WO2021167378A1 - Multilayer film and laminate comprising same - Google Patents

Abstract

A multilayer film according to the present invention comprises a primer layer, an inorganic deposition layer and an adhesive layer, which have different colors from one another, and thus can implement three-dimensional colors by means of the colors reflected from the respective layers and mixed colors thereof. In addition, the multilayer film can be layered on glass so as to improve strength, and thus can be applied as a film for scattering prevention and decoration on various products such as displays, cars and home appliances.

Description

Multilayer film and laminate comprising same

The present invention relates to a multilayer film that is applied to a glass substrate, an electronic device case, etc. and has a scattering prevention and decoration function.

In the field of electricity and electronics, display devices are developed in various forms in consideration of the purpose of use, portability, convenience, and the like. In particular, various designs of displays are being studied because consumers place importance on designs according to the uses of displays. A design that has recently been spotlighted in the electrical and electronic field is a metal design, and the metal design is commonly applied to the color and appearance of recently released mobile and communication electronic devices. Metal is a material that is in the spotlight in terms of design due to its inherent luster and excellent luminance, but has disadvantages such as blocking radio waves, heavy weight, and high manufacturing cost.

In order to compensate for this, a display using glass instead of metal is being developed. Glass has advantages in that it costs less to manufacture than metal and has a low sense of weight. However, since glass has a fatal disadvantage of low strength, a method of applying a shatterproof film capable of realizing a color to increase the strength of a display made of glass and further improve the design is being studied.

As an example, Korean Patent Application Laid-Open No. 2014-0110325 discloses a scattering prevention film including a hard coating layer containing a transparent film and an azo-based dye, and Korean Patent Publication No. 2015-0096860 discloses at 400 to 700 nm. Disclosed are a hard coating layer including a colored dye having a maximum absorption rate and a transparent conductive film including the same. However, the above patents disclose only the physical properties related to the transparency and durability of the film, and do not disclose at all in relation to the design, particularly the implementation of various colors.

[Prior art literature]

(Patent Document 1) Republic of Korea Patent Publication No. 2014-0110325

(Patent Document 2) Republic of Korea Patent Publication No. 2015-0096860

The role of a general shatterproof film is a protective film that prevents glass breakage, but recently, colors and designs have been introduced into shatterproof films to perform various color and decoration functions in products. However, in the past, only two-dimensional colors were expressed with a single color or a gradation of one or two colors, but three-dimensional colors could not be realized.

As a result of research by the present inventors, it is possible to realize three-dimensional colors due to the colors reflected from each layer and their mixed colors by a multilayer film including a primer layer, an inorganic deposition layer, and an adhesive layer having different colors. found that there is

Accordingly, an object of the present invention is to provide a multilayer film capable of increasing strength by being laminated to glass while implementing a three-dimensional color than before, and a laminate of the same with glass.

According to the above object, the present invention includes a primer layer having a first color, a base layer, an inorganic deposition layer having a second color, and an adhesive layer having a third color in a laminated form, the first color, the A multilayer film is provided, wherein the second color and the third color are different colors.

According to the other object, the present invention is a glass substrate; and the multilayer film attached to at least one surface of the glass substrate such that an adhesive layer is in contact with it.

The multilayer film according to the present invention includes a structure in which a primer layer, a base layer, an inorganic deposition layer and an adhesive layer are laminated, and by giving different colors to the primer layer, the inorganic deposition layer and the adhesive layer, the colors reflected from each layer And it is possible to realize three-dimensional colors due to their mixed colors.

Specifically, when a specific color is given to the primer layer, the inorganic deposition layer, and the adhesive layer, various colors may be displayed depending on the viewing angle to implement a three-dimensional color.

Therefore, since the multilayer film can be laminated to glass to increase the strength while realizing a three-dimensional color than before, it can be applied as an anti-shattering and decoration film to various products such as displays, automobiles, and home appliances.

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

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.

