WO2024005517A1 - Color film for paint protection - Google Patents

Color film for paint protection Download PDF

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Publication number
WO2024005517A1
WO2024005517A1 PCT/KR2023/008975 KR2023008975W WO2024005517A1 WO 2024005517 A1 WO2024005517 A1 WO 2024005517A1 KR 2023008975 W KR2023008975 W KR 2023008975W WO 2024005517 A1 WO2024005517 A1 WO 2024005517A1
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Prior art keywords
layer
color
color pigment
weight
film
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PCT/KR2023/008975
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French (fr)
Korean (ko)
Inventor
이동헌
차현수
김진호
Original Assignee
주식회사 상보
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Priority claimed from KR1020220079946A external-priority patent/KR102657310B1/en
Application filed by 주식회사 상보 filed Critical 주식회사 상보
Publication of WO2024005517A1 publication Critical patent/WO2024005517A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • the present invention relates to a color film for paint protection, and more specifically, has a multi-layer structure, comprising a thermosetting polyurethane layer containing pearl and color pigment as the first layer, a thermoplastic polyurethane layer as the second layer, and a top coating layer as the third layer.
  • the color film for paint protection may preferably include an adhesive layer formed of a pressure-sensitive adhesive.
  • a release liner is peelably bonded to the adhesive layer
  • the first layer includes a thermosetting polyurethane resin, a curing agent, a pearl mixed into the polyurethane resin, and a color pigment, but the average particle diameter is different. It is about a color film for paint protection, which is characterized by having a single layer with pearls and color pigments smoothly dispersed to sufficiently shield visible light and having an appropriate range of visible light reflection and discoloration performance.
  • Paint formed by mixing color pigments and solvents is applied to the surface of transportation vehicles such as ships and automobiles to protect the surface of the transportation vehicle. If the paint is damaged and peels off, its anti-corrosive and moisture-proof functions are weakened.
  • Previously developed paint protection films have been mainly developed to protect the surfaces of ships/aircraft/helicopters from sand or flying debris, and are mainly focused on protecting the paint from peeling off the surface of the vehicle. Development has been carried out with a purpose in mind.
  • color films containing pearls sold on the market are mainly made by mixing pearls into the color layer to make them translucent, adding the sparkling effect of pearls to the color of the paint.
  • these products have a problem in that the pearl sparkling effect varies depending on the color of the painted surface.
  • the present invention was devised to solve the above problems,
  • the object of the present invention is to include a first layer containing a thermosetting polyurethane-based resin, a curing agent, pearls mixed into the polyurethane-based resin, and a color pigment, wherein the pearls and the color pigment have different average particle diameters so that the different particles are one.
  • the goal is to provide a color film for paint protection that is smoothly dispersed in the film layer.
  • thermosetting polyurethane resin has a weight average molecular weight of 40,000 to 60,000, a glass transition temperature of 20 °C to 60 °C, and the particle diameter of the pearl mixed in the first layer is 5 ⁇ m to 45 ⁇ m.
  • the particle diameter of the color pigment mixed in the first layer is set to be 1 ⁇ m or more and 5 ⁇ m or less to provide a color film for paint protection in which pearls and color pigments are dispersed smoothly and do not agglomerate during dispersion.
  • the object of the present invention is to produce a pigment containing 1 to 3 parts by weight of pearl and 5 to 20 parts by weight of color pigment along with a polyurethane resin, preferably 10 to 15 parts by weight of the color pigment, depending on the dispersion of pearl and color pigment.
  • the goal is to provide a color film for paint protection that has excellent visible light shielding efficiency and has excellent visual effects due to pearls.
  • the purpose of the present invention is to provide a color film for paint protection that has a discoloration effect in which the color of the first layer changes depending on the angle due to the pearl mixed in the first layer, and the color of the film changes depending on the viewing angle. There is something to do.
  • the object of the present invention is a second layer formed on one side of the first layer and containing thermoplastic polyurethane, a third layer formed on one side of the second layer and protecting the second layer, and the other side of the first layer. It includes an adhesive layer formed on, and the first layer is to provide a color film for paint protection formed between the second layer and the adhesive layer.
  • the present invention is implemented by an embodiment having the following configuration.
  • the color film for paint protection according to the present invention includes a first layer containing a thermosetting polyurethane-based resin, a curing agent, a pearl mixed into the polyurethane-based resin, and a color pigment, and the pearl and color Pigments are characterized by different average particle diameters.
  • the thermosetting polyurethane-based resin has a weight average molecular weight of 40,000 to 60,000, a glass transition temperature of 20°C to 60°C, and the particle diameter of the pearl mixed in the first layer is 5 ⁇ m. It is characterized in that it is 100 ⁇ m or less, and the particle diameter of the color pigment mixed in the first layer is 1 ⁇ m or more and 10 ⁇ m or less.
  • the particle diameter of the pearl mixed in the first layer is 5 ⁇ m or more and 45 ⁇ m or less, and the particle diameter of the color pigment mixed in the first layer is 1 ⁇ m or more and 5 ⁇ m or less. It is characterized by .
  • the first layer is characterized in that it contains 1 to 3 parts by weight of pearl and 5 to 20 parts by weight of color pigment along with a polyurethane resin.
  • the first layer preferably contains 10 to 15 parts by weight of the color pigment.
  • the first layer is characterized in that its color changes depending on the angle due to pearls incorporated into the first layer.
  • the present invention includes a second layer formed on one side of the first layer and containing thermoplastic polyurethane, a third layer formed on one side of the second layer and protecting the second layer, It includes an adhesive layer formed on the other side of the first layer, and the first layer is formed between the second layer and the adhesive layer.
  • the color film for paint protection is characterized by a transmittance of 3% or less and a reflectance of 5 to 15% in the visible light region with a wavelength of 380 to 780 nm.
  • the present invention provides a second layer formed on one side of the first layer and containing thermoplastic polyurethane, and a third layer formed on the other side of the first layer to protect the first layer. layer, and an adhesive layer formed on one side of the second layer, wherein the second layer is formed between the first layer and the adhesive layer.
  • the present invention can achieve the following effects by combining the above-mentioned embodiment with the configuration, combination, and use relationship described below.
  • the present invention includes a first layer comprising a thermosetting polyurethane resin, a curing agent, pearls mixed into the polyurethane resin, and a color pigment, and the pearls and the color pigment have different average particle diameters so that the different particles form one film.
  • the effect is to provide a color film for paint protection that is smoothly distributed throughout the layer.
  • the thermosetting polyurethane resin has a weight average molecular weight of 40,000 to 60,000, a glass transition temperature of 20 °C to 60 °C, and the particle diameter of the pearl mixed in the first layer is 5 ⁇ m to 45 ⁇ m,
  • the particle diameter of the color pigment mixed in the first layer is set to be 1 ⁇ m or more and 5 ⁇ m or less to ensure smooth dispersion of pearls and color pigments while preventing agglomeration from occurring during dispersion.
  • the present invention includes 1 to 3 parts by weight of pearl and 5 to 20 parts by weight of color pigment along with a polyurethane resin, and preferably 10 to 15 parts by weight of the color pigment, so that the color pigment can be used according to the dispersion of the pearl and color pigment. It has excellent visible light shielding efficiency and has excellent visual effects due to the pearl.
  • the first layer is provided so that its color changes depending on the angle due to pearls incorporated into the first layer, so there is a discoloration effect in which the color of the film changes depending on the viewing angle.
  • the present invention relates to a second layer formed on one side of the first layer and containing thermoplastic polyurethane, a third layer formed on one side of the second layer and protecting the second layer, and a third layer formed on the other side of the first layer. and an adhesive layer, wherein the first layer has the effect of providing a color film for protecting the paint formed between the second layer and the adhesive layer.
  • the present invention includes a second layer formed on one side of the first layer and containing thermoplastic polyurethane, a third layer formed on the other side of the first layer and protecting the first layer, and a third layer formed on one side of the second layer. It includes an adhesive layer, and the second layer has the effect of providing a color film for protecting the paint formed between the first layer and the adhesive layer.
  • Figure 1 is a cross-sectional view showing a color film (1) for paint protection according to an embodiment of the present invention.
  • Figure 2 is a photograph of the surface of the paint protection color film (1) according to Examples 1, 2, 4, and 6 of the present invention observed under an indoor light source under a microscope.
  • Figure 3 is a photograph of the surface of the paint protection color film (1) according to Examples 8, 9, 11, and 13 of the present invention observed under an indoor light source under a microscope.
  • Figure 4 is a photograph of the surface of the paint protection color film (1) according to Examples 15 to 18 of the present invention observed under an indoor light source under a microscope.
  • Figure 5 is a photograph of the surface of the paint protection color film (1) according to Examples 19 to 22 of the present invention observed under a microscope under a microscope light source.
  • Figure 6 is a photograph of the surface of the paint protection color film (1) according to Examples 23 to 26 of the present invention observed under a microscope light source.
  • Figure 7 is a photograph of the surface of the paint protection color film (1) according to Examples 27 to 30 of the present invention observed under a microscope under a microscope light source.
  • Figure 8 is a cross-sectional view showing a color film (1) for paint protection according to another embodiment of the present invention.
  • Figure 9 is a photograph of the surface of the color film (1) for paint protection according to Example 11 of the present invention.
  • Figure 10 is a photograph of the surface of the color film (1) for paint protection according to Example 11 of the present invention.
  • FIG. 1 is a cross-sectional view showing a color film (1) for paint protection according to an embodiment of the present invention.
  • the paint protection color film (1) has a multi-layer structure, and includes a thermosetting polyurethane layer (11) containing pearl and color pigment as the first layer, a thermoplastic polyurethane layer (TPU, 13) as the second layer, and a third layer (TPU, 13) as the third layer. It includes a top coating layer (15).
  • the paint protection color film 1 may preferably include an adhesive layer 17 formed of a pressure-sensitive adhesive. In order to protect the adhesive layer 17, a release liner may be peelably bonded to the adhesive layer 17.
  • thermosetting polyurethane layer 11 as the first layer is formed by lamination on one side of the thermoplastic polyurethane layer 13, which is a base layer described later.
  • Thermosetting polyurethane is formed by mixing a diol or polyol with a solvent and an isocyanate-based curing agent, and a reaction retardant may be added.
  • the thermosetting polyurethane layer 11 according to the present invention is a thermosetting polyurethane resin mixed with pearls and color pigments, and has the property of excellent dispersion of pearls and color pigments with different average particle diameters within the thermosetting polyurethane resin. .
  • the pearl 11a and color pigment 11b incorporated into the thermosetting polyurethane layer 11 are a type of pigment and can be defined as a particulate inorganic or organic compound that is insoluble in a solvent and has a predetermined color.
  • the pearl 11a can be used to reflect light from a light source to make the film shine or give a sparkling effect.
  • a discolored pearl whose color changes depending on the angle at which the film is viewed can be used.
  • Color pigment 11b can be used to impart color to the film.
  • the reflectance (VLR) for visible light can be good
  • the transmittance to visible light can be good.
  • VLT may appear low. That is, when the compatibility between the resin and the pearl is good, the reflectance (VLR) tends to increase, and when the compatibility between the resin and the color pigment is good, the transmittance (VLT) tends to decrease.
  • the pearl 11a may have a metal oxide coating on plate-shaped particles called flakes, and may be formed to have a different color depending on the viewing angle.
  • the pearl is preferably incorporated in an amount of 0.5 parts by weight or more and 3 parts by weight or less based on the total weight of the thermosetting polyurethane layer 11. If the amount of pearl is less than 0.5 parts by weight, the sparkling effect due to discoloration and reflection is reduced, and if it is more than 3 parts by weight, visibility, which is the basic performance of the film, is reduced.
  • the color pigment 11b is preferably incorporated in an amount of 10 to 15 parts by weight based on the thermosetting polyurethane layer 11.
  • the amount of color pigment (11b) mixed is small, the shielding performance of the film deteriorates and the paint color on the adhered surface is visible, and if the amount mixed is too large, it is uneconomical and the pearl (11a) is damaged due to the excessive color pigment. The reflection effect actually decreases.
