WO2021167377A1 - Multilayer film and laminate comprising same - Google Patents

Abstract

A multilayer film, according to the present invention, has an organic fixing layer formed on the surface of a base layer, and then an inorganic deposition layer formed on top thereof, and thus damage to the surface of the base layer caused by heat applied in a deposition process is prevented, thereby enabling the implementation of a clear metal texture. In addition, the multilayer film may be laminated on glass so as to increase strength, and thus may be applied as a scattering prevention and decorative film.

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

In the past, various colors in the visible light region were realized by using an appropriate amount of pigment in the manufacturing process of the anti-shattering film. Also, recently, a method of realizing metallic luster without using a metallic material by depositing an inorganic material by non-conductive vacuum deposition has been developed. In this method, it is possible to reduce the cost of raw materials while reducing the heavy weight, which is a disadvantage of the metal material, and it is possible to manufacture it with a thin thickness even by stacking various functional layers.

However, when the inorganic material is directly deposited on the base layer, the surface of the base layer is damaged by heat applied during the deposition process, and thus the appearance of the base layer is cloudy.

As a result of research by the present inventors, it was found that by forming an organic fixing layer on the surface of the base layer and then forming an inorganic deposition layer thereon, the existing problems can be solved and a target color can be realized.

Accordingly, an object of the present invention is to provide a multilayer film capable of increasing strength by being laminated to glass while realizing a clear metal texture by preventing deformation caused by heat when forming an inorganic deposition layer, a method for manufacturing the same, and a laminate with the glass will provide

According to the above object, the present invention provides a multilayer film comprising a primer layer, a base layer, an organic fixing layer, an inorganic deposition layer and an adhesive layer in a laminated form, and wherein the organic fixing layer includes a binder resin and an inorganic oxide.

According to another object, the present invention provides a method comprising: forming an organic fixing layer including a binder resin and an inorganic oxide on one surface of a base layer; depositing an inorganic material on the surface of the organic fixing layer to form an inorganic deposition layer; and forming a primer layer on the other surface of the base layer and forming an adhesive layer on the surface of the inorganic deposition layer.

According to another object, the present invention provides 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 does not directly form the inorganic deposition layer on the surface of the substrate layer, but forms the organic fixing layer on the surface of the substrate layer and then forms the inorganic deposition layer thereon. to prevent damage to the surface of As a result, even if the multilayer film includes an inorganic deposition layer for a metal texture, an appearance does not change from being cloudy after manufacturing, and thus a target color can be clearly implemented.

In addition, since the multilayer film is laminated to glass to increase strength and implement various colors and designs including metal texture, 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 is a laminated form of a primer layer 106, a base layer 105, an organic fixing layer 104, an inorganic deposition layer 103 and an adhesive layer 102. and the organic fixing layer 104 includes a binder resin and an inorganic oxide.

In addition, the multilayer film 100 may further include a release layer 101 for protecting the surface of the adhesive layer 102 .

Hereinafter, each component will be described in detail.

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 85% 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.

organic fixed layer

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. There was a problem with degradation. However, according to the present invention, after forming the organic fixing layer on the surface of the substrate layer and then forming the inorganic deposition layer thereon, the impact applied to the substrate layer by heat can be eliminated to solve the problem that the appearance of the product is cloudy, and as a result, the target color can be realized.

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 the 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 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.

inorganic deposition layer

The inorganic deposition layer 103 is formed on the surface of the organic fixing layer 104, and improves luminance and reflectance while providing a metal texture by including an inorganic deposition material.

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

The inorganic composite oxide and the inorganic composite sulfide may be formed by bonding an inorganic component 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 composite 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 thickness of the inorganic deposition layer may be 10 nm to 500 nm, for example, 10 nm to 100 nm, 10 nm to 50 nm, 30 nm to 70 nm. 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.

primer layer

The primer layer 106 is formed on the other surface of the base layer 105 (the surface on which the organic fixing layer 104 is not formed). 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 be colorless and transparent or may have a color.

For example, the primer layer may include a dye or a pigment to implement a color in the visible region. For example, the primer 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.

The pigment is not limited as long as it can implement a color in the visible region as commonly used in the art, and may be, for example, an anthraquinone-based, 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.

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 be colorless and transparent or may have a color.

As an example, the adhesive layer may be colorless and transparent including an optical clear adhesive (OCA).

As another example, 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 in the primer layer 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 thickness of the adhesive layer may be 10 μm to 50 μm, specifically, 10 μm to 25 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.

As the release layer, a conventional release film used to protect the surface of the adhesive layer may be used.

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.

Properties

The multilayer film may have a higher 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.

