KR102578783B1 - Anti-scattering film with pearl texture and preparation method thereof - Google Patents

Abstract

The film according to the present invention can provide two or more constituent layers with different colors to create three-dimensional colors depending on the observation angle due to the colors reflected from each layer and their mixed colors. In particular, according to the present invention, by adding colored inorganic particles having a particle size within a specific range to the adhesive layer of the film, it is possible to achieve a metallic particle feel or pearl texture while maintaining the adhesive force necessary to prevent scattering.

Description

Anti-scattering film with pearl texture and manufacturing method thereof {ANTI-SCATTERING FILM WITH PEARL TEXTURE AND PREPARATION METHOD THEREOF}

The present invention relates to an anti-shattering film for attachment to glass, etc., and a method of manufacturing the same. More specifically, the present invention relates to an anti-shatter film with a pearl texture and a decoration function added thereto, and a method for manufacturing the same.

In the electrical and electronics field, display devices are developed in various forms considering the purpose of use, portability, convenience, etc. In particular, because consumers value design according to the purpose of the display, various designs of displays are being researched. A design that has recently been in the spotlight in the electrical and electronics field is a metallic design, and metallic designs are 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 gloss and excellent brightness, but it has disadvantages such as blocking radio waves, being heavy, and having high production costs.

To compensate for this, displays using glass or transparent plastic instead of metal are being developed. Glass or plastic materials have the advantage of lower manufacturing costs and lower weight compared to metal, but they have the fatal disadvantage of being low in strength and particularly weak against impact. Therefore, to improve the design of displays made of these materials, shatterproof films are being applied that embody color while simultaneously increasing strength, reinforcing against impact, and considering safety in case of damage.

For example, Republic of Korea Patent Publication No. 2014-0110325 discloses an anti-shattering film in which a hard coating layer containing an azo dye is formed on a transparent film, and Republic of Korea Patent Publication No. 2015-0096860 discloses an absorption wavelength band of 400 to 700 nm. A film including a hard coating layer to which a phosphorus colored dye is added is disclosed.

Republic of Korea Patent Publication No. 2014-0110325 Republic of Korea Patent Publication No. 2015-0096860

Recently, films with various colors and designs are being developed to prevent shattering films used to prevent damage to glass or transparent plastic. However, existing films only expressed two-dimensional colors with a single color or a gradation of one or two colors and could not create three-dimensional colors.

In addition, there have been attempts to create a metallic texture by mixing colored additives in the adhesive layer provided in the anti-shattering film, but these additives have reduced the adhesive strength, making it difficult to achieve anti-shattering performance.

Accordingly, as a result of the present inventors' research, three-dimensional colors are realized by mixing different colors in two or more constituent layers, and colored inorganic particles with a specific range of particle diameters are added to the adhesive layer to create a metallic particle feel, while preventing scattering. We were able to develop a film that could maintain the necessary adhesive strength.

Therefore, the object of the present invention is to provide an anti-shattering film that can increase strength by being laminated to glass while realizing three-dimensional color and metallic texture effects.

According to the above problem, the present invention provides a base layer; A color coating layer having a first color; and an adhesive layer containing colored inorganic particles with a particle size of 1 ㎛ to 100 ㎛ and having a second color different from the first color, the adhesive layer being pressed and laminated on the surface of the glass substrate with a 1 kg roller for 300 minutes. Provided is a film having a 180 degree peel adhesion of at least 10 N/inch, measured at a speed of mm/min.

In addition, the present invention includes forming a color coating layer on one side of a base layer using a first resin composition containing a dye or pigment; and forming an adhesive layer on the other side of the base layer using a second resin composition containing colored inorganic particles with a particle size of 1 ㎛ to 100 ㎛.

The film according to the present invention can provide two or more constituent layers with different colors to create three-dimensional colors depending on the observation angle due to the colors reflected from each layer and their mixed colors. In particular, according to the present invention, by adding colored inorganic particles having a particle size within a specific range to the adhesive layer of the film, it is possible to achieve a metallic particle feel or pearl texture while maintaining the adhesive force necessary to prevent scattering.