  • the color film for paint protection resulting from the mixing of the pearl (11a) and the color pigment (11b) has a transmittance (VLT) of 3% or less and a reflectance (VLR) of 5 to 15% in the visible light range of 380 to 780 nm wavelength. It is desirable to have it.
  • the pearl 11a and the color pigment 11b incorporated into the thermosetting polyurethane layer 11 have different average particle diameters.
  • the particle diameter of the pearl 11a is preferably 5 ⁇ m or more and 45 ⁇ m or less, and the average particle diameter may be about 25 ⁇ m. If the particle size is smaller than 5 ⁇ m, the original purpose of the shielding and color film, which is the shielding and discoloration effect, is not implemented due to the too small particle size. In the case of pearls over 100 ⁇ m, the particle size is too large, so it appears as a foreign matter or reduces visibility during coating. may result in
  • the particle diameter of the color pigment 11b is preferably 1 ⁇ m or more and 5 ⁇ m or less, and the average particle diameter may be about 2 to 2.5 ⁇ m. If the color pigment has a particle size smaller than 1 ⁇ m, light shielding and color effects are reduced due to the small particle size, and if the particle size is larger than 10 ⁇ m, dispersion is difficult and visibility may be reduced.
  • the dispersibility of other materials may be affected by changes in the particle size of a certain material.
  • the dispersibility of the pearl 11a varies depending on the particle size of the color pigment 11b.
  • the particle diameter of the color pigment (11b) is 1 ⁇ m or more for the pearl (11a) with a particle diameter of 5 ⁇ m or more and 45 ⁇ m or less. It is preferable that it is 5 ⁇ m or less.
  • Thermosetting polyurethane resins may be polyester-based, polyacrylic-based, polyether-based, polycarbonate-based, polyalkylene-based, and mixtures of one or more of these, but it is preferable to use polyester-based resin.
  • the thermosetting polyurethane resin requires that the pearls and color pigments mixed in are smoothly dispersed within the resin, but the inventors of the present invention proposed that the pearls and color pigments be smoothly dispersed within a polyester resin having a molecular weight and glass transition temperature within a predetermined range. After confirming the dispersion, we arrived at the present invention.
  • the polyester resin preferably has a weight average molecular weight of 40,000 to 60,000 and a glass transition temperature of 20°C to 60°C. Pearls 11a and color pigments 11b of different particle sizes within the above molecular weight and glass transition temperature ranges can be simultaneously and smoothly dispersed in the resin.
  • Thermosetting polyurethane resin may be used in an amount of 30% to 40% by weight.
  • the pearl (11a) and color pigment (11b) are not smoothly dispersed within the resin. That is, the compatibility of the pearl (11a) and the color pigment (11b) with the resin does not show the same tendency.
  • the molecular weight of the resin is too low, the dispersion of pearls and color pigments is not constant, which results in a high transmittance (VLT) of the film to visible light.
  • the solvent may be MEK (methyl ethyl ketone), toluene, or a mixture thereof, and the solvent may be mixed in an amount of 50 to 70 parts by weight based on the weight of the thermosetting polyurethane layer.
  • the curing agent may be one or more of isocyanate, epoxy, and metal chelate, and may be used in an amount of 3 to 5 parts by weight based on the weight of the thermosetting polyurethane layer.
  • the thermosetting polyurethane layer may have elasticity that increases when stretched. Accordingly, the color film for paint protection according to the present invention can be smoothly attached or installed on the adhered surface.
  • Acetylacetone is preferably used as a reaction retardant, and may be used in an amount of 0.1 to 1 part by weight based on the thermosetting polyurethane layer.
  • thermoplastic polyurethane layer 13 as the second layer and the base layer can be made of thermoplastic polyurethane mixed with a known polyol such as polycarbonate-based or polyester-based polyol and a curing agent such as isocyanate.
  • the polyurethane layer may be formed using conventional methods, for example, by casting or otherwise coating an aqueous dispersion or solution mixture onto a peelable carrier web or liner.
  • the top coating layer 15 as the third layer can be applied on one side of the thermoplastic polyurethane layer 13, which is the base layer, to protect the base layer from collision with foreign substances such as dirt, sand, and asphalt debris. Protects the base layer.
  • the top coating layer 15 may be formed using thermosetting, thermoplastic, or photocurable resin.
  • Polycarbonate resin, acrylic resin, polyester resin, phenoxy resin, epoxy resin, polyolefin resin, and fluoroethyl vinyl ether (FEVE) resin can be used as thermosetting resins
  • polypropylene resin and polycarbonate resin can be used as thermosetting resins.
  • acrylic resin, polystyrene resin, etc. can be used as thermoplastic resins.
  • Resins such as urethane acrylate resin and polyester acrylate resin can be used as photocurable resins. It is desirable that the top coating layer 15 has self-healing properties.
  • the adhesive layer 17 can be formed by lamination of an acrylic pressure-sensitive adhesive on a release liner through heat, and the release liner 19 can be made of a known release paper or the like.
  • polyester-based polyurethane resin with a glass transition temperature (Tg) of 20 to 60°C and a weight average molecular weight of 40,000 to 60,000 (urethane resin from Toyo Ink Paint, Japan), and 37% by weight of MEK (methyl ethyl ketone) as a solvent (Korea) Samjeon Pure Pharmaceutical Co., Ltd.), 20% by weight of toluene as a solvent (Samjeon Pure Pharmaceutical Co., Ltd., Korea), 3% by weight isocyanate-based hardener (Coronate HX, Tosoh, Japan) as a hardener, and 1% by weight of acetylacetone (Daejeong Chemical Co., Ltd., Korea) as a reaction retardant.
  • Tg glass transition temperature
  • MEK methyl ethyl ketone
  • thermosetting polyurethane layer (11) in which carbon black) was dispersed was formed.
  • thermoplastic polyurethane (TPU, 49510-60DV, SWM, USA) solution mixed with polycarbonate-based and polyester-based polyol and isocyanate-based curing agent was used, and as the top coating layer (15), polycarbohydrate Nate resin (thermosetting polycarbonate resin manufactured by AICA, Japan) was used.
  • polycarbohydrate Nate resin thermosetting polycarbonate resin manufactured by AICA, Japan
  • adhesive layer 17 an acrylic pressure-sensitive adhesive (op-3510-2, AICA, Japan) on a release liner was used.
  • thermoplastic polyurethane (TPU) solution which is the base layer 13 is formed by casting or coating on a peelable carrier web or liner, and the thermosetting polyurethane layer 11 and the top coating layer 15 are of the base layer 13. It was formed by casting on one side.
  • the adhesive layer 17 was formed by applying a coating layer to a release film and then applying transfer coating.
  • thermosetting polyurethane layer 11 of Example 1 A film in which 8% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 1 A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 1 A film in which 12.5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 1 A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 1 A film in which 17% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
  • the particle diameter of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was 1 ⁇ m or more and 5 ⁇ m or less, and a film in which 1% by weight of the color pigment was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 8 A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 8 A film in which 8% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 8 A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 8 A film in which 12.5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 8 A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 8 A film in which 17% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
  • VLT visible light transmittance
  • VLR reflectance
  • Table 1 and Table 2 the visible light transmittance
  • the transmittance is the amount of visible light measured on the back of the film compared to the visible light irradiated to the top coating layer of the film
  • the reflectance is the amount of visible light reflected from one side of the film compared to the visible light irradiated to the top coating layer. This was measured with a spectrometer, Jasco V-770.
  • Table 1 shows the visible light transmittance as a percentage according to the content (% by weight) of the color pigment and particle size
  • Table 2 shows the visible light reflectance as a percentage according to the content (% by weight) of the color pigment and the particle size.
  • Both types of color pigments have good compatibility with thermosetting polyurethane resin, but when the visible light transmittance is less than 1%, when a color pigment in the nm unit is used, the visible light reflectance is about 5%, and when the color pigment in the um unit is used, the visible light reflectance is about 5%.
  • the light reflectance was about 9%, and in the case of nm units, the reflection of the pearl was not clearly visible to the naked eye.
  • the degree of reflection of the pearls was visible to the naked eye, and the color shift phenomenon in which the color changes depending on the angle was also unreasonable. It was possible to check without it. Referring to the above data, when the visible light transmittance is less than 1% and the visible light reflectance is 9% or more, it is considered desirable to use it as a material and mixing ratio for manufacturing single-layer products.
  • an acrylic resin (op-3510-2, AICA, Japan) was used.
  • the acrylic resin has a weight average molecular weight of 400,000 to 800,000 and a glass transition temperature of -45°C to -15°C.
  • the color pigment had a particle diameter of 10 nm or more and 100 nm or less, and a film in which 1% by weight of the color pigment was dispersed was formed.
  • the particle size and content of pearls were the same as in Example 1.
  • thermosetting polyurethane layer 11 of Example 15 A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 15 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 15 A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 15 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 15 A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 15 was dispersed was formed.
  • the particle diameter of the color pigment constituting the thermosetting polyurethane layer 11 of Example 15 was 1 ⁇ m or more and 5 ⁇ m or less, and a film in which 1% by weight of the color pigment was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 19 A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 19 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 19 A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 19 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 19 A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 19 was dispersed was formed.
  • VLT visible light transmittance
  • VLR reflectance
  • Figure 5 is a photograph of a film using a color pigment with a particle size of ⁇ m measured under a microscope after being irradiated with a microscope light source. Referring to this, it is observed that as the content of color pigment increases, the number of black particles agglomerated increases. This is because agglomeration occurred due to poor dispersion of the color pigment, which explains the phenomenon in which transmittance does not decrease as the color pigment content in Table 3 increases.
  • acrylic resin With respect to acrylic resin, it can be confirmed that the dispersibility of pearls and color pigments is good when mixing color pigments with a particle size in nm units with pearls when the color pigment content is 10 parts by weight or more. However, even if the dispersibility of the pearl and the color pigment is good, the visible light reflectance (VLR) is 5 to 6%, so there is a problem that it is impossible to distinguish the reflected color of the pearl. Therefore, the acrylic resins of Examples 15 to 22 can be judged to be unsuitable as the resin for the first layer.
  • VLR visible light reflectance
  • the weight average molecular weight of the polyester-based polyurethane resin constituting the thermosetting polyurethane layer 11 of Example 1 was changed to 10,000 to 30,000 (low molecular weight urethane resin from Toyo Ink Paint, Japan) to prepare a dispersion of the polyurethane layer 11. formed.
  • the particle size and content of color pigment and pearl are the same as in Example 1.
  • thermosetting polyurethane layer 11 of Example 23 A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 23 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 23 A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 23 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 23 A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 23 was dispersed was formed.
  • the particle diameter of the color pigment constituting the thermosetting polyurethane layer 11 of Example 23 was 1 ⁇ m or more and 5 ⁇ m or less, and a film in which 1% by weight of the color pigment was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 27 A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 27 was dispersed was formed.
  • thermosetting polyurethane layer 11 of Example 27 A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 27 was dispersed was formed.
  • VLT visible light transmittance
  • VLR reflectance
  • the visible light transmittance is measured to be about 8% higher than when the content of the color pigment is 10 parts by weight.
  • the visible light transmittance is about 6%. This is higher than other examples with the same color pigment content, and it is judged that an excessive amount of color pigment must be mixed in order to make the visible light transmittance less than 1%.
  • Examples 23 to 30 if the visible light transmittance of the film is to be lowered to 1% or less, an excessive amount of color pigment must be mixed, and in this case, the visible light reflectance is lowered to 5% or less, and the low molecular weight resin is pearl with a different particle size. It is unsuitable as a material for dispersing color pigments.
  • thermosetting polyurethane layer 11 as a first layer containing pearl and color pigment is composed of a thermoplastic polyurethane layer 13 as a second layer and a top coating layer as a third layer. It may be formed between (15).
  • thermosetting polyurethane layer 11 containing pearl and color pigment is formed between the thermoplastic polyurethane layer 13 and the top coating layer 15, the distance through which visible light passes through the medium is shortened.