In addition, the multilayer film may implement various colors while showing a metallic texture. Specifically, the multilayer film may have a color in which L*, a*, and b* values are adjusted according to the CIE color system. For example, the L* value of the color of the multilayer film may be 10 to 70, more specifically 20 to 60. 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 a specific example, the multilayer film may have an L* value of 10 to 70, an a* value of -40 to 40, and a b* value of -40 to 40 according to the CIE color system. As a more specific example, the multilayer film may have an L* value of 40 to 50, an a* value of -4 to 2, and a b* value of -12 to -6 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, may be a value of a reflected color.

In addition, the multilayer film may exhibit three-dimensional and various colors by giving different colors to the primer layer, the inorganic deposition layer, and the adhesive layer. For example, the multilayer film may include a primer layer having a first color and an inorganic deposition layer having a second color, and the first color and the second color may have different colors. In this case, the color coordinates L*, a*, and b* of these colors may each have a difference of 1 or more, specifically 5 or more, and more specifically 10 or more. Accordingly, the multilayer film can be viewed in different colors depending on the viewing angle, thereby enabling three-dimensional and various colors to be expressed. For example, when the multilayer film is observed at 2 degrees and 10 degrees, respectively, 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 with respect to the plane direction of the multilayer film, and the a* value may be a measured value for the transmitted color.

In addition, as described above, 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.

Manufacturing method of multilayer film

The method for manufacturing a multilayer film according to the present invention comprises the steps of: forming an organic fixing layer comprising a binder resin and an inorganic oxide on one surface of a base layer; depositing an inorganic material on the surface of the organic fixing layer to form an inorganic deposition layer; and forming a primer layer on the other surface of the base layer and forming an adhesive layer on the surface of the inorganic deposition layer.

First, an organic fixing layer including a binder resin and an inorganic oxide is formed on one surface of the base layer.

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 inorganic deposition layer may be formed by sputtering or electron-beam evaporation. 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. According to the present invention, the deformation of the substrate layer can be suppressed due to the presence of the organic fixing layer even during high-temperature deposition as described above.

Preferred embodiment

The multilayer film according to a preferred embodiment includes a primer layer, a base layer, an organic fixing layer, an inorganic deposition layer and an adhesive layer in a laminated form, the organic fixing layer includes a binder resin and an inorganic oxide, and the total light transmittance of the multilayer film is 85% or more, the haze is 1% or less, the primer layer and the inorganic vapor deposition layer have different colors, and the a* value changes according to the CIE color system when the multilayer film is observed at 2 degrees and 10 degrees, respectively is 5 or more.

In addition, the method of manufacturing a multilayer film according to a preferred embodiment comprises the steps of: forming an organic fixing layer comprising a binder resin and an inorganic oxide on one surface of a base layer; depositing an inorganic material on the surface of the organic fixing layer to form an inorganic deposition layer; and forming a primer layer on the other surface of the base layer and forming an adhesive layer on the surface of the inorganic deposition layer, wherein the multilayer film has a total light transmittance of 85% or more and a haze of 1% or less, and When the primer layer and the inorganic deposition layer have different colors, and when the multilayer film is observed at 2 degrees and 10 degrees, respectively, the change in a* value according to the CIE color system is 5 or more.

Effects and uses

The multilayer film does not directly form an inorganic deposition layer on the surface of the substrate layer, but forms an organic fixing layer on the surface of the substrate layer and then forms an inorganic deposition layer thereon. damage can be prevented.

As a result, even if the multilayer film includes an inorganic deposition layer for a metal texture, an appearance does not change from being cloudy after manufacturing, and thus a target color can be clearly implemented.

In addition, since the multilayer film is laminated to glass to increase strength and implement various colors and designs including metal texture, it can be used as a decoration film of scattering prevention 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, and the like. For example, tempered glass may be used and may have a thickness of 300 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 a multilayer film having an organic fixed layer

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 A (BV231, Iridos) and 1 part by weight of pigment B (BO260, Iridos) were used as pigments. The primer layer composition was coated on one surface of the base layer (PET film) having a thickness of 100 μm to a thickness of 3 μm using a Mayer bar, 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 coated on the other surface of the base layer to a thickness of 3 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. Then, an optically transparent adhesive (OCA, SKC HT&M) was coated on the surface of the color inorganic deposition layer to obtain a multilayer film.

Comparative Example 1: Preparation of a multilayer film without an organic fixing layer

A color primer layer was formed on one surface of the base layer (PET film) in the same manner as in Example 1. Niobium (Nb) was sputter-deposited on the other surface of the base 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 having no inorganic oxide in the organic fixed layer

A color primer layer was formed on one surface of the base layer (PET film) in the same manner as in Example 1. In addition, an organic fixing layer was formed on the other surface of the substrate layer in the manner of Example 1, but a composition was prepared without adding organosilicon-based nanoparticles and then coated to obtain an organic fixing layer. Then, niobium (Nb) was sputtered and 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 thereon to obtain a multilayer film.

test example

Each of the multilayer films prepared in Examples and Comparative Examples was evaluated as follows, and the results are shown in Table 1 below.

