PC), and polypropylene. Specifically, the polymer resin of the base material layer may be at least one selected from the group consisting of polyethylene terephthalate (PET), polyimide (PI), and Cyclic Olefin Polymer (COP).

The base material layer may have excellent strength so as to prevent scattering of tempered glass or the like of the touch panel.

Further, the base material 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 substrate 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. The organic particles or inorganic particles as described above may function as an anti-blocking agent (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 contains an inorganic deposition material, and thus provides a metallic texture and improves brightness and reflectance.

The inorganic deposition layer may include at least one selected from the group consisting of an inorganic single substance, an inorganic composite oxide, and an inorganic composite sulfide.

The inorganic single substance may be one or more selected from the group consisting of a metal, a nonmetal, a metalloid, and a rare earth metal.

For example, the inorganic single substance may be one or more selected from the group consisting of metals, non-metals, metalloids, and rare earth metals belonging to 3 to 7 cycles of the periodic table. Specifically, the inorganic single substance may be at least one 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 cubes, face-centered cubes, and body-centered cubes.

The above inorganic composite oxide may contain a metal, a nonmetal, a metalloid, a rare earth metal, or the like as an inorganic component. Specifically, the inorganic composite oxide may contain 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 contain one or more inorganic components selected from the group consisting of lithium, potassium, strontium, niobium, silicon, and cesium.

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

The inorganic deposition layer may be formed by a physical deposition method, for example, sputtering (sputtering) or electron-beam deposition (electron-beam deposition). As a specific example, the inorganic deposition layer may be formed by non-conductive vacuum plating (NCVM, non-conductive vacuum metalizing).

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

In the step of forming the inorganic deposition layer, the deposition of the inorganic substance may be performed under heating. For example, the temperature at which the above inorganic substances are evaporated 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 may realize a color in the visible light region, or may improve bonding force with other layers.

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

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

The 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 primer layer or the primer layer composition used to prepare the same. When in 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 slot coating method, or the like.

The thickness of the primer layer may be 2 μm to 10 μm, and in particular, may have a thickness of 3 μm to 6 μm. When in 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 adhered to the surface of a product such as glass, the adhesive layer imparts adhesion, and the visibility and heat insulation can be improved 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 turn yellow by 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 may be used. Among them, an acrylic resin excellent in optical characteristics, weather resistance, adhesion to a substrate, and the like is preferably used.

The curing agent is not particularly limited as long as it is capable of curing the binder resin. Specifically, one or more selected from the group consisting of an isocyanate curing agent, an epoxy curing agent, and an aziridine curing agent which are not yellowing by ultraviolet rays may be used. And, the content of the above-mentioned curing agent may be 0.2 to 0.5 weight percent, 0.3 to 0.45 weight percent, or 0.35 to 0.45 weight percent with respect to the total weight of the adhesive layer. When it is within the above range, it is advantageous to prevent the lowering of the adhesion or the lowering of the durability in heat-resistant and moisture-resistant environments.

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

In addition, the adhesive layer may further contain additives such as antioxidants, light stabilizers, photoinitiators, and the like. As an example, the photoinitiator may be one or more selected from the group consisting of benzophenones (benzophenones), thioxanthones (thioxanthones), α -hydroxyketones (α -hydroxyketones), ketones (ketones), phenylglyoxylates (phenyl glyoxylate) and propylenephosphine oxides (acryl phosphine oxide).

In order to prevent scattering of glass due to damage, the adhesive layer may have an adhesive force of 10N/inch or more to glass, and specifically may have an adhesive force of 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 defective processes, it is advantageous to perform reworking for recycling of glass.

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

The thickness of the 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 amount is within the above range, it is advantageous to prevent the trouble caused by the 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.

As an example, the release layer may be made of epoxy, epoxy-melamine, amino acids, acrylic, melamine, silicon, fluorine, cellulose, urea-formaldehyde resin, polyolefin, paraffin, or the like.

Organic fixing layer

The organic fixing 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 producing a scatter-preventing film, if an inorganic deposition layer is directly 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 deposition process, and the appearance of the product may be blurred and the color visibility may be lowered. However, when the inorganic deposition layer is formed above the surface of the base material layer after the organic fixing layer is formed thereon, impact due to heat applied to the base material layer can be eliminated, and thus the product appearance characteristics and color visibility can be further improved.

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

The organic substance is fixed so that the bonding force between the layers can be improved by the inorganic oxide.