  • thermosetting polyurethane layer 11 on the thermoplastic polyurethane layer 13, which is a base layer, and then coating the top coating layer 15 on the thermosetting polyurethane layer 11, the top coating layer 15 )
  • a swelling phenomenon occurs between the solvent contained in the solution and a portion of the thermosetting polyurethane layer 11, resulting in disadvantages in terms of visible light reflectance and gloss.
  • thermosetting polyurethane layer 11 is formed as in Example 11, which is one of the preferred embodiments of the present invention, but the structure of each layer is as shown in FIG. 8, and the thermosetting polyurethane layer 11 as the first layer is It was formed between the thermoplastic polyurethane layer 13 as the second layer and the top coating layer 15 as the third layer.
  • Example 11 The appearance of the color film for paint protection according to Example 11 is shown in Figure 9, and the appearance of the color film for paint protection according to Example 31 is shown in Figure 10.
  • the amount of light entering the glossmeter was measured compared to the light source according to the gloss measurement angle according to ISO2813, and is listed in Table 7. In this way, the paint protection color film according to Example 11 is superior to that of Example 31, and in appearance, Example 31 has a matte surface due to diffuse reflection.

Abstract

The present invention relates to a color film for paint protection and, more specifically, the color film for paint protection has a multi-layer structure and comprises: a thermosetting polyurethane layer containing pearl and a color pigment as a first layer; a thermoplastic polyurethane layer as a second layer; and a top coating layer as a third layer. In addition, the color film for paint protection may preferably comprise an adhesive layer formed of a pressure-sensitive adhesive. The color film for paint protection is characterized in that a release liner is releasably bound to the adhesive layer to protect the adhesive layer and the first layer has a single layer, which contains a thermosetting polyurethane resin, a curing agent, and pearl and a color pigment incorporated into the polyurethane resin and allows for the reflection of visible light within an appropriate range and color-changing performance while providing sufficient shielding of visible light, through the smooth dispersion of the pearl and color pigment with different average particle diameters.

Description

페인트 보호용 색상필름Color film for paint protection
본 발명은 페인트 보호용 색상필름에 관한 것으로, 더욱 상세하게는 다층 구조를 가지며, 제1층으로서의 펄과 색상안료를 포함한 열경화성 폴리우레탄층, 제2층으로서의 열가소성 폴리우레탄층, 제3층으로서의 탑코팅층을 포함한다. 또한 상기 페인트 보호용 색상필름은 바람직하게는 감압성 점착제로 형성된 점착층을 포함할 수 있다. 상기 점착층을 보호하기 위해 점착층에 박리 라이너가 박리가능하게 결합되고, 상기 제1층은 열경화성 폴리우레탄계 수지, 경화제, 상기 폴리우레탄계 수지에 혼입되는 펄과 색상안료를 포함하되 평균입자직경이 상이한 펄과 색상안료가 원활하게 분산되어 가시광을 충분히 차폐하면서도 적절한 범위의 가시광 반사와 변색 성능을 가지는 단일층을 가지는 것을 특징으로 하는 페인트 보호용 색상필름에 대한 것이다. The present invention relates to a color film for paint protection, and more specifically, has a multi-layer structure, comprising a thermosetting polyurethane layer containing pearl and color pigment as the first layer, a thermoplastic polyurethane layer as the second layer, and a top coating layer as the third layer. Includes. Additionally, the color film for paint protection may preferably include an adhesive layer formed of a pressure-sensitive adhesive. In order to protect the adhesive layer, a release liner is peelably bonded to the adhesive layer, and the first layer includes a thermosetting polyurethane resin, a curing agent, a pearl mixed into the polyurethane resin, and a color pigment, but the average particle diameter is different. It is about a color film for paint protection, which is characterized by having a single layer with pearls and color pigments smoothly dispersed to sufficiently shield visible light and having an appropriate range of visible light reflection and discoloration performance.
선박, 자동차 등의 운송수단 표면에는 색상안료와 용매 등을 혼합하여 형성한 페인트가 도포되어 운송수단의 표면을 보호하게 된다. 페인트가 손상되어 벗겨지는 경우 페인트의 방식, 방습 기능이 약화된다. 종래 개발된 페인트 도장 보호필름(Paint protection Film)은 주로 선박/항공기/헬리콥터 등의 표면을 모래나 날아다니는 파편으로부터 보호하기 위해서 개발되어왔으며, 페인트가 운송수단의 표면에서 벗겨지지 않도록 보호하는 것에 주 목적을 두고 개발이 이루어져왔다.Paint formed by mixing color pigments and solvents is applied to the surface of transportation vehicles such as ships and automobiles to protect the surface of the transportation vehicle. If the paint is damaged and peels off, its anti-corrosive and moisture-proof functions are weakened. Previously developed paint protection films have been mainly developed to protect the surfaces of ships/aircraft/helicopters from sand or flying debris, and are mainly focused on protecting the paint from peeling off the surface of the vehicle. Development has been carried out with a purpose in mind.
이러한 필름들은 근래에 그 사용분야가 차량, 가구, 가전과 같은 생활제품 분야로 확대 됨으로써 도장면 보호 기능 외에 보호필름에 심미적 효과를 얻으려는 움직임이 있고 필름에 펄이나 색상 안료를 혼입하여 사용자가 원하는 다양한 색상과 반짝거리는 외관을 가진 도장 보호필름들이 개발 되었다.In recent years, the field of use of these films has expanded to the field of household products such as vehicles, furniture, and home appliances, and there is a movement to obtain aesthetic effects in protective films in addition to the function of protecting the painted surface. Pearls or color pigments are mixed into the films to create the desired effect for the user. Paint protection films with various colors and shiny appearances have been developed.
일반적으로 시중에 판매되고 있는 펄을 넣은 색상필름의 경우 색상층에 펄을 혼합하여 반투명하게 만든 형태로 도장의 색상에 펄의 스파클링 효과를 더하는 제품들이 주를 이룬다. 그러나 이러한 제품들은 펄의 스파클링 효과가 도장면의 색상에 따라 차이가 발생하게 되는 문제점이 있다. In general, color films containing pearls sold on the market are mainly made by mixing pearls into the color layer to make them translucent, adding the sparkling effect of pearls to the color of the paint. However, these products have a problem in that the pearl sparkling effect varies depending on the color of the painted surface.
도장면의 색상에 따른 차이를 줄이고자 색상안료를 혼입시키는 경우 색상안료가 도장면을 가려 색상안료의 색상을 기반으로 펄의 스파클링 효과를 재현할 수는 있지만, 색상안료의 혼입을 위해 별도의 층을 만들어야 하는 단점이 있다. 또한 색상안료를 펄과 같은 층에 혼입하려고 하는 경우, 색상안료 또는 펄 입자와 수지 사이의 상용성 문제로 인해 펄과 색상안료가 분산되지 못하여 색상필름으로 분화되었다. When color pigment is mixed to reduce the difference in color of the painted surface, the color pigment covers the painted surface and the sparkling effect of pearl can be reproduced based on the color of the color pigment. However, a separate layer is required to mix the color pigment. There is a disadvantage of having to create a . Additionally, when trying to mix color pigments into the same layer as pearls, the pearls and color pigments could not be dispersed due to compatibility issues between the color pigments or pearl particles and the resin, resulting in differentiation into color films.
본 발명은 상기와 같은 문제점을 해결하기 위해 출안된 것으로,The present invention was devised to solve the above problems,
본 발명의 목적은 열경화성 폴리우레탄계 수지, 경화제, 상기 폴리우레탄계 수지에 혼입되는 펄과 색상안료를 포함하는 제1층을 포함하며, 상기 펄과 색상안료는 평균입자직경이 상이하도록 하여 상이한 입자가 하나의 필름층에 원활하게 분산된 페인트 보호용 색상필름을 제공하는 데 있다.The object of the present invention is to include a first layer containing a thermosetting polyurethane-based resin, a curing agent, pearls mixed into the polyurethane-based resin, and a color pigment, wherein the pearls and the color pigment have different average particle diameters so that the different particles are one. The goal is to provide a color film for paint protection that is smoothly dispersed in the film layer.
본 발명의 목적은 상기 열경화성 폴리우레탄계 수지는 중량평균분자량이 40,000 이상 60,000 이하, 유리전이온도가 20℃ 이상 60℃ 이하이며, 상기 제1층에 혼입되는 펄의 입자직경은 5㎛ 이상 45㎛ 이하이고, 상기 제1층에 혼입되는 색상안료의 입자직경은 1㎛ 이상 5㎛ 이하이도록 하여 펄과 색상안료의 분산이 원활하면서도 분산 중 응집 발생하지 않는 페인트 보호용 색상필름을 제공하는 데 있다.The object of the present invention is that the thermosetting polyurethane resin has a weight average molecular weight of 40,000 to 60,000, a glass transition temperature of 20 ℃ to 60 ℃, and the particle diameter of the pearl mixed in the first layer is 5 ㎛ to 45 ㎛. The particle diameter of the color pigment mixed in the first layer is set to be 1 ㎛ or more and 5 ㎛ or less to provide a color film for paint protection in which pearls and color pigments are dispersed smoothly and do not agglomerate during dispersion.
본 발명의 목적은 폴리우레탄 수지와 함께 펄 1 내지 3 중량부, 색상안료 5 내지 20 중량부를 포함하고, 상기 색상안료를 바람직하게는 10 내지 15중량부 포함하여 펄과 색상안료의 분산에 따라 안료에 의한 가시광선 차폐효율이 뛰어나면서도 펄에 의한 시각적 효과가 우수한 페인트 보호용 색상필름을 제공하는 데 있다.The object of the present invention is to produce a pigment containing 1 to 3 parts by weight of pearl and 5 to 20 parts by weight of color pigment along with a polyurethane resin, preferably 10 to 15 parts by weight of the color pigment, depending on the dispersion of pearl and color pigment. The goal is to provide a color film for paint protection that has excellent visible light shielding efficiency and has excellent visual effects due to pearls.
본 발명의 목적은 상기 제1층은 상기 제1층에 혼입된 펄에 의해 각도에 따라 색상이 변화하도록 구비되어 필름을 보는 각도에 따라 필름의 색상이 변하는 변색효과가 있는 페인트 보호용 색상필름을 제공하는 데 있다.The purpose of the present invention is to provide a color film for paint protection that has a discoloration effect in which the color of the first layer changes depending on the angle due to the pearl mixed in the first layer, and the color of the film changes depending on the viewing angle. There is something to do.
본 발명의 목적은 상기 제1층의 일면에 형성되며 열가소성 폴리우레탄을 포함하는 제2층, 상기 제2층의 일면에 형성되어 제2층을 보호하는 제3층, 상기 제1층의 다른 일측에 형성되는 점착층을 포함하고, 상기 제1층은 제2층과 점착층 사이에 형성되는 페인트 보호용 색상필름을 제공하는 데 있다.The object of the present invention is a second layer formed on one side of the first layer and containing thermoplastic polyurethane, a third layer formed on one side of the second layer and protecting the second layer, and the other side of the first layer. It includes an adhesive layer formed on, and the first layer is to provide a color film for paint protection formed between the second layer and the adhesive layer.
본 발명은 앞서 본 목적을 달성하기 위해서 다음과 같은 구성을 가진 실시예에 의해서 구현된다.In order to achieve the above-described object, the present invention is implemented by an embodiment having the following configuration.
본 발명의 일 실시예에 따르면, 본 발명에 따른 페인트 보호용 색상필름은 열경화성 폴리우레탄계 수지, 경화제, 상기 폴리우레탄계 수지에 혼입되는 펄과 색상안료를 포함하는 제1층을 포함하며, 상기 펄과 색상안료는 평균입자직경이 상이한 것을 특징으로 한다.According to one embodiment of the present invention, the color film for paint protection according to the present invention includes a first layer containing a thermosetting polyurethane-based resin, a curing agent, a pearl mixed into the polyurethane-based resin, and a color pigment, and the pearl and color Pigments are characterized by different average particle diameters.