Therefore, the film of the present invention can be attached to various displays containing glass or transparent plastic substrates, automobiles, home appliances, etc. to not only serve as a decoration but also function as an anti-shattering film that prevents damage, and is made of a thin film, making it a flexible electronic device that has recently attracted attention. It can also be applied.

1 is a perspective view of a film according to one embodiment.
Figure 2 is a cross-sectional view of a film according to one embodiment (AA' in Figure 1).
Figure 3 shows a film according to another embodiment applied to a glass substrate.
Figure 4 shows a method for measuring the 180 degree peel adhesion of a film.
Figure 5 is an example of images of films produced in various colors.

Hereinafter, various implementation examples and embodiments of the present invention will be described in detail with reference to the drawings.

In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted. Additionally, the size of each component in the drawings may be exaggerated or omitted for explanation and may differ from the actual size.

In this specification, the description that one component is formed above/below another component, or is connected or combined with each other, includes all those formed, connected, or combined directly between these components or indirectly through another component. . Additionally, it should be understood that the standards for the top/bottom of each component may vary depending on the direction in which the object is observed.

In this specification, terms referring to each component are used to distinguish them from other components and are not intended to limit the present invention. Additionally, in this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

In this specification, terms such as first and second are used to describe various components, and the components should not be limited by the terms. The above terms are used for the purpose of distinguishing one component from another.

In this specification, the term "include" is intended to specify specific characteristics, areas, steps, processes, elements and/or components, and unless specifically stated to the contrary, other characteristics, areas, steps, processes, elements and /or does not exclude the presence or addition of ingredients.

shatterproof film

The film according to one embodiment of the present invention includes a base layer; A color coating layer having a first color; and an adhesive layer containing colored inorganic particles with a particle size of 1 ㎛ to 100 ㎛ and having a second color different from the first color, the adhesive layer being pressed and laminated on the surface of the glass substrate with a 1 kg roller for 300 minutes. The 180-degree peel adhesion measured at a speed of mm/min is greater than 10 N/inch.

Figures 1 and 2 show a perspective view and a cross-sectional view of a film according to an embodiment of the present invention, respectively.

The film 100 according to one embodiment has a metallic particle feel or a pearly texture due to the colored inorganic particles added to the adhesive layer 110, and the color saturation is improved so that the color can be clearly seen (see FIG. 5). Accordingly, the sum of the absolute value of the a* value and the absolute value of the b* value according to the CIE colorimetric system of the transmission color measured from the front may be above a certain level. For example, the sum of the absolute value of the a* value and the absolute value of the b* value according to the CIE colorimetric system of the transmission color measured from the front of the film may be 5 or more. Specifically, the sum of the absolute value of the a* value and the absolute value of the b* value according to the CIE colorimetric system of the transmission color measured from the front of the film may be 5 or more, 10 or more, or 15 or more, and may also be 50 or less, or 40 or less. , may be 30 or less, or 20 or less. More specifically, the sum of the absolute values of the a* value and the absolute value of the b* value according to the CIE colorimetric system of the transmission color measured from the front of the film may be 5 to 50, 5 to 40, or 5 to 30.

In addition, the film 100 according to one embodiment provides different colors, that is, a first color and a second color, to the adhesive layer 110 and the color coating layer 130, so that the colors reflected from each layer and their mixture Due to the color, it is possible to implement a three-dimensional color in which the color is viewed differently depending on the observation direction (L1, L2) of the film 100.

For example, the difference between the a* value or the b* value between the first color and the second color according to the CIE color system may be 5 or more. Specifically, the difference in a* value between the first color and the second color according to the CIE colorimetric system may be 5 or more, 10 or more, or 15 or more. Additionally, the difference in b* values between the first color and the second color according to the CIE colorimetric system may be 5 or more, 10 or more, or 15 or more. The first color can be obtained by measuring the transmission color from the front after forming the adhesive layer on a transparent substrate, and the second color can be obtained by measuring the transmission color from the front after forming the color coating layer on a transparent substrate. It can be obtained by measuring.

According to one embodiment, the film may satisfy the following equation (1):

5 ≤ │a5 - a10│ ... (1)

Here, a5 is the CIELAB a* value measured in a direction forming a 5° angle with the front direction of the film, and a10 is the CIELAB a* value measured in a direction forming a 10° angle with the front direction of the film.