<Explanation of code>

100: multilayer film, 101: release layer,

102: adhesive layer, 103: inorganic deposition layer,

104: organic fixed layer, 105: base layer,

106: primer layer, 200: glass substrate,

301: mold pattern layer, 302: inorganic reflective layer,

303: light-shielding printed layer.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings. In the accompanying drawings, the size or spacing may be exaggerated to help understanding, and the contents obvious to those of ordinary skill in the art may be omitted.

In the following description, when each component is described as being disposed above or below another component, it should be understood that all cases with or without another component between these components are included.

In the present specification, "including" any component means that other components may be further included in addition to these components, unless otherwise specified.

multilayer film

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

1, the multilayer film 100 according to the present invention has a primer layer 106 having a first color, a base layer 105, an inorganic deposition layer 103 having a second color, and a third color. It includes the adhesive layer 102 having a laminated form, and the first color, the second color, and the third color are different colors.

In addition, the multilayer film 100 may further include an organic fixing layer 104 including a binder resin and an inorganic oxide between the base layer 105 and the inorganic deposition layer 103 .

In addition, 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 includes a structure in which a primer layer, a base layer, an inorganic deposition layer and an adhesive layer are laminated, and by giving different colors to the primer layer, the inorganic deposition layer and the adhesive layer, the colors reflected from each layer and their A three-dimensional color can be realized by mixing colors.

According to one embodiment, 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 according to the CIE color space; 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 according to the CIE color system; 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 according to the CIE color space system. The L*, a*, and b* values exemplified above may be values of a reflected color or a transmitted color, and more specifically, a value of a transmitted color.

In this case, L*, a*, and b* of the first color, the second color, and the third color may represent different values. First, for the L* value, the first color may be the largest and the second color may be the smallest. Also, for a* value, the second color may be the largest and the first color may be the smallest. Also, for the b* value, 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 within a specific range. For example, each of these colors may have a difference of 1 or more, specifically 5 or more, and more specifically 10 or more. As an example, each of these colors may have a difference of 1 to 40, 5 to 30, or 10 to 20. In particular, the a* value 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 is a difference between the first color and/or the third color by at least 5, or at least 10, specifically 5 to 30, or 10 to 20 in a* value according to the CIE color system. can have a difference of

Accordingly, the multilayer film may have a color in which the first color, the second color, and the third color are combined. For example, the L* value of the color of the multilayer film may be 25 to 90, more specifically, 65 to 85. In addition, the a* value of the color of the multilayer film may be -40 to 40, more specifically -30 to 30. In addition, the b* value of the color of the multilayer film may be -40 to 40, more specifically -30 to 30.

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

The L*, a*, and b* values exemplified above may be values of a reflected color or a transmitted color, and more specifically, a value of a transmitted color.

In particular, the multilayer film is visually recognized in different colors depending on the viewing angle, so that three-dimensional and various colors can be expressed. For example, when the observation angle of the multilayer film is changed by 5 degrees or more, for example, 5 degrees to 10 degrees, the change in a* value may be 5 or more, specifically 10 or more, 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 with respect to 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 may include a dye or a pigment to implement a color in a visible light region. For example, the primer layer and the adhesive layer may include a pigment dispersion, and the pigment dispersion may include a pigment and an oligomeric compound having 3 to 8 at least one of a hydroxyl group and a carbonyl group. have.

The pigment is not limited as long as it can implement a color in the visible region as commonly used in the art. For example, the primer layer and the adhesive layer may each include at least one of an anthraquinone-based pigment and a phthalocyanine-based pigment. Examples of the oligomeric compound having 3 to 8 at least one of a hydroxyl group and a carboxyl group may be N-vinylpyrrolidone, pentaerythritol triacrylate, tricyclodecanedimethanol diacrylate, and the like, specifically , pentaerythritol triacrylate, tricyclodecane dimethanol diacrylate, and the like.

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

In addition, the multilayer film may have an improved reflectance than before by including an organic fixing layer. For example, the visible light reflectance of the multilayer film may be 10% to 50%, more specifically 10% to 30%. Here, the visible light reflectance may be an average reflectance in the visible light wavelength range (400 to 700 nm).