본 발명의 일 실시예에 따르면, 상기 열경화성 폴리우레탄계 수지는 중량평균분자량이 40,000 이상 60,000 이하, 유리전이온도가 20℃ 이상 60℃ 이하이며, 상기 제1층에 혼입되는 펄의 입자직경은 5㎛ 이상 100㎛ 이하이고, 상기 제1층에 혼입되는 색상안료의 입자직경은 1㎛ 이상 10㎛ 이하인 것을 특징으로 한다.According to one embodiment of the present invention, the thermosetting polyurethane-based resin has a weight average molecular weight of 40,000 to 60,000, a glass transition temperature of 20°C to 60°C, and the particle diameter of the pearl mixed in the first layer is 5㎛. It is characterized in that it is 100㎛ or less, and the particle diameter of the color pigment mixed in the first layer is 1㎛ or more and 10㎛ or less.
본 발명의 일 실시예에 따르면, 상기 제1층에 혼입되는 펄의 입자직경은 5㎛ 이상 45㎛ 이하이고, 상기 제1층에 혼입되는 색상안료의 입자직경은 1㎛ 이상 5㎛ 이하인 것을 특징으로 하는 것을 특징으로 한다.According to one embodiment of the present invention, the particle diameter of the pearl mixed in the first layer is 5 ㎛ or more and 45 ㎛ or less, and the particle diameter of the color pigment mixed in the first layer is 1 ㎛ or more and 5 ㎛ or less. It is characterized by .
본 발명의 일 실시예에 따르면, 상기 제1층은 폴리우레탄 수지와 함께 펄 1 내지 3 중량부, 색상안료 5 내지 20 중량부를 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the first layer is characterized in that it contains 1 to 3 parts by weight of pearl and 5 to 20 parts by weight of color pigment along with a polyurethane resin.
본 발명의 일 실시예에 따르면, 상기 제1층은 상기 색상안료를 바람직하게는 10 내지 15중량부 포함하는 것을 특징으로 한다.According to one embodiment of the present invention, the first layer preferably contains 10 to 15 parts by weight of the color pigment.
본 발명의 일 실시예에 따르면, 상기 제1층은 상기 제1층에 혼입된 펄에 의해 각도에 따라 색상이 변화하도록 구비되는 것을 특징으로 한다.According to one embodiment of the present invention, the first layer is characterized in that its color changes depending on the angle due to pearls incorporated into the first layer.
본 발명의 일 실시예에 따르면, 본 발명은 상기 제1층의 일면에 형성되며 열가소성 폴리우레탄을 포함하는 제2층, 상기 제2층의 일면에 형성되어 제2층을 보호하는 제3층, 상기 제1층의 다른 일측에 형성되는 점착층을 포함하고, 상기 제1층은 제2층과 점착층 사이에 형성되는 것을 특징으로 한다.According to one embodiment of the present invention, the present invention includes a second layer formed on one side of the first layer and containing thermoplastic polyurethane, a third layer formed on one side of the second layer and protecting the second layer, It includes an adhesive layer formed on the other side of the first layer, and the first layer is formed between the second layer and the adhesive layer.
본 발명의 일 실시예에 따르면, 상기 페인트 보호용 색상필름은 380 내지 780nm 파장의 가시광선 영역에서 투과율이 3% 이하, 반사율이 5 내지 15%인 것을 특징으로 한다.According to one embodiment of the present invention, the color film for paint protection is characterized by a transmittance of 3% or less and a reflectance of 5 to 15% in the visible light region with a wavelength of 380 to 780 nm.
본 발명의 일 실시예에 따르면, 본 발명은 상기 제1층의 일면에 형성되며 열가소성 폴리우레탄을 포함하는 제2층, 상기 제1층의 다른 일면에 형성되어 상기 제1층을 보호하는 제3층, 상기 제2층의 일측에 형성되는 점착층을 포함하고, 상기 제2층은 제1층과 점착층 사이에 형성되는 것을 특징으로 한다.According to one embodiment of the present invention, the present invention provides a second layer formed on one side of the first layer and containing thermoplastic polyurethane, and a third layer formed on the other side of the first layer to protect the first layer. layer, and an adhesive layer formed on one side of the second layer, wherein the second layer is formed between the first layer and the adhesive layer.
본 발명은 앞서 본 실시예와 하기에 설명할 구성과 결합, 사용관계에 의해 다음과 같은 효과를 얻을 수 있다.The present invention can achieve the following effects by combining the above-mentioned embodiment with the configuration, combination, and use relationship described below.
본 발명은 열경화성 폴리우레탄계 수지, 경화제, 상기 폴리우레탄계 수지에 혼입되는 펄과 색상안료를 포함하는 제1층을 포함하며, 상기 펄과 색상안료는 평균입자직경이 상이하도록 하여 상이한 입자가 하나의 필름층에 원활하게 분산된 페인트 보호용 색상필름을 제공하는 효과를 도출한다.The present invention includes a first layer comprising a thermosetting polyurethane resin, a curing agent, pearls mixed into the polyurethane resin, and a color pigment, and the pearls and the color pigment have different average particle diameters so that the different particles form one film. The effect is to provide a color film for paint protection that is smoothly distributed throughout the layer.
본 발명은 상기 열경화성 폴리우레탄계 수지는 중량평균분자량이 40,000 이상 60,000 이하, 유리전이온도가 20℃ 이상 60℃ 이하이며, 상기 제1층에 혼입되는 펄의 입자직경은 5㎛ 이상 45㎛ 이하이고, 상기 제1층에 혼입되는 색상안료의 입자직경은 1㎛ 이상 5㎛ 이하이도록 하여 펄과 색상안료의 분산이 원활하면서도 분산 중 응집 발생하지 않는 효과를 준다.In the present invention, the thermosetting polyurethane resin has a weight average molecular weight of 40,000 to 60,000, a glass transition temperature of 20 ℃ to 60 ℃, and the particle diameter of the pearl mixed in the first layer is 5 ㎛ to 45 ㎛, The particle diameter of the color pigment mixed in the first layer is set to be 1 ㎛ or more and 5 ㎛ or less to ensure smooth dispersion of pearls and color pigments while preventing agglomeration from occurring during dispersion.
본 발명은 폴리우레탄 수지와 함께 펄 1 내지 3 중량부, 색상안료 5 내지 20 중량부를 포함하고, 상기 색상안료를 바람직하게는 10 내지 15중량부 포함하여 펄과 색상안료의 분산에 따라 안료에 의한 가시광선 차폐효율이 뛰어나면서도 펄에 의한 시각적 효과가 우수하다.The present invention includes 1 to 3 parts by weight of pearl and 5 to 20 parts by weight of color pigment along with a polyurethane resin, and preferably 10 to 15 parts by weight of the color pigment, so that the color pigment can be used according to the dispersion of the pearl and color pigment. It has excellent visible light shielding efficiency and has excellent visual effects due to the pearl.
본 발명은 상기 제1층은 상기 제1층에 혼입된 펄에 의해 각도에 따라 색상이 변화하도록 구비되어 필름을 보는 각도에 따라 필름의 색상이 변하는 변색효과가 있다.In the present invention, the first layer is provided so that its color changes depending on the angle due to pearls incorporated into the first layer, so there is a discoloration effect in which the color of the film changes depending on the viewing angle.
본 발명은 상기 제1층의 일면에 형성되며 열가소성 폴리우레탄을 포함하는 제2층, 상기 제2층의 일면에 형성되어 제2층을 보호하는 제3층, 상기 제1층의 다른 일측에 형성되는 점착층을 포함하고, 상기 제1층은 제2층과 점착층 사이에 형성되는 페인트 보호용 색상필름을 제공하는 효과를 가진다.The present invention relates to a second layer formed on one side of the first layer and containing thermoplastic polyurethane, a third layer formed on one side of the second layer and protecting the second layer, and a third layer formed on the other side of the first layer. and an adhesive layer, wherein the first layer has the effect of providing a color film for protecting the paint formed between the second layer and the adhesive layer.
본 발명은 상기 제1층의 일면에 형성되며 열가소성 폴리우레탄을 포함하는 제2층, 상기 제1층의 다른 일면에 형성되어 상기 제1층을 보호하는 제3층, 상기 제2층의 일측에 형성되는 점착층을 포함하고, 상기 제2층은 제1층과 점착층 사이에 형성되는 페인트 보호용 색상필름을 제공하는 효과가 있다.The present invention includes a second layer formed on one side of the first layer and containing thermoplastic polyurethane, a third layer formed on the other side of the first layer and protecting the first layer, and a third layer formed on one side of the second layer. It includes an adhesive layer, and the second layer has the effect of providing a color film for protecting the paint formed between the first layer and the adhesive layer.
도 1은 본 발명의 일 실시예에 따른 페인트 보호용 색상필름(1)을 도시한 단면도Figure 1 is a cross-sectional view showing a color film (1) for paint protection according to an embodiment of the present invention.
도 2는 본 발명의 실시예 1, 실시예 2, 실시예 4, 실시예 6에 따른 페인트 보호용 색상필름(1)의 표면을 실내 광원 하에서 현미경으로 관찰한 사진Figure 2 is a photograph of the surface of the paint protection color film (1) according to Examples 1, 2, 4, and 6 of the present invention observed under an indoor light source under a microscope.
도 3은 본 발명의 실시예 8, 실시예 9, 실시예 11, 실시예 13에 따른 페인트 보호용 색상필름(1)의 표면을 실내 광원 하에서 현미경으로 관찰한 사진Figure 3 is a photograph of the surface of the paint protection color film (1) according to Examples 8, 9, 11, and 13 of the present invention observed under an indoor light source under a microscope.
도 4는 본 발명의 실시예 15 내지 18에 따른 페인트 보호용 색상필름(1)의 표면을 실내 광원 하에서 현미경으로 관찰한 사진Figure 4 is a photograph of the surface of the paint protection color film (1) according to Examples 15 to 18 of the present invention observed under an indoor light source under a microscope.
도 5는 본 발명의 실시예 19 내지 22에 따른 페인트 보호용 색상필름(1)의 표면을 현미경 광원 하에서 현미경으로 관찰한 사진Figure 5 is a photograph of the surface of the paint protection color film (1) according to Examples 19 to 22 of the present invention observed under a microscope under a microscope light source.
도 6은 본 발명의 실시예 23 내지 26에 따른 페인트 보호용 색상필름(1)의 표면을 현미경 광원 하에서 현미경으로 관찰한 사진Figure 6 is a photograph of the surface of the paint protection color film (1) according to Examples 23 to 26 of the present invention observed under a microscope light source.
도 7은 본 발명의 실시예 27 내지 30에 따른 페인트 보호용 색상필름(1)의 표면을 현미경 광원 하에서 현미경으로 관찰한 사진Figure 7 is a photograph of the surface of the paint protection color film (1) according to Examples 27 to 30 of the present invention observed under a microscope under a microscope light source.
도 8은 본 발명의 다른 실시예에 따른 페인트 보호용 색상필름(1)을 도시한 단면도Figure 8 is a cross-sectional view showing a color film (1) for paint protection according to another embodiment of the present invention.
도 9는 본 발명의 실시예 11에 따른 페인트 보호용 색상필름(1)의 표면의 사진Figure 9 is a photograph of the surface of the color film (1) for paint protection according to Example 11 of the present invention.
도 10은 본 발명의 실시예 11에 따른 페인트 보호용 색상필름(1)의 표면의 사진Figure 10 is a photograph of the surface of the color film (1) for paint protection according to Example 11 of the present invention.