Specifically, the value of │a5 - a10│ in equation (1) may be 5 or more, 10 or more, or 15 or more, and may also be 50 or less, 30 or less, or 20 or less. More specifically, in equation (1), the value of │a5 - a10│ may be 5 to 50, 50 to 30, or 5 to 20.

According to one embodiment, the film may have a structure in which the color coating layer, the base layer, and the adhesive layer are laminated in that order.

According to another embodiment, the film may have a structure in which the base layer, the color coating layer, and the adhesive layer are laminated in that order.

Films according to the invention may further comprise additional colored layers.

For example, the film further includes an inorganic deposition layer formed between the base layer and the color coating layer or between the base layer and the adhesive layer, and the inorganic deposition layer has the first color and the second color. It may have a third color that is different from the color.

According to one embodiment, the film may have a structure in which the color coating layer, the inorganic deposition layer, the base layer, and the adhesive layer are laminated in that order.

According to another embodiment, the film may have a structure in which the color coating layer, the base layer, the inorganic deposition layer, and the adhesive layer are laminated in that order.

According to another embodiment, the film may have a structure in which the inorganic deposition layer, the color coating layer, the base layer, and the adhesive layer are laminated in that order.

The film according to the present invention may further include one or more additional functional layers.

Referring to FIG. 3, the film 100 includes an adhesive layer 110, a base layer 120, a color coating layer 130, and an inorganic deposition layer 140, as well as a pattern layer 150, a reflective layer 160, and a blocking layer. It may further include at least one of the layers 170.

Hereinafter, each layer constituting the film of the present invention will be described in detail.

base layer

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

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

The base layer needs to be stable from elements that can impede the uniformity of the coating layer, such as static charges, without causing a reaction with the chemical substance coated on the surface. For this, polyethylene terephthalate (PET) or Stretched polypropylene (OPP) is preferred.

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

The base layer may be a uniaxially stretched film, for example, a film stretched 2 to 5 times in the longitudinal direction (i.e., machine direction, MD) or the width direction (i.e., tenter direction, TD). Alternatively, the base layer may be a biaxially stretched film, for example, a film stretched 2 to 5 times in the longitudinal direction (MD) and 2 to 5 times in the transverse direction (TD).

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

The thickness of the base layer may be 10㎛ to 200㎛, specifically 20㎛ to 125㎛, more specifically 23㎛ to 100㎛.

Additionally, the base layer may additionally 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 ㎛ or more, for example, 0.1 ㎛ to 5 ㎛, or 0.1 ㎛ to 1 ㎛.

Color coating layer

The sheet according to the present invention includes a color coating layer formed on one side of the base layer. The color coating layer can implement colors in the visible light region and improve bonding strength with adjacent layers.

The color coating layer may include one or more selected from thermosetting resin and UV curable resin, and may specifically include urethane resin, acrylic resin, and urethane acrylate resin.

The color coating layer may include dye or pigment to adjust color. As an example, the color coating layer may include acrylic or urethane resin, and dye or pigment.

The pigment is not limited as long as it is commonly used in the industry and can implement colors in the visible light range. For example, it may be an organic pigment such as an anthraquinone-based pigment or a phthalocyanine-based pigment. Specifically, the color coating layer may include a pigment dispersion, and the pigment dispersion may include, for example, a pigment and an oligomeric compound having at least one of 3 to 8 hydroxyl groups and carbonyl groups. Examples of oligomeric compounds having 3 to 8 at least one of the hydroxyl group and carboxyl group may be N-vinylpyrrolidone, pentaerythritol triacrylate, tricyclodecane dimethanol diacrylate, etc., specifically , pentaerythritol triacrylate, tricyclodecane dimethanol diacrylate, etc. 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 color coating layer or the color coating layer composition for producing the color coating layer. . When within the above range, it is advantageous to implement colors in the entire visible light range.

The thickness of the color coating layer may be 1㎛ to 10㎛, specifically 1㎛ to 7㎛, more specifically 1㎛ to 5㎛.

Adhesive layer

Since the adhesive layer provides adhesive strength when attached to the surface of a product such as glass or transparent plastic, the film can be used to prevent glass or transparent plastic from scattering. Additionally, the adhesive layer can eliminate air layers when attached to the surface of a product such as glass, thereby improving visibility and enhancing insulation.