Furthermore, the organic anchoring layer can improve the 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 increases due to the organic particles or inorganic particles that are usually contained as the anti-blocking agent on the surface of the base material layer, and thus the optical characteristics may be impaired, but the organic fixing layer is interposed between the base material layer and the inorganic deposition layer and functions as a buffer layer, so that the increase in surface roughness can be suppressed.

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

The acrylic resin may be polymerized from at least one acrylic monomer and a carboxyl group-containing unsaturated monomer. 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 alpha-methylolacrylate, ethyl alpha-methylolacrylate, propyl alpha-methylolmethacrylate, butyl alpha-methylolacrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiglycol (meth) acrylate, methoxytriglycol (meth) acrylate, methoxypropiodiol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1, 3-hexafluorodecyl (meth) acrylate, or octafluoro (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenoxyethyl (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 may contain silicon (Si) oxide, for example. More specifically, the inorganic oxide may include silicon monoxide (SiO) and silicon dioxide (SiO ₂ ) At least one of them.

The content of the inorganic oxide may be 10 to 50 weight percent, more specifically 20 to 40 weight percent, based on the weight of the organic fixing layer. When the content is within the above range, the bonding force between the organic fixing layer and the inorganic deposition layer can be improved, and reworking (reworking) when the adhesive layer is peeled off after the adhesion to the glass is facilitated.

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

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

The organic anchoring layer may be formed by wet coating (wet coating). For example, the binder resin and the inorganic oxide are applied by a wet method using an additive such as a curing agent and a coating composition formulated with a solvent. As an example, the coating method by which the wet method is performed may be spin coating, gap coating, roll coating, screen printing, applicator coating, or the like. For example, after forming a wet coating layer having a thickness of 2 μm to 25 μm using the above-described coating method, the organic fixing layer may be formed by drying for 1 minute to 10 minutes at a temperature of 50 ℃ to 150 ℃.

Subsequently, the curable organic fixing layer may 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 ultra-high-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 as appropriate. Although the exposure amount varies depending on the structure and thickness of the organic fixing layer, in the case of using a high-pressure mercury lamp, the exposure amount may be 100mJ/cm at a wavelength of 365nm ² The following is given.

The thickness of the above-mentioned organic fixing layer may be 0.15 μm to 3 μm, more specifically, may be 0.5 μm to 1.5 μm. Preferably, the organic anchoring layer may have a thickness of 0.5 μm to 1 μm. When the thickness is within the above range, the coating film of the inorganic vapor 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 example includes, in a laminated form: a primer layer having a first color; a substrate layer; an inorganic vapor layer having a second color; and a bonding layer having a third color, wherein the first color, the second color, and the third color are different colors, and a difference in a value of a x based on a CIE color system between the second color and the first color or the third color is 5 or more, and a value of a x based on a transmission color of a CIE color system is 10 or more when an observation angle of the multilayer film is changed by 5 to 10 degrees.

Effects and uses

Specifically, when the primer layer, the inorganic vapor layer, and the adhesive layer described above impart specific colors, a plurality of colors can be realized depending on the viewing angle to realize a stereoscopic color.

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 multilayer film or the Ra surface roughness of the inorganic deposition layer may be 0 μm to 1 μm or 0 μm to 0.1 μm.

In particular, the multilayer film can be used as a scattering preventing film and a metallic decorative film by realizing a more three-dimensional color than before and increasing strength by bonding to glass.

Laminate body

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

Referring to fig. 2, the laminate of the present invention includes: a glass substrate 200; and the multilayer film 100 of the above example 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 described above has the same structure and characteristics as the multilayer film described in the above-described one example.

The glass substrate 200 is not particularly limited as long as it is a glass substrate commonly used in displays, automobiles, home 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 print layer 303 on the primer layer 106 of the multilayer film.

Pattern layer of mould

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

For example, after injection molding a raw material 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-mentioned 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 metallic luster.

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

The non-conductive inorganic substance may be at least one 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 μm to 0.1 μm, specifically 0.02 μm to 0.05 μm. When in the above range, it is advantageous to maintain adhesion between layers and provide a proper level of metallic luster.

Shading printing layer

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

The light-shielding printed layer may include a desired picture, pattern, various colors, lines, etc. according to preference.

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.