이하에서는 본 발명에 따른 페인트 보호용 색상필름을 첨부된 도면을 참조하여 상세히 설명한다. 또한 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 상세한 설명은 생략한다. 특별한 정의가 없는 한 본 명세서의 모든 용어는 본 발명이 속하는 기술분야의 통상의 지식을 가진 기술자가 이해하는 당해 용어의 일반적 의미와 동일하고 만약 본 명세서에 사용된 용어의 의미와 충돌하는 경우에는 본 명세서에 사용된 정의에 따른다. Hereinafter, the color film for paint protection according to the present invention will be described in detail with reference to the attached drawings. Additionally, detailed descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention are omitted. Unless otherwise specified, all terms in this specification have the same general meaning as understood by a person skilled in the art to which the present invention pertains, and if there is a conflict with the meaning of the terms used in this specification, this specification Follow the definitions used in the specification.
도 1은 본 발명의 일 실시예에 따른 페인트 보호용 색상필름(1)을 도시한 단면도이다. 상기 페인트 보호용 색상필름(1)은 다층 구조를 가지며, 제1층으로서의 펄과 색상안료를 포함한 열경화성 폴리우레탄층(11), 제2층으로서의 열가소성 폴리우레탄층(TPU, 13), 제3층으로서의 탑코팅층(15)을 포함한다. 또한 상기 페인트 보호용 색상필름(1)은 바람직하게는 감압성 점착제로 형성된 점착층(17)을 포함할 수 있다. 상기 점착층(17)을 보호하기 위해 점착층(17)에 박리 라이너가 박리가능하게 결합될 수 있다. Figure 1 is a cross-sectional view showing a color film (1) for paint protection according to an embodiment of the present invention. The paint protection color film (1) has a multi-layer structure, and includes a thermosetting polyurethane layer (11) containing pearl and color pigment as the first layer, a thermoplastic polyurethane layer (TPU, 13) as the second layer, and a third layer (TPU, 13) as the third layer. It includes a top coating layer (15). In addition, the paint protection color film 1 may preferably include an adhesive layer 17 formed of a pressure-sensitive adhesive. In order to protect the adhesive layer 17, a release liner may be peelably bonded to the adhesive layer 17.
제1층으로서의 상기 열경화성 폴리우레탄 층(11)은 후술하는 기재층인 열가소성 폴리우레탄 층(13)의 일면 상에 라미네이트되어 형성된다. 열경화성 폴리우레탄은 디올 또는 폴리올과 용제, 이소시아네이트계 경화제를 혼합하여 형성되며, 반응지연제가 혼입될 수 있다. 본 발명에 따른 열경화성 폴리우레탄 층(11)은 열경화성 폴리우레탄 수지에 펄과 색상안료가 혼입되어 있으며, 상기 열경화성 폴리우레탄 수지 내에서 평균입자직경이 상이한 펄과 색상안료가 우수하게 분산되는 특성을 가진다. The thermosetting polyurethane layer 11 as the first layer is formed by lamination on one side of the thermoplastic polyurethane layer 13, which is a base layer described later. Thermosetting polyurethane is formed by mixing a diol or polyol with a solvent and an isocyanate-based curing agent, and a reaction retardant may be added. The thermosetting polyurethane layer 11 according to the present invention is a thermosetting polyurethane resin mixed with pearls and color pigments, and has the property of excellent dispersion of pearls and color pigments with different average particle diameters within the thermosetting polyurethane resin. .
열경화성 폴리우레탄 층(11) 내에 혼입되는 펄(11a) 및 색상안료(11b)는 안료(pigment)의 일종으로, 용제에 용해되지 않고 소정 색상을 가지는 미립자상의 무기 또는 유기화합물로 정의될 수 있다. 여기서 펄(11a)은 광원으로부터의 빛을 반사하여 필름에 빛나거나 스파클링 효과를 부여하기 위해 사용될 수 있으며, 바람직하게는 필름을 바라보는 각도에 따라 색상이 변하는 변색 펄이 사용될 수 있다. 색상안료(11b)는 필름에 색상을 부여하기 위해 사용될 수 있다. 이와 같은 펄과 색상안료의 특성으로 인해, 수지 내에서 펄의 분산이 양호한 경우 가시광선에 대한 반사율(VLR)이 양호하게 나타날 수 있으며, 수지 내에서 색상안료의 분산이 양호한 경우 가시광선에 대한 투과율(VLT)이 낮게 나타날 수 있다. 즉 수지와 펄의 상용성이 양호한 경우 반사율(VLR)이 높아지는 경향을 보이고, 수지와 색상안료의 상용성이 양호한 경우 투과율(VLT)이 낮아지는 경향을 보인다.The pearl 11a and color pigment 11b incorporated into the thermosetting polyurethane layer 11 are a type of pigment and can be defined as a particulate inorganic or organic compound that is insoluble in a solvent and has a predetermined color. Here, the pearl 11a can be used to reflect light from a light source to make the film shine or give a sparkling effect. Preferably, a discolored pearl whose color changes depending on the angle at which the film is viewed can be used. Color pigment 11b can be used to impart color to the film. Due to these characteristics of pearls and color pigments, if the dispersion of the pearls within the resin is good, the reflectance (VLR) for visible light can be good, and if the dispersion of the color pigments within the resin is good, the transmittance to visible light can be good. (VLT) may appear low. That is, when the compatibility between the resin and the pearl is good, the reflectance (VLR) tends to increase, and when the compatibility between the resin and the color pigment is good, the transmittance (VLT) tends to decrease.
상기 펄(11a)은 플레이크(Flake)라고 불리는 판상의 미립자에 금속산화물이 코팅된 형태를 가질 수 있으며, 보는 각도에 따라 컬러감이 다르게 느껴지도록 형성될 수 있다. 상기 펄은 열경화성 폴리우레탄 층(11) 총 중량을 기준으로 0.5 중량부 이상 3 중량부 이하로 혼입되는 것이 바람직하다. 상기 펄은 0.5 중량부 이하일 경우 변색 및 반사에 의한 스파클링효과가 떨어지며, 3중량부 이상일 경우 필름의 기본성능인 시인성이 떨어진다. 또한 상기 색상안료(11b)는 열경화성 폴리우레탄 층(11)을 기준으로 10 중량부 이상 15 중량부 이하로 혼입되는 것이 바람직하다. 후술하는 바와 같이, 색상안료(11b)의 혼입량이 적은 경우 필름의 차폐성능이 떨어져 피착면의 도장 색상이 비쳐보이게 되며, 혼입량이 지나치게 많은 경우 비경제적이며 과량 혼입된 색상안료에 의해 펄(11a)의 반사 효과가 오히려 떨어지게 된다. The pearl 11a may have a metal oxide coating on plate-shaped particles called flakes, and may be formed to have a different color depending on the viewing angle. The pearl is preferably incorporated in an amount of 0.5 parts by weight or more and 3 parts by weight or less based on the total weight of the thermosetting polyurethane layer 11. If the amount of pearl is less than 0.5 parts by weight, the sparkling effect due to discoloration and reflection is reduced, and if it is more than 3 parts by weight, visibility, which is the basic performance of the film, is reduced. In addition, the color pigment 11b is preferably incorporated in an amount of 10 to 15 parts by weight based on the thermosetting polyurethane layer 11. As described later, if the amount of color pigment (11b) mixed is small, the shielding performance of the film deteriorates and the paint color on the adhered surface is visible, and if the amount mixed is too large, it is uneconomical and the pearl (11a) is damaged due to the excessive color pigment. The reflection effect actually decreases.
상기 펄(11a)과 색상안료(11b)가 혼입됨에 따른 페인트 보호용 색상필름은 380 내지 780nm 파장의 가시광선 영역에서 투과도(VLT)가 3% 이하, 반사도(VLR)가 5 내지 15%의 범위를 가지는 것이 바람직하다.The color film for paint protection resulting from the mixing of the pearl (11a) and the color pigment (11b) has a transmittance (VLT) of 3% or less and a reflectance (VLR) of 5 to 15% in the visible light range of 380 to 780 nm wavelength. It is desirable to have it.
열경화성 폴리우레탄 층(11) 내에 혼입되는 펄(11a) 및 색상안료(11b)는 상이한 평균입자직경을 가진다. 상기 펄(11a)의 입자직경은 바람직하게는 5㎛ 이상 45㎛ 이하로 평균입경이 약 25㎛일 수 있다. 입경이 5㎛보다 작은 경우 너무 작은 입도 사이즈로 인하여 차폐 및 색상필름의 원래 목적인 차폐 및 변색효과가 미비하게 구현되며, 100㎛ 이상의 펄의 경우 너무 큰 입도로 인하여 코팅시 이물로 보이거나 시인성의 저하를 초래할 수 있다. 색상안료(11b)의 입자직경은 바람직하게는 1㎛ 이상 5㎛ 이하로 평균입경이 약 2 내지 2.5㎛일 수 있다. 상기 색상안료 또한 입경이 1㎛보다 작은 경우 작은 입도 사이즈로 인하여 빛의 차폐 및 색상효과가 떨어지며, 입경이 10㎛보다 큰 경우 분산이 어렵고 시인성의 저하를 초래할 수 있다.The pearl 11a and the color pigment 11b incorporated into the thermosetting polyurethane layer 11 have different average particle diameters. The particle diameter of the pearl 11a is preferably 5 ㎛ or more and 45 ㎛ or less, and the average particle diameter may be about 25 ㎛. If the particle size is smaller than 5㎛, the original purpose of the shielding and color film, which is the shielding and discoloration effect, is not implemented due to the too small particle size. In the case of pearls over 100㎛, the particle size is too large, so it appears as a foreign matter or reduces visibility during coating. may result in The particle diameter of the color pigment 11b is preferably 1 ㎛ or more and 5 ㎛ or less, and the average particle diameter may be about 2 to 2.5 ㎛. If the color pigment has a particle size smaller than 1㎛, light shielding and color effects are reduced due to the small particle size, and if the particle size is larger than 10㎛, dispersion is difficult and visibility may be reduced.
특히, 펄(11a) 및 색상안료(11b)가 동일한 수지에 분산됨에 따라, 소정 재료의 입경 변화에 의해 다른 재료의 분산성이 영향을 받을 수 있다. 후술하는 실시예에서 설명되는 바와 같이, 색상안료(11b)의 입경에 따라 펄(11a)의 분산성이 달라진다. 동일한 층 내에서 펄(11a) 및 색상안료(11b)가 열경화성 폴리우레탄 수지에 분산되는 경우, 입자직경이 5㎛ 이상 45㎛ 이하인 펄(11a)에 대해 색상안료(11b)의 입경은 1㎛ 이상 5㎛ 이하인 것이 바람직하다.In particular, as the pearl 11a and the color pigment 11b are dispersed in the same resin, the dispersibility of other materials may be affected by changes in the particle size of a certain material. As will be explained in the examples described later, the dispersibility of the pearl 11a varies depending on the particle size of the color pigment 11b. When the pearl (11a) and the color pigment (11b) are dispersed in a thermosetting polyurethane resin in the same layer, the particle diameter of the color pigment (11b) is 1 μm or more for the pearl (11a) with a particle diameter of 5 μm or more and 45 μm or less. It is preferable that it is 5㎛ or less.
열경화성 폴리우레탄 수지는 폴리에스테르계, 폴리아크릴계, 폴리에테르계, 폴리카보네이트계, 폴리알킬렌계 및 이중 1종 이상의 혼합물이 사용될 수 있으나, 폴리에스터계 수지를 사용함이 바람직하다. 상기 열경화성 폴리우레탄 수지는 혼입되는 펄과 색상안료가 수지 내에서 원활하게 분산되어야 하는데, 본 발명의 발명자들은 소정 범위의 분자량과 유리전이온도를 가지는 폴리에스테르계 수지 내에서 펄과 색상안료가 원활하게 분산됨을 확인하고 본 발명에 이르렀다. 상기 폴리에스테르계 수지는 중량평균분자량이 40,000 이상 60,000 이하이고, 유리전이온도는 20℃ 이상 60℃ 이하인 것이 바람직하다. 상기 분자량 및 유리전이온도 범위 내에서 상이한 입경의 펄(11a)과 색상안료(11b)가 동시에 원활하게 수지 내에 분산될 수 있다. 열경화성 폴리우레탄 수지는 30중량% 내지 40중량% 사용될 수 있다.Thermosetting polyurethane resins may be polyester-based, polyacrylic-based, polyether-based, polycarbonate-based, polyalkylene-based, and mixtures of one or more of these, but it is preferable to use polyester-based resin. The thermosetting polyurethane resin requires that the pearls and color pigments mixed in are smoothly dispersed within the resin, but the inventors of the present invention proposed that the pearls and color pigments be smoothly dispersed within a polyester resin having a molecular weight and glass transition temperature within a predetermined range. After confirming the dispersion, we arrived at the present invention. The polyester resin preferably has a weight average molecular weight of 40,000 to 60,000 and a glass transition temperature of 20°C to 60°C. Pearls 11a and color pigments 11b of different particle sizes within the above molecular weight and glass transition temperature ranges can be simultaneously and smoothly dispersed in the resin. Thermosetting polyurethane resin may be used in an amount of 30% to 40% by weight.