The adhesive layer provides adhesive strength to the film and contains colored inorganic particles to provide a color in the visible light region and a metallic texture.

The adhesive layer may include an adhesive resin and a curing agent. The adhesive resin is not particularly limited, but may be a resin that does not yellow by ultraviolet rays and has good dispersibility of the UV absorber. For example, the adhesive resin may include polyester resin, acrylic resin, alkyd resin, amino resin, etc. The adhesive resin can be used alone, or two or more types of copolymers or mixtures can be used. Among them, acrylic resins having excellent optical properties, weather resistance, adhesion to the substrate, etc. are preferable.

The curing agent is not particularly limited as long as it is a material capable of curing the adhesive resin. Specifically, one or more types may be selected from the group consisting of isocyanate curing agents, epoxy curing agents, and aziridine curing agents that do not yellow by ultraviolet rays. Additionally, the curing agent may be included in an amount of 0.2 to 0.5 wt%, 0.3 to 0.5 wt%, 0.3 to 0.45 wt%, or 0.35 to 0.45 wt% based on the total weight of the adhesive layer. If it is within the above range, it is advantageous in preventing a decrease in adhesion or a decrease in durability in a heat-resistant and moisture-resistant environment.

The particle size of the colored inorganic particles may be 1 ㎛ or more, 3 ㎛ or more, 5 ㎛ or 10 ㎛ or more, and may also be 100 ㎛ or less, 70 ㎛ or less, and 50 ㎛ or less. It may be 30 ㎛ or less or 20 ㎛ or less. As an example, the particle size of the colored inorganic particles may be in the range of 5 ㎛ to 30 ㎛. Within the above particle size range, it is advantageous to achieve a metallic particle feel or pearl texture while not reducing adhesive strength.

The particle size of the colored inorganic particles can be obtained by laser diffraction particle size distribution measurement method, and can be measured, for example, using a laser particle size analyzer from Horiba. As an example, in the particle size distribution of the colored inorganic particles, when the particle size of the inorganic particles is in the range of 5 ㎛ to 30 ㎛, D50 may be 15 ㎛ to 20 ㎛, D10 may be 7 ㎛ to 12 ㎛, and D90 may be 23 ㎛ It may be from 28 μm.

Additionally, the particle size of the colored inorganic particles contained in the film can be measured using an electron microscope or an optical microscope.

The content of the colored inorganic particles may be 0.1% by weight, 0.2% by weight, 0.5% by weight, 1% by weight, or 2% by weight, and 30% by weight or less, 10% by weight, based on the weight of the adhesive layer. It may be 5% by weight or less, 3% by weight or less, 2.5% by weight or less, 2% by weight or less, or 1% by weight or less. As an example, the content of the colored inorganic particles may be 0.1% by weight to 2.5% by weight. When the content is within the above range, it is advantageous for achieving adhesion to glass and pearl texture and color.

For example, the colored inorganic particles may be pearl particles made of an inorganic material used for decoration purposes. Specifically, the colored inorganic particles may include a metal oxide, for example, one or more selected from the group consisting of aluminum oxide, titanium oxide, tin oxide, and zirconium oxide.

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 One or more types may be selected from the group consisting of acryl phosphine oxide.

According to one embodiment of the present invention, the adhesive layer is pressed and laminated to the surface of a glass substrate with a 1 kg roller, and then the 180-degree peel adhesive force measured at a speed of 300 mm/min is 10 N/inch or more. 180 degree peel adhesion can be measured, for example, as shown in Figure 4. If the peel adhesion of the film is less than 10 N/inch, it is difficult to prevent the glass from scattering when the glass breaks. For example, the 180 degree peel adhesion of the film to the glass substrate may be greater than 10 N/inch, greater than 15 N/inch, or greater than 20 N/inch, and may also be less than 35 N/inch, less than 30 N/inch, or greater than 25 N/inch. It can be N/inch or less. 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 can be advantageous to have a sufficient anti-scattering effect and to rework the glass for recycling in case of a process failure.