(1) Reflectance and specular color coordinates

The release layer of the multilayer film was removed, and reflectance and reflected color were measured using a color measuring device (Colormeter CM-3700A, Konica-Minolta).

(2) Adhesion and residue evaluation

The multilayer film was cut to a size of 2.54 cm × 20 cm, the release layer was removed, and the adhesive layer was laminated on soda-lime glass. Thereafter, it was left at room temperature for 60 minutes, and a peel test was performed at an angle of 180 degrees and a speed of 0.3/min. Upon peeling, it was classified according to the following criteria by visually observing whether the residue of the adhesive layer remained on the glass substrate.

- None: There is no residue of the transparent adhesive layer on the soda-lime glass.

- Occurrence: A transparent adhesive layer residue is generated on the soda-lime glass.

(3) Measurement of light transmittance and haze

In the manufacturing process of the multilayer film of the Examples and Comparative Examples, for the samples produced before the formation of the inorganic deposition layer and lamination of the optically transparent adhesive tape, using a haze meter (NDH-5000, Nippon Denshoku Co., Ltd.) All light according to ASTM D1003 Transmittance and haze were measured.

The results are summarized in the table below.

division	Reflectance (550nm)	Reflection color (L*, a*, b*)	Adhesion (N/in.)	adhesive residue	haze	total light transmittance
Example 1	14%	43.2, -1.5, -7.6	15.1	radish	0.6%	87.2%
Comparative Example 1	12%	38.1, -1.0, -6.4	10.3	generation	1.1%	85.9%
Comparative Example 2	12%	42.2, -1.4, -7.4	10.3	generation	0.7%	86.7%

As shown in Table 1, the multilayer film having an organic fixing layer having an inorganic oxide as in Example 1 had high reflectance and high L* of the reflective color, so it had excellent visibility, and had high adhesion to the glass substrate and adhesion during peeling. Since no residue was generated, the coating appearance and adhesion properties were excellent.

On the other hand, as in Comparative Example 1, the multilayer film without the organic fixing layer had low reflectance and low L* of the reflective color, so visibility was relatively low, haze was high and transmittance was low, and also the adhesion to the glass substrate was low and peeling was clean. There was a problem that the adhesive remained because it was not supported. This is a result of the lack of an organic fixing layer, the surface being damaged by the heat applied during the deposition of the inorganic material, and the low adhesion between the inorganic deposition layer and the base layer.

In addition, even when an organic fixing layer having no inorganic oxide was provided as in Comparative Example 2, the adhesive force to the glass substrate was low and peeling was not performed cleanly, so that the adhesive remained, and the reflectance was also low. From this, it can be seen that the presence or absence of an inorganic oxide in the organic fixed layer is an important factor in the bonding force between the inorganic deposition layer and the base layer.

Claims (15)

1. A multilayer film comprising a primer layer, a base layer, an organic fixing layer, an inorganic deposition layer and an adhesive layer in a laminated form, wherein the organic fixing layer includes a binder resin and an inorganic oxide.
2. The method of claim 1,

   The binder resin of the organic fixing layer is a multilayer film comprising at least one of an acrylic resin and a urethane resin.
3. The method of claim 1,

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

   The organic fixing layer is a multilayer film comprising the inorganic oxide in an amount of 20% to 40% by weight based on the weight of the organic fixing layer.
5. The method of claim 1,

   A multilayer film, wherein the organic fixing layer has a thickness of 0.5 μm to 1 μm.
6. The method of claim 1,

   A multilayer film, wherein the primer layer is colorless and transparent or has a color.
7. The method of claim 1,

   wherein the multilayer film has a visible light reflectance of 10% to 50%.
8. The method of claim 1,

   wherein the multilayer film has an L* value of 10 to 70, an a* value of -40 to 40 and a b* value of -40 to 40 according to the CIE colorimetric system.
9. The method of claim 1,

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

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

    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 is used as a decorative film of scattering prevention and metal texture, a multilayer film.
12. The method of claim 1,

    The multilayer film further comprises a release layer on the surface of the adhesive layer, the multilayer film.
13. forming an organic fixing layer including a binder resin and an inorganic oxide on one surface of the base layer;

    depositing an inorganic material on the surface of the organic fixing layer to form an inorganic deposition layer; and

    Forming a primer layer on the other surface of the base layer and forming a pressure-sensitive adhesive layer on the surface of the inorganic deposition layer, the method for producing a multilayer film.
14. 14. The method of claim 13,

    A method for producing a multilayer film, wherein the organic fixing layer is formed by wet coating.
15. glass substrate; and

    A laminate comprising 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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