수지의 분자량이 지나치게 높으면 펄(11a)과 색상안료(11b)가 수지 내에 원활하게 분산되지 않는다. 즉 펄(11a)과 색상안료(11b)의 수지에 대한 상용성이 동일한 경향을 나타내지 못한다. 또한 수지의 분자량이 지나치게 낮으면 펄과 색상안료의 분산이 일정하지 않으며, 이에 의해 가시광선에 대한 필름의 투과율(VLT)이 높게 나타난다.If the molecular weight of the resin is too high, the pearl (11a) and color pigment (11b) are not smoothly dispersed within the resin. That is, the compatibility of the pearl (11a) and the color pigment (11b) with the resin does not show the same tendency. In addition, if the molecular weight of the resin is too low, the dispersion of pearls and color pigments is not constant, which results in a high transmittance (VLT) of the film to visible light.
용제로는 MEK(메틸에틸케톤), 톨루엔 또는 이들의 혼합물이 사용될 수 있으며, 용제는 열경화성 폴리우레탄 층의 중량을 기준으로 50중량부 내지 70중량부가 혼합될 수 있다. The solvent may be MEK (methyl ethyl ketone), toluene, or a mixture thereof, and the solvent may be mixed in an amount of 50 to 70 parts by weight based on the weight of the thermosetting polyurethane layer.
경화제는 이소시아네이트 및 에폭시, 금속킬레이트 중 하나 이상을 사용할 수 있으며, 열경화성 폴리우레탄 층의 중량 기준 3중량부 내지 5중량부 사용될 수 있다. 상기 경화제가 3중량부 내지 5중량부 사용됨에 따라 열경화성 폴리우레탄 층이 연신 시 늘어나는 신축성을 가질 수 있다. 이에 따라 본 발명에 따른 페인트 보호용 색상필름을 피착면에 원활하게 부착 또는 시공할 수 있다.The curing agent may be one or more of isocyanate, epoxy, and metal chelate, and may be used in an amount of 3 to 5 parts by weight based on the weight of the thermosetting polyurethane layer. As the curing agent is used in an amount of 3 to 5 parts by weight, the thermosetting polyurethane layer may have elasticity that increases when stretched. Accordingly, the color film for paint protection according to the present invention can be smoothly attached or installed on the adhered surface.
반응지연제로는 아세틸아세톤이 사용되는 것이 바람직하며, 열경화성 폴리우레탄 층을 기준으로 0.1 내지 1중량부 사용될 수 있다. Acetylacetone is preferably used as a reaction retardant, and may be used in an amount of 0.1 to 1 part by weight based on the thermosetting polyurethane layer.
제2층 및 기재층으로서의 열가소성 폴리우레탄 층(13)은 폴리카보네이트계나 폴리에스테르계 폴리올 등의 공지된 폴리올과 이소시아네이트 등의 경화제를 혼합한 열가소성 폴리우레탄을 사용할 수 있다. 통상적인 방법을 사용하여, 예를 들면 수성 분산액 또는 용액 혼합물을 박리가능한 캐리어 웹 또는 라이너 상에 캐스팅하거나 달리 코팅하여 폴리우레탄 층이 형성될 수 있다.The thermoplastic polyurethane layer 13 as the second layer and the base layer can be made of thermoplastic polyurethane mixed with a known polyol such as polycarbonate-based or polyester-based polyol and a curing agent such as isocyanate. The polyurethane layer may be formed using conventional methods, for example, by casting or otherwise coating an aqueous dispersion or solution mixture onto a peelable carrier web or liner.
제3층으로서의 상기 탑코팅층(15)은 기재층인 열가소성 폴리우레탄층(13)의 일면상에 도포되어 기재층을 보호하도록 구비될 수 있으며, 흙이나 모래, 아스팔트 파편 등의 이물질과의 충돌로부터 기재층을 보호한다. 상기 탑코팅층(15)은 열경화성, 열가소성 또는 광경화성 수지를 통해 형성될 수 있다. 폴리카르보네이트 수지, 아크릴 수지, 폴리에스테르수지, 페녹시 수지, 에폭시 수지, 폴리올레핀 수지, 플루오로에틸비닐에테르(FEVE) 수지 등이 열경화성 수지로 사용될 수 있으며, 폴리프로필렌 수지, 폴리카르보네이트 수지, 아크릴 수지, 폴리스티롤 수지 등이 열가소성 수지로 사용될 수 있다. 우레탄아크릴레이트 수지, 폴리에스테르아크릴레이트 수지 등의 수지가 광경화성 수지로 사용될 수 있다. 상기 탑코팅층(15)은 자가복원성을 가지도록 함이 바람직하다.The top coating layer 15 as the third layer can be applied on one side of the thermoplastic polyurethane layer 13, which is the base layer, to protect the base layer from collision with foreign substances such as dirt, sand, and asphalt debris. Protects the base layer. The top coating layer 15 may be formed using thermosetting, thermoplastic, or photocurable resin. Polycarbonate resin, acrylic resin, polyester resin, phenoxy resin, epoxy resin, polyolefin resin, and fluoroethyl vinyl ether (FEVE) resin can be used as thermosetting resins, and polypropylene resin and polycarbonate resin can be used as thermosetting resins. , acrylic resin, polystyrene resin, etc. can be used as thermoplastic resins. Resins such as urethane acrylate resin and polyester acrylate resin can be used as photocurable resins. It is desirable that the top coating layer 15 has self-healing properties.
점착층(17)으로는 박리라이너 상의 아크릴릭 감압성 점착제 등을 열을 통해 라미네이션하여 형성할 수 있으며, 박리라이너(19)로는 공지된 구성으로서의 이형지 등이 사용될 수 있다. The adhesive layer 17 can be formed by lamination of an acrylic pressure-sensitive adhesive on a release liner through heat, and the release liner 19 can be made of a known release paper or the like.
(실시예 1)(Example 1)
유리전이온도(Tg) 20~60℃, 중량평균분자량 40,000~60,000의 폴리에스터계 폴리우레탄 수지 35중량%(일본 도요잉크페인트사 우레탄수지), 용제로서 MEK(메틸에틸케톤) 37중량%(한국 삼전순약공업), 용제로서 톨루엔 20중량%(한국 삼전순약공업), 경화제로서 이소시아네이트계 경화제 3중량%(일본 Tosoh사 Coronate HX), 반응지연제로서 아세틸아세톤 1중량%(한국 대정화금)를 혼합하고, 여기에 입자직경이 5㎛ 이상 45㎛ 이하인 변색 펄이 2중량%(독일 BASF사 Gemtone Radiant Nude G016), 카본 블랙 색상을 띄는 입자직경이 10nm 이상 100nm 이하인 색상안료 1중량%(한국 OCI 카본블랙)가 분산된 열경화성 폴리우레탄 층(11) 분산액을 형성하였다.35% by weight of polyester-based polyurethane resin with a glass transition temperature (Tg) of 20 to 60°C and a weight average molecular weight of 40,000 to 60,000 (urethane resin from Toyo Ink Paint, Japan), and 37% by weight of MEK (methyl ethyl ketone) as a solvent (Korea) Samjeon Pure Pharmaceutical Co., Ltd.), 20% by weight of toluene as a solvent (Samjeon Pure Pharmaceutical Co., Ltd., Korea), 3% by weight isocyanate-based hardener (Coronate HX, Tosoh, Japan) as a hardener, and 1% by weight of acetylacetone (Daejeong Chemical Co., Ltd., Korea) as a reaction retardant. Mix, and add 2% by weight of discolored pearl with a particle diameter of 5㎛ to 45㎛ (Gemtone Radiant Nude G016, BASF, Germany), and 1% by weight of color pigment with a particle diameter of 10nm to 100nm (Korea OCI) with a carbon black color. A dispersion of a thermosetting polyurethane layer (11) in which carbon black) was dispersed was formed.
기재층(13)으로는 폴리카보네이트계 및 폴리에스테르계 폴리올과 이소시아네이트계 경화제를 혼합한 열가소성 폴리우레탄(TPU, 미국 SWM사 49510-60DV) 용액을 사용하고, 탑코팅층(15)으로는 폴리카르보네이트 수지(일본 AICA사 열경화성 폴리카르보네이트 수지)를 사용하였다. 점착층(17)으로는 박리 라이너 상의 아크릴릭 감압성 점착제(일본 AICA사 op-3510-2)를 사용하였다.As the base layer (13), a thermoplastic polyurethane (TPU, 49510-60DV, SWM, USA) solution mixed with polycarbonate-based and polyester-based polyol and isocyanate-based curing agent was used, and as the top coating layer (15), polycarbohydrate Nate resin (thermosetting polycarbonate resin manufactured by AICA, Japan) was used. As the adhesive layer 17, an acrylic pressure-sensitive adhesive (op-3510-2, AICA, Japan) on a release liner was used.
이들 용액을 막 형태로 적층하여 페인트 보호필름을 형성하였다. 상기 기재층(13)인 열가소성 폴리우레탄(TPU) 용액은 박리가능한 캐리어 웹 또는 라이너 상에 캐스팅하거나 코팅하여 형성되고, 열경화성 폴리우레탄 층(11), 탑코팅층(15)은 기재층(13)의 일면상에 캐스팅하여 형성되었다. 점착층(17)은 이형필름에 코팅층을 도포한 후 전사코팅하여 필름을 형성하였다.These solutions were laminated in the form of a film to form a paint protection film. The thermoplastic polyurethane (TPU) solution, which is the base layer 13, is formed by casting or coating on a peelable carrier web or liner, and the thermosetting polyurethane layer 11 and the top coating layer 15 are of the base layer 13. It was formed by casting on one side. The adhesive layer 17 was formed by applying a coating layer to a release film and then applying transfer coating.
(실시예 2)(Example 2)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 5중량% 분산되고, 용제인 MEK 함량이 색상안료 함량의 증분만큼 감소된 필름을 형성하였다. 이하 실시예들에서도 색상안료의 함량 변화에 대응하도록 용제의 함량을 변화시켰다.5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed, and a film was formed in which the MEK content as a solvent was reduced by the increment of the color pigment content. In the following examples, the content of the solvent was changed to correspond to the change in the content of the color pigment.
(실시예 3)(Example 3)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 8중량% 분산된 필름을 형성하였다.A film in which 8% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
(실시예 4)(Example 4)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 10중량% 분산된 필름을 형성하였다.A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
(실시예 5)(Example 5)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 12.5중량% 분산된 필름을 형성하였다.A film in which 12.5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
(실시예 6)(Example 6)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 15중량% 분산된 필름을 형성하였다.A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
(실시예 7)(Example 7)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 17중량% 분산된 필름을 형성하였다.A film in which 17% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was dispersed was formed.
(실시예 8)(Example 8)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료의 입자직경이 1㎛ 이상 5㎛ 이하가 되도록 하고, 상기 색상안료가 1중량% 분산된 필름을 형성하였다.The particle diameter of the color pigment constituting the thermosetting polyurethane layer 11 of Example 1 was 1 μm or more and 5 μm or less, and a film in which 1% by weight of the color pigment was dispersed was formed.