The adhesive layer may have a glass transition temperature of -40°C or higher, specifically -40°C to -15°C, or -30°C to -15°C, in order to suppress compression by processes and external foreign substances. You can.

The thickness of the adhesive layer may be 10㎛ to 30㎛, 15㎛ to 25㎛, 15㎛ to 20㎛, or 15㎛ to 17㎛. Specifically, the thickness of the adhesive layer may be in the range of 15 ㎛ to 25 ㎛. If the thickness is within the above range, it is advantageous to prevent defects due to pressing and maintain adhesive strength while ensuring the flexibility of the film.

The film of the present invention may additionally include a release paper (liner) on the surface of the adhesive layer. The release paper can protect the surface of the adhesive layer and can be removed when the film is later applied to a product. The release paper may include epoxy, epoxy-melamine, aminoalkyd, acrylic, melamine, silicone, fluorine, cellulose, urea resin, polyolefin, paraffin, etc.

Inorganic deposition layer

The inorganic deposition layer contains inorganic deposits and can improve luminance and reflectance while providing a metallic texture. Additionally, the inorganic deposition layer may have a different color from the adhesive layer and the color coating layer.

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

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

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

The inorganic complex oxide and the inorganic complex sulfide may be formed by combining an inorganic component with oxygen (O) or sulfur (S) through an ionic bond, covalent bond, etc. Additionally, the inorganic composite oxide and the inorganic composite sulfide may have one or more types of lattice structures selected from the group consisting of simple cubic, face-centered cubic, and body-centered cubic.

The inorganic composite oxide may include metals, non-metals, metalloids, rare earth metals, etc. as inorganic components. Specifically, the inorganic composite oxide is one or more selected from the group consisting of Li, Al, K, Ti, V, Cr, Mn, Co, Zn, Sr, Nb, Mo, In, Si, Sn, Sb and Cs. May contain inorganic components. More specifically, the inorganic oxide may include one or more inorganic components selected from the group consisting of Li, K, Sr, Nb, Si, and Cs.

The inorganic complex sulfide may include inorganic components 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 brightness and metal texture without deteriorating the 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 deposition of the inorganic material may be 40°C to 200°C, more specifically 60°C to 150°C.

Additional functional layer

In addition, optical properties and decoration functions can be added by further forming a pattern layer, reflection layer, light blocking layer, etc. on the film.

The pattern layer may be a layer formed with a pattern to implement a design such as a specific shape, character, or texture. For example, by applying a prism, lenticular lens, or hemispherical lens pattern to the surface of the pattern layer, a unique effect can be created by additionally providing light refraction and reflection. Specifically, the pattern layer may include a prism lens layer or a lenticular lens layer in the form of a single layer or a double layer. The pattern layer can be formed into a desired pattern by in-mold injection molding a polymer resin composition and then UV curing it. For example, the pattern layer may include a polymer resin polymerized with one or more selected from urethane acrylate-based oligomers, amine-based monomers, and carboxyl-based monomers. Additionally, the thickness of the pattern layer may be 10 ㎛ to 20 ㎛, specifically 10 ㎛ to 17 ㎛, or 15 ㎛ to 17 ㎛.

The light blocking layer can further increase reflection efficiency by including a material that blocks light. Accordingly, the light blocking layer may have a function of blocking light from leaking to the rear. Additionally, the light blocking layer may include desired photos, patterns, various colors, patterns, etc., depending on preference. The thickness of the light blocking layer may be 10 ㎛ to 50 ㎛, specifically 15 ㎛ to 20 ㎛.

Additionally, the sheet of the present invention may additionally include a reflective layer to maximize reflective efficiency or provide a metallic texture. For example, the sheet may further include a reflective layer with a metallic texture deposited between the pattern layer and the blocking layer. The reflective layer may be a layer deposited with an inorganic material, and may specifically include one or more inorganic materials selected from Nb, Si, Ti, In, Ag, and Sn. Additionally, the reflective layer can be formed by non-conductive vacuum deposition (NCVM) of one or more inorganic materials. The reflective layer may have not only a reflective effect but also a metallic luster effect due to the color of the inorganic material. The reflective layer may also function as a planarization layer to attenuate the steps of the pattern layer, or a separate planarization layer may be provided in addition to the reflective layer.