In addition, 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.

base layer

The base layer 105 is a base layer for supporting another functional layer.

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

The base layer may have excellent strength to prevent scattering of the tempered glass of the touch screen panel.

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

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

In addition, the base layer may further include organic or inorganic particles on the surface. Such organic or inorganic particles can function as an anti-blocking agent. The size of the organic 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 deposition layer

The inorganic deposition layer 103 includes an inorganic deposition material to provide a metallic texture while improving luminance and reflectance.

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

The inorganic single material may be at least one selected from the group consisting of metals, nonmetals, metalloids, and rare earth metals.

For example, the inorganic single material may be at least one selected from the group consisting of metals, nonmetals, metalloids, and rare earth metals belonging to periods 3 to 7 of the periodic table. Specifically, the single inorganic material may be at least one selected from the group consisting of Al, Si, Sc, Ti, V, Cr, Mn, Co, Cu, Zn, Ge, Rb, Nb, Mo, In, Sn, and Sb. can

In the inorganic composite oxide and the inorganic composite sulfide, an inorganic component may be bonded to oxygen (O) or sulfur (S) through an ionic bond, a covalent bond, or the like. In addition, the inorganic composite oxide and the inorganic composite sulfide may have at least one lattice structure selected from the group consisting of simple cubic, face-centered cubic, and body-centered cubic.

The inorganic composite oxide may include a metal, a nonmetal, a metalloid, a rare earth metal, etc. as an inorganic component. Specifically, the inorganic composite oxide is at least one selected from the group consisting of Li, Al, K, Ti, V, Cr, Mn, Co, Zn, Sr, Nb, Mo, In, Si, Sn, Sb, and Cs. It may contain inorganic ingredients. More specifically, the inorganic oxide may include at least one inorganic component selected from the group consisting of Li, K, Sr, Nb, Si, and Cs.

The inorganic complex sulfide may include an inorganic component belonging to Groups 3 to 12 of the periodic table. Specifically, the inorganic composite sulfide may include one or more inorganic components selected from the group consisting of Ti, V, Cr, Mn, Co, Zn, Nb, and Mo.

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

The inorganic deposition layer may have a thickness of 10 nm to 500 nm, and specifically, the inorganic deposition layer may have a thickness of 30 nm to 70 nm. When it is within the above range, it is advantageous to have an appropriate level of luminance and metal texture without lowering adhesion between layers.

In the step of forming the inorganic deposition layer, the deposition of the inorganic material may be performed under heating conditions. For example, the temperature during the deposition of the inorganic material may be 40 °C to 200 °C, more specifically, 60 °C to 150 °C.

primer layer

The primer layer 106 is formed on the surface of the base layer 105 . The primer layer may implement a color in the visible light region or improve bonding strength with other layers.

The primer layer may include at least one selected from a thermosetting resin and a UV curable resin, and specifically, may include a urethane resin, an acrylic resin, and the like.

The primer layer may include a dye or a pigment to implement a color in the visible light region. Specifically, the primer layer may include a pigment dispersion, and the type of pigment or pigment dispersion used in this case is the same as previously exemplified.

The content of the pigment dispersion may be 1 to 30% by weight, 5 to 20% by weight, 0.1 to 10% by weight, or 0.2 to 8% by weight based on the total weight of the primer layer or a primer layer composition for preparing the same. . When it is within the above range, it is advantageous to implement a color in the entire visible light region.

The primer layer may be formed using a method such as micro gravure coating or slot die coating.

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

adhesive layer

The adhesive layer 102 is formed on the surface of the inorganic deposition layer 103 . The adhesive layer can provide adhesive strength when attached to the surface of a product such as glass, improve visibility by removing an air layer, and increase thermal insulation.