(실시예 9)(Example 9)
실시예 8의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 5중량% 분산된 필름을 형성하였다.A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
(실시예 10)(Example 10)
실시예 8의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 8중량% 분산된 필름을 형성하였다.A film in which 8% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
(실시예 11)(Example 11)
실시예 8의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 10중량% 분산된 필름을 형성하였다.A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
(실시예 12)(Example 12)
실시예 8의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 12.5중량% 분산된 필름을 형성하였다.A film in which 12.5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
(실시예 13)(Example 13)
실시예 8의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 15중량% 분산된 필름을 형성하였다.A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
(실시예 14)(Example 14)
실시예 8의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 17중량% 분산된 필름을 형성하였다.A film in which 17% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 8 was dispersed was formed.
가시광선에 대한 투과 및 반사 시험Transmission and reflection tests for visible light
실시예 1 내지 14에 의해 형성된 필름에 대해 가시광선 투과 및 반사 비율을 수행하였다. 색상안료의 입경과 함량에 따라 아래 표 1 및 표 2와 같은 가시광선 투과율(VLT) 및 반사율(VLR) 결과가 도출되었다. 이때 투과율은 필름의 탑코팅층 측에 조사된 가시광선대비 필름의 이면에서 측정 되는 가시광선의 광량이고 반사율은 필름의 일측면에서 탑코팅층 측에 조사된 가시광선 대비 반사되는 가시광선의 광량이다. 이를 분광계(Spectrometer) Jasco社 V-770으로 측정하였다. 표 1은 색상안료의 함량(중량%) 및 입경에 따른 가시광선 투과율을 백분율로 나타낸 것이며, 표 2는 색상안료의 함량(중량%) 및 입경에 따른 가시광선 반사율을 백분율로 나타낸 것이다.Visible light transmission and reflection ratios were performed on the films formed by Examples 1 to 14. Depending on the particle size and content of the color pigment, the visible light transmittance (VLT) and reflectance (VLR) results shown in Table 1 and Table 2 below were derived. At this time, the transmittance is the amount of visible light measured on the back of the film compared to the visible light irradiated to the top coating layer of the film, and the reflectance is the amount of visible light reflected from one side of the film compared to the visible light irradiated to the top coating layer. This was measured with a spectrometer, Jasco V-770. Table 1 shows the visible light transmittance as a percentage according to the content (% by weight) of the color pigment and particle size, and Table 2 shows the visible light reflectance as a percentage according to the content (% by weight) of the color pigment and the particle size.
함량/입경Content/particle size 1One 55 88 1010 12.512.5 1515 1717
10~100㎚10~100㎚ 27.0427.04 10.8410.84 7.587.58 5.475.47 2.972.97 0.5450.545 0.390.39
1~5㎛1~5㎛ 32.0432.04 9.389.38 4.474.47 2.762.76 1.131.13 0.350.35 0.170.17
함량/입경Content/particle size 1One 55 88 1010 12.512.5 1515 1717
10~100㎚10~100㎚ 20.220.2 11.8611.86 9.779.77 8.878.87 6.346.34 5.245.24 4.384.38
1~5㎛1~5㎛ 22.0322.03 16.7216.72 14.2514.25 13.0213.02 11.1611.16 9.159.15 7.337.33
표 1에 나타난 바와 같이 색상안료 함량이 증가함에 따라 투과율이 비례적으로 감소하였는데, 이를 통해 색상안료가 수지 내에 양호하게 분산되었음을 알 수 있다. 다만 표 2에 나타난 반사율과 도 2 및 도 3에 도시된 실내 광원 하에서 필름의 현미경 관찰 사진을 참고하면 펄의 분산성은 색상안료의 입경에 따라 달라짐을 확인할 수 있다.As shown in Table 1, as the color pigment content increased, the transmittance decreased proportionally, which shows that the color pigment was well dispersed in the resin. However, referring to the reflectance shown in Table 2 and the microscopic observation photos of the film under an indoor light source shown in Figures 2 and 3, it can be confirmed that the dispersibility of the pearl varies depending on the particle size of the color pigment.
펄과 함께 nm 단위 입경을 가진 색상안료의 혼합 시 색상안료의 함량 증가에 따라 펄의 분산성이 양호하지 않은 것이 나타난다. 도 2에 표시된 부분에서 안료의 뭉침 현상이 발생하였음을 확인할 수 있으며, 색상안료의 함량이 증가할수록 뭉침현상이 적어져 펄의 분산성이 양호해짐을 확인할 수 있다. 이는 안료의 함량 증가 시 안료가 펄의 입자사이에 배치되어 펄의 분산에 도움을 주는 것으로 파악된다. 이에 반해 도 3에서는 색상안료 10 내지 15중량% 사이에서 펄의 분산이 양호하게 나타나 검은색 표면 상에 백색 펄 색상이 균일하게 분산됨을 확인할 수 있다.When mixing color pigments with a particle size in nm units with pearls, the dispersibility of the pearls is not good as the content of the color pigments increases. It can be seen that agglomeration of the pigment occurred in the area shown in Figure 2, and as the content of the color pigment increases, the agglomeration phenomenon decreases and the dispersibility of the pearl becomes better. It is understood that as the pigment content increases, the pigment is placed between pearl particles, helping to disperse the pearl. On the other hand, in Figure 3, it can be seen that the dispersion of the pearls is good between 10 and 15% by weight of the color pigment, and the white pearl color is uniformly dispersed on the black surface.
열경화성 폴리우레탄 수지에 대해 색상안료 2종 모두 상용성이 양호하나 가시광선 투과율이 1% 이하 일 때 nm단위의 색상안료를 사용한 경우 가시광선 반사율은 약 5%, um단위의 색상안료를 사용한 경우 가시광선 반사율은 약 9%로 nm 단위의 경우 펄의 반사가 육안으로 잘 확인되지 않았나, um단위 색상안료의 경우 펄의 반사 정도가 육안으로 관찰가능하였으며, 각도에 따라 색이 변하는 color shift 현상도 무리 없이 확인 가능하였다. 상기 데이터를 참고할 때 가시광선 투과율이 1% 미만일 때 가시광 반사율 9% 이상인 경우 단일층 제품 제작의 재료 및 배합비로 사용이 바람직한 것으로 판단된다. Both types of color pigments have good compatibility with thermosetting polyurethane resin, but when the visible light transmittance is less than 1%, when a color pigment in the nm unit is used, the visible light reflectance is about 5%, and when the color pigment in the um unit is used, the visible light reflectance is about 5%. The light reflectance was about 9%, and in the case of nm units, the reflection of the pearl was not clearly visible to the naked eye. In the case of color pigments in the um unit, the degree of reflection of the pearls was visible to the naked eye, and the color shift phenomenon in which the color changes depending on the angle was also unreasonable. It was possible to check without it. Referring to the above data, when the visible light transmittance is less than 1% and the visible light reflectance is 9% or more, it is considered desirable to use it as a material and mixing ratio for manufacturing single-layer products.
(실시예 15)(Example 15)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 폴리에스테르계 폴리우레탄 수지 대신 아크릴 수지(일본 AICA사 op-3510-2)를 사용하였다. 상기 아크릴 수지는 중량평균분자량 400,000 내지 800,000, 유리전이온도 -45℃ 내지 -15℃이다. 색상안료는 입자직경이 입자직경이 10nm 이상 100nm 이하가 되도록 하고, 상기 색상안료가 1중량% 분산된 필름을 형성하였다. 펄의 입경과 함량은 실시예 1과 동일하다.Instead of the polyester-based polyurethane resin constituting the thermosetting polyurethane layer 11 of Example 1, an acrylic resin (op-3510-2, AICA, Japan) was used. The acrylic resin has a weight average molecular weight of 400,000 to 800,000 and a glass transition temperature of -45°C to -15°C. The color pigment had a particle diameter of 10 nm or more and 100 nm or less, and a film in which 1% by weight of the color pigment was dispersed was formed. The particle size and content of pearls were the same as in Example 1.
(실시예 16)(Example 16)
실시예 15의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 5중량% 분산된 필름을 형성하였다.A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 15 was dispersed was formed.
(실시예 17)(Example 17)
실시예 15의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 10중량% 분산된 필름을 형성하였다.A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 15 was dispersed was formed.
(실시예 18)(Example 18)
실시예 15의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 15중량% 분산된 필름을 형성하였다.A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 15 was dispersed was formed.
(실시예 19)(Example 19)
실시예 15의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료의 입자직경이 1㎛ 이상 5㎛ 이하가 되도록 하고, 상기 색상안료가 1중량% 분산된 필름을 형성하였다.The particle diameter of the color pigment constituting the thermosetting polyurethane layer 11 of Example 15 was 1 μm or more and 5 μm or less, and a film in which 1% by weight of the color pigment was dispersed was formed.
(실시예 20)(Example 20)
실시예 19의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 5중량% 분산된 필름을 형성하였다.A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 19 was dispersed was formed.
(실시예 21)(Example 21)
실시예 19의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 10중량% 분산된 필름을 형성하였다.A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 19 was dispersed was formed.
(실시예 22)(Example 22)
실시예 19의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 15중량% 분산된 필름을 형성하였다.A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 19 was dispersed was formed.
가시광선에 대한 투과 및 반사 시험Transmission and reflection tests for visible light
실시예 15 내지 22에 의해 형성된 필름에 대해 가시광선 투과 및 반사 비율을 수행하였다. 색상안료의 입경과 함량에 따라 아래 표 3 및 표 4와 같은 가시광선 투과율(VLT) 및 반사율(VLR) 결과가 도출되었다. 표 3은 색상안료의 함량(중량%) 및 입경에 따른 가시광선 투과율을 백분율로 나타낸 것이며, 표 4는 색상안료의 함량(중량%) 및 입경에 따른 가시광선 반사율을 백분율로 나타낸 것이다.Visible light transmission and reflection ratios were performed on the films formed by Examples 15-22. Depending on the particle size and content of the color pigment, the visible light transmittance (VLT) and reflectance (VLR) results shown in Table 3 and Table 4 below were derived. Table 3 shows the visible light transmittance as a percentage according to the content (% by weight) of the color pigment and particle size, and Table 4 shows the visible light reflectance as a percentage according to the content (% by weight) of the color pigment and the particle size.
함량/입경Content/particle size 1One 55 1010 1515
10~100㎚10~100㎚ 16.8416.84 4.74.7 0.050.05 0.020.02
1~5㎛1~5㎛ 28.6828.68 32.732.7 32.0832.08 25.7925.79
함량/입경Content/particle size 1One 55 1010 1515
10~100㎚10~100㎚ 17.0517.05 8.868.86 5.935.93 5.525.52
1~5㎛1~5㎛ 27.227.2 22.322.3 18.718.7 12.5512.55
표 3에 나타난 바와 같이 색상안료의 입경이 nm 단위인 경우 색상안료의 함량이 증가함에 따라 투과율이 비례적으로 감소하였는데, 이를 통해 nm 단위 입경을 가진 색상안료가 수지 내에 양호하게 분산되었음을 알 수 있다. 이에 반해 색상안료의 입경이 ㎛단위인 경우 색상안료 함량 증가에 따라 가시광선 투과율이 비례하여 감소하는 것이 확인되지 않는다. As shown in Table 3, when the particle size of the color pigment is in the nm unit, the transmittance decreased proportionally as the content of the color pigment increased. This shows that the color pigment with the particle size in the nm unit was well dispersed in the resin. . On the other hand, when the particle size of the color pigment is in the ㎛ unit, it is not confirmed that the visible light transmittance decreases proportionally as the color pigment content increases.
도 4에 도시된 실내 광원 하 현미경 관찰 사진을 참고하면, 색상안료의 입경이 nm 단위인 경우 펄이 응집되어 분산되지 않은 현상을 확인할 수 있다. 색상안료의 함량이 증가할수록 펄의 분산성은 양호해지는데, 펄의 분산이 양호해지더라도 분산된 색상안료가 증가함에 따라 가시광 반사율이 낮아지는 것을 표 4에서 확인할 수 있다.Referring to the microscope observation photo under an indoor light source shown in Figure 4, it can be seen that when the particle size of the color pigment is in nm, the pearls are aggregated and not dispersed. As the content of the color pigment increases, the dispersibility of the pearl becomes better. It can be seen in Table 4 that even if the dispersion of the pearl becomes better, the visible light reflectance decreases as the dispersed color pigment increases.