Film manufacturing method

A method for manufacturing a film according to an embodiment of the present invention includes forming a color coating layer on one side of a base layer using a first resin composition containing a dye or pigment; and forming an adhesive layer on the other side of the base layer using a second resin composition containing colored inorganic particles with a particle size of 1 ㎛ to 100 ㎛.

The forming step of the color coating layer and the forming step of the adhesive layer may be performed sequentially, for example, forming the color coating layer and then forming the adhesive layer, or forming the adhesive layer and then forming the color coating layer. can be formed. Alternatively, the color coating layer forming step and the adhesive layer forming step may be performed simultaneously.

The first resin composition used to form the color coating layer may include, for example, a pigment or a pigment dispersion, and the specific type and content of the pigment or pigment dispersion are as previously exemplified. Additionally, the first resin composition may further include a thermosetting resin or UV-curable resin, and may further include a solvent for controlling viscosity.

In addition, the formation of the color coating layer can be performed by coating the first resin composition on one surface of the base layer, for example, methods such as micro gravure coating and slot die coating can be used.

The second composition used to form the adhesive layer may include colored inorganic particles and an adhesive resin, and specific types of the colored inorganic particles and adhesive are as previously exemplified.

The content of the colored inorganic particles in the second resin composition may be 0.01% by weight or more, 0.02% by weight or more, 0.05% by weight or more, 0.1% by weight or more, or 0.3% by weight or more, and may be 5% by weight or less, 3% by weight or less. , may be 1% by weight or less, 0.7% by weight or less, 0.5% by weight or less, or 0.3% by weight or less. Specifically, the content of the colored inorganic particles in the second resin composition may be 0.01 to 0.5% by weight. When the content is within the above range, it is advantageous for achieving adhesion to glass and pearl texture and color.

Additionally, the second resin composition may include a curing agent, for example, at least one curing agent from the group consisting of an isocyanate curing agent, an epoxy curing agent, and an aziridine curing agent.

When the colored inorganic particles are added to the adhesive resin, agglomeration or agglomeration may occur between the particles, which may cause appearance problems. To prevent this, it is better to mix the colored inorganic particles with a dispersant before adding them to the adhesive resin and then add them to the adhesive resin. Such dispersants may be, for example, polymeric dispersants. Specifically, the colored inorganic particles may be mixed in advance with a polyurethane-based or polyacrylic-based dispersant and then included in the second resin composition. The amount of the dispersant used may be 0.5 parts by weight to 1.0 parts by weight based on 100 parts by weight of the colored inorganic particles.

In addition, the second composition may further include additives such as antioxidants, light stabilizers, and photoinitiators.

Additionally, the second composition may further include a solvent for adjusting viscosity. For example, the second composition may include a solvent so that the solid content is 10% by weight to 50% by weight, or 10% by weight to 30% by weight.

Characteristics and Application

The film according to the present invention can provide two or more constituent layers with different colors to create three-dimensional colors depending on the observation angle due to the colors reflected from each layer and their mixed colors. In particular, according to the present invention, by adding colored inorganic particles having a particle size within a specific range to the adhesive layer of the film, it is possible to achieve a metallic particle feel or pearl texture while maintaining the adhesive force necessary to prevent scattering.

Figure 3 shows a cross-sectional view of a film applied to a glass substrate. Referring to FIG. 3, the film 100 of the present invention is laminated to a glass substrate 200 to increase strength while exhibiting a three-dimensional color and a metallic particle or pearl texture, so it can be used for decoration and prevention of scattering.

Therefore, the film of the present invention can be attached to various displays containing glass or transparent plastic substrates, automobiles, home appliances, etc. to not only serve as a decoration but also function as an anti-shattering film that prevents damage, and is made of a thin film, making it a flexible electronic device that has recently attracted attention. It can also be applied.

The present invention will be described in more detail through examples below. 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 shatterproof film

To prepare the color coating layer composition, 80 parts by weight of urethane acrylic oligomer (UV1700B, NIPPON GOHSEI), 15 parts by weight of pentaerythritol triacrylate (M340, Miwon), and 5 parts by weight of 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 pigment was added based on 100 parts by weight of 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. The color coating layer composition was applied to one side of a base layer (PET film) with a thickness of 100 ㎛ to a thickness of 3 ㎛ using a Mayer bar, dried at 80°C for 2 minutes, and then UV cured (light intensity 0.4 J/cm2). A color coating layer was formed.