The adhesive layer may include an adhesive resin and a curing agent. The pressure-sensitive adhesive resin is not particularly limited, but may be a resin that is not yellowed by ultraviolet rays and has good dispersibility of the UV absorber. For example, as for the said adhesive resin, a polyester resin, an acrylic resin, an alkyd resin, an amino resin, etc. are mentioned. The pressure-sensitive adhesive resin may be used alone, or two or more types of copolymers or mixtures may be used. Among them, an acrylic resin excellent in optical properties, weather resistance, adhesion to a substrate, and the like is preferable.

The curing agent is not particularly limited as long as it is a material capable of curing the pressure-sensitive adhesive resin. Specifically, at least one selected from the group consisting of an isocyanate curing agent, an epoxy curing agent, and an aziridine curing agent that is not yellowed by ultraviolet rays. In addition, the curing agent may be included in an amount of 0.2 to 0.5% by weight, 0.3 to 0.5% by weight, 0.3 to 0.45% by weight, or 0.35 to 0.45% by weight based on the total weight of the adhesive layer. When it is within the above range, it is advantageous to prevent a decrease in adhesive strength or a decrease in durability in heat-resistant and moisture-resistant environments.

The adhesive layer may include a dye or a pigment to implement a color in the visible light region. Specifically, the pressure-sensitive adhesive layer may include a pigment dispersion, and the type of pigment or pigment dispersion used in this case is as exemplified above. The content of the pigment dispersion may be 1 to 30% by weight, 5 to 20% by weight, 0.1 to 10% by weight, or 0.2 to 5% by weight based on the total weight of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive layer composition for preparing the same. . When it is within the above range, it is advantageous to implement a color in the entire visible light region.

In addition, the adhesive layer may further include additives such as antioxidants, light stabilizers, and photoinitiators. For example, the photoinitiator is benzophenone-based, thioxanthone-based, α-hydroxy ketone-based, ketone-based, phenyl glyoxylate-based and At least one kind may be selected from the group consisting of acryl phosphine oxide.

The adhesive layer may have an adhesive force of 10 N/inch or more to the glass in order to prevent scattering of the glass when the glass is broken. Specifically, the adhesive layer may have an adhesive force of 10 to 30 N/inch to glass. When it is within the above range, it may be advantageous to rework for glass recycling in case of sufficient scattering prevention effect and process failure.

The pressure-sensitive adhesive layer has a glass transition temperature of -40°C or higher, specifically -40°C to -15°C, or a glass transition temperature of -30°C to -15°C, in order to suppress the pressing property by the process and external foreign matter. can

The adhesive layer may have a thickness of 10 μm to 30 μm, 15 μm to 25 μm, 15 μm to 20 μm, or 15 μm to 17 μm. If it is within the above range, it is advantageous to prevent defects due to pressing and maintain adhesive strength.

release layer

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

The release layer may protect the surface of the adhesive layer, and may be removed later when the multilayer film is applied to the product.

Examples of the material of the release layer include epoxy-based, epoxy-melamine-based, aminoalkyd-based, acrylic, melamine-based, silicone-based, fluorine-based, cellulose-based, urea resin-based, polyolefin-based, and paraffin-based materials.

organic fixed layer

In addition, the multilayer film 100 may further include an organic fixing layer 104 including a binder resin and an inorganic oxide between the base layer 105 and the inorganic deposition layer 103 .

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

In the case of directly depositing an inorganic deposition layer on the substrate layer to give a metallic texture in the manufacturing process of the existing shatterproof film, the surface of the substrate layer is damaged by the heat applied during the deposition process, resulting in a cloudy appearance and color visibility. may be lowered. However, when the inorganic deposition layer is formed thereon after forming the organic fixing layer on the surface of the substrate layer, the impact applied to the substrate layer by heat can be eliminated to further improve product appearance characteristics and color visibility.

In addition, the organic fixing layer functions as an optical layer having a different refractive index between the existing base layer and the inorganic deposition layer, thereby improving the reflectance by optical compensation of the product.

In addition, the organic pinned layer may improve interlayer bonding strength by an inorganic oxide.