Embodiments of the invention

The invention is illustrated in further detail by the following 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 (UV 1700B, NIPPON gossei corporation), 15 parts by weight of pentaerythritol triacrylate (M340, MIWEN corporation) and 5 parts by weight of photoinitiator (1-184, ciba corporation) were mixed and methyl ethyl ketone was added to make the solid content 20 weight percent, and then 4 parts by weight of pigment was added to 100 parts by weight of the solid content. In this case, 3 parts by weight of pigment 1 (BV 231, iridos Co.) and 1 part by weight of pigment 2 (BO 260, iridos Co.) were used as pigments. The primer layer composition was applied to one side of a base layer (PET film) having a thickness of 100 μm with a thickness of 3 μm by using a Mailer bar (Mayer bar), dried at 80℃for 2 minutes, and then cured by ultraviolet rays (light amount 0.4J/cm) ² ) A color primer layer is formed.

Next, to prepare the organic anchoring layer composition, 60 parts by weight of urethane acrylate oligomer (UV 1700B, NIPPON GOHSEI Co.), 15 parts by weight of pentaerythritol triacrylate (M340, MIWEN Co.), 20 parts by weight of silicon nanoparticles (MAC 2000, TOYOINK Co.) and 5 parts by weight of photoinitiator (1-184, ciba Co.) were mixed and methyl ethyl ketone was added to make a solidThe components reach 20 weight percent. The organic anchoring layer composition was applied to the other surface of the base layer with a thickness of 1. Mu.m using a Mailer bar, dried at 80℃for 2 minutes, and then cured by ultraviolet rays (light quantity 0.4J/cm) ² ) An organic fixing layer is formed.

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

Further, in order to prepare the adhesive layer composition, 35 parts by weight of a pressure sensitive adhesive (305S, saiden Co.) 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 red dye (RD-01, iridos Co.) were added, respectively. The adhesive layer composition was applied to the surface of the colored inorganic deposition layer by a gap coater (gap coater) and dried and cured to form a colored adhesive layer having a thickness of 25. Mu.m. Subsequently, a release film is attached to the surface of the colored adhesive layer to form a multilayer film.

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

A color primer layer was formed on one side of the base material layer (PET film) and an organic fixing layer was formed on the other side in the manner of example 1. Subsequently, a colored inorganic deposition layer was formed by sputtering and depositing niobium (Nb) on the surface of the organic fixing layer, and finally, an optically clear adhesive (OCA, SKC HT & M company) was applied to the surface of the inorganic deposition layer to obtain a multilayer film.

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

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

Test example: transmitted color coordinates

In removing the release film from each of the multilayer films prepared by the above examples and comparative examples, the transmission color was measured using a color measuring device (UV Spectrometer U4100, hitachi corporation). The transmitted color of the same portion was measured separately from the angle. The results are summarized 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 according to angle, compared to the multilayer films of comparative examples 1 and 2, and it was confirmed that a plurality of colors could be exhibited at each angle.

Claims

1. A multilayer film comprising, in a layered form:

a primer layer having a first color;

a substrate layer;

an inorganic vapor 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;

the difference of a-value based on CIE color system between the second color and the first color or the third color is above 5;

the first color has an L-value of 40 to 90, -an a-value of 40 to 40 and a b-value of-40 to 40 based on the CIE color system,

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

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

when the viewing angle of the multilayer film is changed by 5 degrees or more, the a-value of the transmission color based on the CIE color system is changed to 10 or more.

2. The multilayer film of claim 1, wherein the color of the multilayer film has a value of L x of 25 to 90, -a x of 40 to 40, and-b x of 40 to 40 based on the CIE color system.

3. The multilayer film according to claim 1, wherein the primer layer and the adhesive layer each include at least one of an anthraquinone pigment and a phthalocyanine pigment.

4. The multilayer film according to claim 1, wherein the inorganic deposition layer has a thickness of 10nm to 500 nm.

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

6. The multilayer film according to claim 1, wherein the inorganic deposition layer comprises at least one selected from the group consisting of an inorganic single substance, an inorganic composite oxide, and an inorganic composite sulfide.

7. The multilayer film according to claim 6, wherein the inorganic single substance is at least one selected from the group consisting of a metal, a nonmetal, a metalloid, and a rare earth metal,

the inorganic composite oxide contains at least one inorganic component 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 composite sulfide contains one or more inorganic components selected from the group consisting of titanium, vanadium, chromium, manganese, cobalt, zinc, niobium, and molybdenum.

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

9. The multilayer film according to claim 8, wherein the binder resin of the organic fixing layer contains one or more of an acrylic resin and a urethane resin.

10. The multilayer film according to claim 8, wherein the inorganic oxide comprises an oxide of silicon having an average particle diameter of 20nm to 100nm.

11. The multilayer film according to claim 1, wherein the multilayer film is used as a scattering preventing film and a decorative film having a metallic texture.

12. 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 contact at least one surface of the glass substrate.