Additionally, an adhesive layer composition was prepared by mixing 35 parts by weight of a pressure-sensitive adhesive (305S, Saiden) and 65 parts by weight of methyl ethyl ketone (MEK), and 0.5 parts by weight of colored inorganic particles (T60-21, Merck) were added to the adhesive layer composition. It was added in an amount of % by weight. The adhesive layer composition (solid content of about 20% by weight) was coated on the other side of the base layer using a gap coater, dried and cured to form an adhesive layer with a thickness of 25 ㎛. As a result, an anti-shatter film was obtained, and release paper was laminated to protect the surface of the adhesive layer until use.

Comparative Example 1: Preparation of shatterproof film

The procedure of Example 1 was repeated, but an anti-scattering film with a transparent adhesive layer was obtained without adding colored inorganic particles to the adhesive layer composition.

Test Example 1: Three-dimensional color evaluation

The release paper of each film prepared in Example 1 and Comparative Example 1 was removed, and the transmitted color was measured using a color measuring device (UV Spectrometer U4100, Hitachi). Transmission color was measured at each observation angle based on the frontal direction (i.e., perpendicular to the film plane) for the same area. The results are shown in the table below.

film transparent color 2 degree direction from front Direction 10 degrees from the front L* a* b* L* a* b* Example 1 69.84 16.78 -15.51 69.56 -2.61 -11.36 Comparative Example 1 77.82 -6.01 -14.65 77.42 -5.41 -14.36

As shown in the table above, the transmission color of the film of Example 1 shows a large difference depending on the observation angle compared to the film of Comparative Example 1, so it can be confirmed that various colors can be expressed from various angles.

Test Example 2: Transmission color measurement (change in content of colored inorganic particles)

An anti-scattering film was manufactured by repeating the same procedure as in Example 1, but changing the content of colored inorganic particles in the adhesive layer composition as shown in the table below. Afterwards, the release paper of each film was removed, and the transmitted color from the front direction was measured using a color measurement device (UV Spectrometer U4100, Hitachi). The results are shown in the table below.

colored inorganic particles
Content (% by weight) transparent color L* a* b* 0.01 88.4 2.95 -0.99 0.02 80.2 4.35 -2.12 0.1 74.3 7.62 -6.24 0.5 69.92 16.68 -15.32

As shown in the table above, the transmission color of the film was measured differently depending on the content of colored inorganic particles. In particular, when the content of colored inorganic particles in the adhesive layer composition was more than 0.02% by weight, the transmission color of a* and b* in the front direction was The sum of the absolute values was more than 5, indicating that the color saturation was high and the color appeared clearly.

Test Example 3: Adhesion measurement (change in content of colored inorganic particles)

An anti-scattering film was manufactured by repeating the same procedure as in Example 1, but changing the content of colored inorganic particles in the adhesive layer composition as shown in the table below. Afterwards, the release paper of each film was removed, and an adhesive layer was attached on the glass substrate according to ASTM D903 or JIS Z 0237 standards, pressed and laminated with a 1 kg roller, and peeled at a speed of 300 mm/min and an angle of 180 degrees to maintain adhesive strength. Measured. The results are shown in the table below.

colored inorganic particles
Content (% by weight) adhesiveness
(N/inch) 0.02 20.1 0.1 20.6 0.5 20.3 0.6 13.2 0.8 13.3 One 7.8

As shown in the table above, the adhesion was measured differently depending on the content of the colored inorganic particles. In particular, when the content of the colored inorganic particles in the adhesive layer composition was 0.5% by weight or less, the adhesion was very excellent at more than 20 N/inch. On the other hand, when the content of colored inorganic particles in the adhesive layer composition was 1% by weight or more, the adhesive strength was low at less than 10 N/inch, making it unsuitable for anti-scattering purposes.