In addition, the organic fixing layer can improve the optical properties by lowering the surface roughness of the multilayer film according to the present invention. Specifically, the surface roughness of the inorganic deposition layer may increase due to organic or inorganic particles typically included as a blocking agent on the surface of the substrate layer, thereby impairing optical properties, but an organic fixing layer between the substrate layer and the inorganic deposition layer This increase in surface roughness can be suppressed by being inserted and serving as a buffer layer.

The binder resin of the organic fixing layer may include at least one selected from a thermosetting resin and a UV curable resin, and specifically, the binder resin may include at least one selected from an acrylic resin and a urethane resin. When it has the binder component, it is advantageous in securing optical transparency and stably forming an inorganic deposition layer.

The acrylic resin may be formed by polymerization of one or more acrylic monomers and carboxyl group-containing unsaturated monomers, respectively. Specifically, examples of the acrylic monomer include 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, tetrahydrofurpril (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylic rate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethyl Acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (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, dicyclopentanyloxyethyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, and mixtures thereof. More specifically, examples of the acrylic monomer include methyl (meth) acrylate, butyl (meth) acrylate, and mixtures thereof.

The inorganic oxide may include at least one inorganic component, for example, an oxide of silicon (Si). More specifically, the inorganic oxide may include at least one _{of SiO and SiO 2 .}

The content of the inorganic oxide may be 10 wt% to 50 wt%, more specifically 20 wt% to 40 wt%, based on the weight of the organic fixing layer. When the content is within the range, the bonding strength between the organic fixing layer and the inorganic deposition layer may be improved, and rework may be advantageous when the adhesive layer is attached to the glass and then peeled off.

The inorganic oxide may have the form of particles. For example, the average particle diameter of the inorganic oxide may be 20 nm to 100 nm, and more specifically, 50 nm to 80 nm. When within the above particle size range, it is possible to exhibit sufficient bonding strength with the inorganic fixing layer, while lowering the surface roughness, it is possible to further improve the optical transmittance of the multilayer film.

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. For example, a coating composition in which a binder resin and an inorganic oxide are blended with an additive such as a curing agent and a solvent may be used for coating by a wet method. Examples of the coating method capable of the wet method include spin coating, slit coating, roll coating, screen printing, applicator coating, and the like. Using this coating method, for example, a wet coating layer is formed to a thickness of 2 to 25 μm, and then dried at a temperature of 50 to 150° C. for 1 to 10 minutes to form an organic fixed layer.

Thereafter, the organic fixing layer may be cured, for example, it may be cured by irradiating actinic rays of 200 to 450 nm. As a light source used for irradiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used, and in some cases, an X-ray, an electron beam, etc. may be used. Although the exposure amount varies depending on the composition and thickness of the organic fixing layer, when a high-pressure mercury lamp is used, it may be ^{100 mJ/cm 2 or less at a wavelength of 365 nm.}

The organic fixing layer may have a thickness of 0.15 μm to 3 μm, more specifically 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 on the organic fixing layer can be formed more stably, it is advantageous to exert the effect of suppressing the increase in surface roughness.

Preferred embodiment

A multilayer film according to a preferred embodiment includes a primer layer having a first color, a base layer, an inorganic deposition layer having a second color, and an adhesive layer having a third color in a laminated form, the first color, the observation of the multilayer film, wherein the second color and the third color are different colors, and the second color has a difference of 5 or more from the first color or the third color in a* value according to the CIE color system; When the angle is changed by 5 degrees to 10 degrees, the change in the a* value of the transmitted color according to the CIE color space is 10 or more.

Effects and uses

The multilayer film according to the present invention includes a structure in which a primer layer, a base layer, an inorganic deposition layer and an adhesive layer are laminated, and by giving different colors to the primer layer, the inorganic deposition layer and the adhesive layer, the colors reflected from each layer And it is possible to realize three-dimensional colors due to their mixed colors.

Specifically, when a specific color is given to the primer layer, the inorganic deposition layer, and the adhesive layer, various colors may be displayed depending on the viewing angle to implement a three-dimensional color.