Test Example 4: Adhesion measurement (change in particle size of colored inorganic particles and thickness of adhesive layer)

An anti-scattering film was manufactured by repeating the same procedure as in Example 1, but changing the particle size of the colored inorganic particles and the thickness of the adhesive layer as shown in the table below. Thereafter, the 180-degree peel adhesion to the glass substrate was measured in the same manner as Test Example 3.

colored inorganic particles
Particle size (㎛) Adhesion according to adhesive layer thickness (N/inch) 15㎛ 20㎛ 25㎛ 5~10 20.1 20.3 20.6 10~20 20.0 20.2 20.9 20~30 19.7 20.1 20.4 40~50 13.3 16.1 16.9 50~60 5.2 6.3 6.8

As shown in the table above, the adhesive strength was measured differently depending on the change in particle size of the colored inorganic particles and the change in the thickness of the adhesive layer. Specifically, as the particle size of the colored inorganic particles increased, segregation or particles protruded on the surface of the adhesive layer, causing a decrease in adhesive strength. In addition, the thicker the adhesive layer, the higher the adhesive strength, which tended to maximize the anti-scattering effect. In addition, when the thickness of the adhesive layer was 15 to 25 ㎛, stable adhesive strength was achieved when the particle size of the colored inorganic particles was in the range of 5 to 30 ㎛. On the other hand, when the particle size of the colored inorganic particles exceeded 30 ㎛, a rough and matte effect appeared in appearance. Conversely, when the particle size of the colored inorganic particles was 30 ㎛ or less, a smooth metallic texture appeared on the surface.

100: Film according to one embodiment of the present invention,
110: Adhesive layer, 120: Base layer,
130: color coating layer, 140: inorganic deposition layer,
150: pattern layer, 160: reflection layer,
170: blocking layer, 200: glass substrate,
A, A': cross section, L1, L2: transparent color.

Claims (15)

Base layer;
A color coating layer having a first color; and
An adhesive layer containing colored inorganic particles with a particle size of 5 ㎛ to 50 ㎛ and having a second color different from the first color,
It has a structure in which the color coating layer, the base layer, and the adhesive layer are laminated in that order,
The colored inorganic particles are contained in an amount of 0.1 to 2.5% by weight based on the weight of the adhesive layer,
The adhesive layer is pressed and laminated to the surface of a glass substrate with a 1 kg roller, and the 180-degree peel adhesive force measured at a speed of 300 mm/min is 10 N/inch to 35 N/inch,
A film in which the sum of the absolute value of the a* value and the absolute value of the b* value according to the CIE colorimetric system of the transmission color measured from the front of the film is 5 to 50.
delete According to claim 1,
The film satisfies the following formula 1:
5 ≤ │a5 - a10│ ... (1)
Here, a5 is the CIELAB a* value measured in a direction forming a 5° angle with the front direction of the film, and a10 is the CIELAB a* value measured in a direction forming a 10° angle with the front direction of the film.
delete According to claim 1,
A film wherein the thickness of the adhesive layer is in the range of 15 ㎛ to 25 ㎛.
According to claim 5,
A film wherein the colored inorganic particles have a particle size in the range of 5 ㎛ to 30 ㎛.
delete According to claim 1,
A film wherein the colored inorganic particles include at least one selected from the group consisting of aluminum oxide, titanium oxide, tin oxide, and zirconium oxide.
delete According to claim 1,
The film further includes an inorganic deposition layer formed between the base layer and the color coating layer or between the base layer and the adhesive layer,
A film wherein the inorganic deposition layer has a third color different from the first color and the second color.
According to claim 1,
The film is used for decoration and to prevent scattering.
Forming a color coating layer on one side of the base layer using a first resin composition containing a dye or pigment; and
Comprising the step of forming an adhesive layer on the other side of the base layer using a second resin composition containing colored inorganic particles with a particle size of 5 ㎛ to 50 ㎛,
The method for producing the film of claim 1, wherein the content of the colored inorganic particles in the second resin composition is 0.02 to 0.5% by weight.
delete According to claim 12,
A method for producing a film, wherein the colored inorganic particles are mixed in advance with a polyurethane-based or polyacrylic-based dispersant and then contained in the second resin composition.
According to claim 12,
The second resin composition is
A method for producing a film, comprising at least one curing agent from the group consisting of isocyanate curing agents, epoxy curing agents, and aziridine curing agents.