In addition, the multilayer film according to the present invention may have excellent optical properties due to low surface roughness. For example, the Ra surface roughness of the multilayer film or the Ra surface roughness of the inorganic deposition layer may be 0 to 1 μm, or 0 to 0.1 μm.

In particular, since the multilayer film can be laminated to glass to increase strength while realizing a three-dimensional color than before, it can be used as a decoration film of anti-scattering and metal texture.

laminate

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 Figure 2, the laminate according to the present invention is a glass substrate 200; and the multilayer film 100 according to the embodiment attached so that the adhesive layer 102 is in contact with at least one surface of the glass substrate.

The multilayer film 100 has the same configuration and characteristics as the multilayer film according to the exemplary embodiment described above.

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

In addition, the laminate may further include an additional 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.

mold pattern layer

The mold pattern layer 301 is a layer for implementing a pattern (design) intended by a user.

For example, the mold pattern layer 301 may be patterned by UV curing a raw material on one surface of the primer layer 106 after in-mold injection molding.

The raw material of the mold pattern layer may include a urethane-acrylic oligomer, an amine-based monomer, a carboxyl-based monomer, and the like as a main component.

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

inorganic reflective layer

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

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

The non-conductive inorganic material may be at least one selected from the group consisting of Nb, Si, and Ti, and specifically may be Nb or Si.

The inorganic reflective layer may have a thickness of 0.01 μm to 0.1 μm, specifically 0.02 μm to 0.05 μm. When it is within the above range, it is advantageous to provide an appropriate level of metallic luster without reducing the adhesion between the layers.

light-shielding print layer

The light-shielding printed layer 303 blocks light to further increase reflection efficiency.

The light-shielding printing layer may include a desired photo, pattern, various colors, patterns, etc. according to preference.

Specifically, the light-shielding printing layer may include black ink, for example, black ink (product name: Black) manufactured by HS chemical.

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

The present invention will be described in more detail with reference to 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 film

For the preparation of the primer layer composition, 80 parts by weight of a urethane acrylic oligomer (UV1700B, NIPPON GOHSEI), 15 parts by weight of pentaerythritol triacrylate (M340, Miwon), and 5 parts by weight of a photoinitiator (1-184, Ciba) The parts were mixed, methyl ethyl ketone was added so that the solid content was 20% by weight, and then 4 parts by weight of the pigment was added based on 100 parts by weight of the solid content. At this time, 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 a thickness of 3 μm using a Mayer bar on one side of the base layer (PET film) having a thickness of 100 μm, dried at 80° C. for 2 minutes, and then cured by UV (light amount of 0.4 J/cm 2 ) to form a color primer layer.

Next, for the preparation of the organic fixed layer composition, 60 parts by weight of urethane acrylic oligomer (UV1700B. NIPPON GOHSEI), pentaerythritol triacrylate (M340, Miwon) 15 parts by weight, silicone nanoparticles (MAC2000, TOYOINK) 20 parts by weight and 5 parts by weight of a photoinitiator (1-184, Ciba Co.) were mixed, and methyl ethyl ketone was added so that the solid content was 20% by weight. The organic fixing layer composition was applied to the other surface of the base layer to a thickness of 1 μm using a Mayer bar, dried at 80° C. for 2 minutes, and then UV cured (light amount of 0.4 J/cm 2 ) to form an organic fixing layer.

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

In addition, for the preparation of the pressure-sensitive adhesive layer composition, 35 parts by weight of a pressure-sensitive adhesive (305S, Saiden) and 65 parts by weight of methyl ethyl ketone (MEK) were mixed, and a red dye (RD-01, Iridos) was added thereto in 0.02, 0.03. or 0.05 parts by weight, respectively. The adhesive layer composition was coated on the surface of the color inorganic deposition layer using a gap coater, dried and cured to form a color adhesive layer having a thickness of 25 μm. Thereafter, a release film was laminated on the surface of the color adhesive layer to obtain a multilayer film.

Comparative Example 1: Preparation of a multilayer film to which a transparent adhesive layer is applied

In the manner of Example 1, a color primer layer was formed on one side of the base layer (PET film), and an organic fixing layer was formed on the other side. Thereafter, niobium (Nb) was sputter deposited on the surface of the organic fixing layer to form a color inorganic deposition layer, and an optically transparent adhesive (OCA, SKC HT&M) was coated on the surface of the inorganic deposition layer to obtain a multilayer film.

Comparative Example 2: Preparation of a multilayer film without an organic fixing layer and an inorganic deposition layer

A color primer layer was formed on one surface of the base layer (PET film) in the same manner as in Example 1. Then, an optically transparent 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 of each multilayer film prepared in Examples and Comparative Examples was removed, and the transmitted color was measured using a color measuring device (UV Spectrometer U4100, Hitachi Corporation). The transmitted color was measured at each angle for the same site. The results are summarized in Table 1 below.

multilayer film	transparent color
	Observation angle: 2 degrees			Observation angle: 10 degrees
	L*	a*	b*	L*	a*	b*
Example 1	50.16	21.26	-35.21	52.54	3.020	-35.05
Comparative Example 1	51.23	2.95	39.11	52.33	2.83	38.98
Comparative Example 2	55.33	2.11	38.18	57.22	1.89	38.22

As can be seen from the results of Table 1, since the transmission color of the multilayer film of Example 1 shows a large difference depending on the angle compared to the multilayer films of Comparative Examples 1 and 2, it can be confirmed that various colors can be expressed at various angles. have.

Claims (15)

1. A primer layer having a first color, a base layer, an inorganic deposition layer having a second color, and an adhesive layer having a third color in a laminated form, the first color, the second color, and the third color This is a multi-layer film of different colors.
2. The method of claim 1,

   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 according to the CIE color space;

   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 according to the CIE color system;

   wherein 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 according to the CIE color system.
3. 3. The method of claim 2,

   wherein the multilayer film has a color according to the CIE colorimetric system with an L* value of 25 to 90, an a* value of -40 to 40 and a b* value of -40 to 40.
4. 3. The method of claim 2,

   wherein the second color has a difference of at least 5 from the first color or the third color in a* value according to the CIE color system.
5. The method of claim 1,

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

   A multilayer film comprising at least one of an anthraquinone-based pigment and a phthalocyanine-based pigment, respectively, in the primer layer and the adhesive layer.
7. The method of claim 1,

   The inorganic deposition layer having a thickness of 10 nm to 500 nm, a multilayer film.
8. The method of claim 1,

   The multilayer film, wherein the inorganic deposition layer is formed by sputtering or electron beam deposition.
9. The method of claim 1,

   The inorganic deposition layer comprising at least one selected from the group consisting of an inorganic single material, an inorganic composite oxide, and an inorganic composite sulfide, a multilayer film.
10. 10. The method of claim 9,

    the single inorganic material is at least one selected from the group consisting of metals, nonmetals, metalloids and rare earth metals;

    The inorganic composite oxide is one or more inorganic components selected from the group consisting of Li, Al, K, Ti, V, Cr, Mn, Co, Zn, Sr, Nb, Mo, In, Si, Sn, Sb and Cs. including;

    The multilayer film, wherein the inorganic composite sulfide includes at least one inorganic component selected from the group consisting of Ti, V, Cr, Mn, Co, Zn, Nb and Mo.
11. The method of claim 1,

    The multilayer film, between the base layer and the inorganic deposition layer, further comprising an organic fixing layer comprising a binder resin and an inorganic oxide, the multilayer film.
12. 12. The method of claim 11,

    The binder resin of the organic fixing layer is a multilayer film comprising at least one of an acrylic resin and a urethane resin.
13. 12. The method of claim 11,

    The inorganic oxide includes an oxide of silicon (Si) and has an average particle diameter of 20 nm to 100 nm, a multilayer film.
14. The method of claim 1,

    The multilayer film is used as a decorative film of scattering prevention and metal texture, a multilayer film.
15. A laminate comprising a glass substrate and the multilayer film of claim 1 attached to at least one surface of the glass substrate so that the adhesive layer is in contact.

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