도 5는 입경이 ㎛단위인 색상안료가 사용된 필름에 대해 현미경 광원을 조사한 후 이를 현미경으로 관찰한 사진이다. 이를 참고하면 색상안료의 함량이 증가함에 따라 흑색 입자가 응집된 것이 증가하여 관찰된다. 이는 색상안료의 분산이 원활하지 못하여 응집이 발생한 것으로, 표 3의 색상안료 함량 증가에 따라 투과율이 감소하지 않는 현상을 설명한다.Figure 5 is a photograph of a film using a color pigment with a particle size of ㎛ measured under a microscope after being irradiated with a microscope light source. Referring to this, it is observed that as the content of color pigment increases, the number of black particles agglomerated increases. This is because agglomeration occurred due to poor dispersion of the color pigment, which explains the phenomenon in which transmittance does not decrease as the color pigment content in Table 3 increases.
아크릴 수지에 대하여, 펄과 함께 nm 단위 입경을 가진 색상안료의 혼합 시 색상안료의 함량 10중량부 이상에서 펄과 색상안료의 분산성이 양호한 것을 확인할 수 있다. 그러나 펄과 색상안료의 분산성이 양호하더라도 가시광선 반사율(VLR)은 5 내지 6%로, 펄의 반사되는 색상 판별이 불가능한 문제가 있다. 따라서 실시예 15 내지 22의 아크릴 수지의 경우 제1층의 수지로는 부적합한 것으로 판단할 수 있다.With respect to acrylic resin, it can be confirmed that the dispersibility of pearls and color pigments is good when mixing color pigments with a particle size in nm units with pearls when the color pigment content is 10 parts by weight or more. However, even if the dispersibility of the pearl and the color pigment is good, the visible light reflectance (VLR) is 5 to 6%, so there is a problem that it is impossible to distinguish the reflected color of the pearl. Therefore, the acrylic resins of Examples 15 to 22 can be judged to be unsuitable as the resin for the first layer.
(실시예 23)(Example 23)
실시예 1의 열경화성 폴리우레탄 층(11)을 구성하는 폴리에스테르계 폴리우레탄 수지의 중량평균분자량을 10,000~30,000으로 변경(일본 도요잉크페인트사 저분자량 우레탄수지)하여 폴리우레탄 층(11) 분산액을 형성하였다. 색상안료 및 펄의 입경과 함량은 실시예 1과 동일하다.The weight average molecular weight of the polyester-based polyurethane resin constituting the thermosetting polyurethane layer 11 of Example 1 was changed to 10,000 to 30,000 (low molecular weight urethane resin from Toyo Ink Paint, Japan) to prepare a dispersion of the polyurethane layer 11. formed. The particle size and content of color pigment and pearl are the same as in Example 1.
(실시예 24)(Example 24)
실시예 23의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 5중량% 분산된 필름을 형성하였다.A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 23 was dispersed was formed.
(실시예 25)(Example 25)
실시예 23의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 10중량% 분산된 필름을 형성하였다.A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 23 was dispersed was formed.
(실시예 26)(Example 26)
실시예 23의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 15중량% 분산된 필름을 형성하였다.A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 23 was dispersed was formed.
(실시예 27)(Example 27)
실시예 23의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료의 입자직경이 1㎛ 이상 5㎛ 이하가 되도록 하고, 상기 색상안료가 1중량% 분산된 필름을 형성하였다.The particle diameter of the color pigment constituting the thermosetting polyurethane layer 11 of Example 23 was 1 μm or more and 5 μm or less, and a film in which 1% by weight of the color pigment was dispersed was formed.
(실시예 28)(Example 28)
*실시예 27의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 5중량% 분산된 필름을 형성하였다.*A film in which 5% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 27 was dispersed was formed.
(실시예 29)(Example 29)
실시예 27의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 10중량% 분산된 필름을 형성하였다.A film in which 10% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 27 was dispersed was formed.
(실시예 30)(Example 30)
실시예 27의 열경화성 폴리우레탄 층(11)을 구성하는 색상안료가 15중량% 분산된 필름을 형성하였다.A film in which 15% by weight of the color pigment constituting the thermosetting polyurethane layer 11 of Example 27 was dispersed was formed.
가시광선에 대한 투과 및 반사 시험Transmission and reflection tests for visible light
실시예 23 내지 30에 의해 형성된 필름에 대해 가시광선 투과 및 반사 비율을 수행하였다. 색상안료의 입경과 함량에 따라 아래 표 5 및 표 6와 같은 가시광선 투과율(VLT) 및 반사율(VLR) 결과가 도출되었다. 표 5는 색상안료의 함량(중량%) 및 입경에 따른 가시광선 투과율을 백분율로 나타낸 것이며, 표 6은 색상안료의 함량(중량%) 및 입경에 따른 가시광선 반사율을 백분율로 나타낸 것이다.Visible light transmission and reflection ratios were performed on the films formed by Examples 23-30. Depending on the particle size and content of the color pigment, the visible light transmittance (VLT) and reflectance (VLR) results shown in Table 5 and Table 6 below were derived. Table 5 shows the visible light transmittance as a percentage according to the content (% by weight) of the color pigment and particle size, and Table 6 shows the visible light reflectance as a percentage according to the content (% by weight) of the color pigment and the particle size.
함량/입경Content/particle size 1One 55 1010 1515
10~100㎚10~100㎚ 23.523.5 2828 1212 6.956.95
1~5㎛1~5㎛ 32.132.1 27.927.9 12.512.5 0.320.32
함량/입경Content/particle size 1One 55 1010 1515
10~100㎚10~100㎚ 19.619.6 16.216.2 12.712.7 6.986.98
1~5㎛1~5㎛ 22.822.8 9.59.5 7.47.4 5.15.1
표 5에 나타난 바와 같이 수지의 분자량이 적은 경우 색상안료의 입경과 함량 증가에 관계없이 가시광선 투과율 감소가 일정하지 않고, 색상안료의 함량이 10중량%인 경우 가시광선 투과율이 약 12% 정도로, 타 실시예에서 색상안료의 함량이 10중량부인 경우에 비해 가시광선 투과율이 약 8%가량 높게 측정된다.10 내지 100nm 입경을 가지는 색상안료의 함량이 15중량%인 경우 가시광선 투과율이 약 6%정도로 동일한 색상안료 함량의 타 실시예 대비 높게 나타나며, 가시광선 투과율을 1% 미만으로 만들기 위해서는 색상안료를 과량 혼입하여야 할 것으로 판단된다.As shown in Table 5, when the molecular weight of the resin is low, the decrease in visible light transmittance is not constant regardless of the increase in the particle size and content of the color pigment, and when the content of the color pigment is 10% by weight, the visible light transmittance is about 12%, In other examples, the visible light transmittance is measured to be about 8% higher than when the content of the color pigment is 10 parts by weight. When the content of the color pigment with a particle size of 10 to 100 nm is 15% by weight, the visible light transmittance is about 6%. This is higher than other examples with the same color pigment content, and it is judged that an excessive amount of color pigment must be mixed in order to make the visible light transmittance less than 1%.
표 6에 나타난 바와 같이, 가시광선 반사율의 경우에도 동일하거나 유사한 가시광 투과율을 보이는 색상안료 함량에서 가시광선 반사율을 다른 실시예들과 비교하면, 1 내지 5㎛의 입경을 가지는 색상안료가 5중량% 혼입된 실시예 9(VLT 9.38%, VLR 16.72%)에 비해 색상안료가 10중량% 혼입된 실시예 29(VLT 12.5%, VLR 7.4%)에서 반사율이 현저하게 떨어짐을 알 수 있다. 이는 낮은 분자량의 수지에서는 펄과 색상안료의 분산이 균일하게 이루어지지 않는 것을 설명하며, 도 6 및 도 7의 저분자량 폴리에스테르계 폴리우레탄 수지를 사용한 실시예 23 내지 30을 현미경 광원 하에서 촬영한 현미경 관찰 사진에서 색상안료의 응집을 확인할 수 있다.As shown in Table 6, when comparing the visible light reflectance with other examples in the color pigment content showing the same or similar visible light transmittance, the color pigment having a particle size of 1 to 5 ㎛ is 5% by weight. It can be seen that the reflectance is significantly lower in Example 29 (VLT 12.5%, VLR 7.4%) containing 10% by weight of color pigment compared to Example 9 (VLT 9.38%, VLR 16.72%). This explains that the dispersion of pearls and color pigments is not uniform in low molecular weight resins, and Examples 23 to 30 using the low molecular weight polyester-based polyurethane resin of Figures 6 and 7 were photographed under a microscope light source. The aggregation of the color pigment can be confirmed in the observation photo.
특히 실시예 23 내지 30에서는 필름의 가시광선 투과율을 1% 이하로 낮추려는 경우 색상안료가 과량 혼입되어야 하며, 이때 가시광선 반사율이 5% 이하로 낮아지는 바 저분자량의 수지는 상이한 입경을 가지는 펄과 색상안료의 분산을 위한 재료로 부적합하다.In particular, in Examples 23 to 30, if the visible light transmittance of the film is to be lowered to 1% or less, an excessive amount of color pigment must be mixed, and in this case, the visible light reflectance is lowered to 5% or less, and the low molecular weight resin is pearl with a different particle size. It is unsuitable as a material for dispersing color pigments.
실시예 1 내지 30의 실험결과를 참고하면, 각 수지에 따라 펄과 색상안료의 상용성 차이는 있으나 색상안료 10 내지 15 중량%를 사용하는 경우 가시광선 투과율(VLT) 1% 미만의 데이터를 얻을 수 있어 가시광 차폐가 가능한 것으로 보인다. 다만 펄과 색상안료를 단일층에 혼입하기 위해서는 가시광선 투과율이 1% 미만일 때 펄의 반사 및 변색현상이 관찰되어야 한다. 실시예들의 가시광선 투과율과 반사율을 비교할 때, 중량평균분자량 40,000 내지 60,000, 유리전이온도 20℃ 내지 60℃의 폴리에스테르계 폴리우레탄 수지와 1 내지 5㎛의 입경을 가지는 색상안료 10 내지 15중량%, 5 내지 45㎛의 입경을 가지는 펄 1 내지 3중량%를 사용하여 가시광을 충분히 차폐하면서도 적절한 범위의 가시광 반사와 변색 성능을 가지는 단일층을 가지는 페인트 보호용 색상필름을 제조할 수 있다.Referring to the experimental results of Examples 1 to 30, although there are differences in compatibility between pearl and color pigment depending on each resin, when 10 to 15% by weight of color pigment is used, data with a visible light transmittance (VLT) of less than 1% can be obtained. It appears that visible light shielding is possible. However, in order to mix pearl and color pigment into a single layer, reflection and discoloration of the pearl must be observed when the visible light transmittance is less than 1%. When comparing the visible light transmittance and reflectance of the examples, a polyester-based polyurethane resin with a weight average molecular weight of 40,000 to 60,000 and a glass transition temperature of 20°C to 60°C and 10 to 15% by weight of color pigment having a particle size of 1 to 5 μm. , by using 1 to 3% by weight of pearl having a particle size of 5 to 45㎛, a color film for paint protection can be manufactured having a single layer that sufficiently shields visible light and has an appropriate range of visible light reflection and discoloration performance.
본 발명의 다른 실시예에서는, 도 8에서와 같이 펄과 색상안료를 포함하는 제1층으로서의 열경화성 폴리우레탄 층(11)이 제2층으로서의 열가소성 폴리우레탄 층(13)과 제3층으로서의 탑코팅층(15) 사이에 형성될 수도 있다. 펄과 색상안료를 포함하는 열경화성 폴리우레탄 층(11)이 열가소성 폴리우레탄 층(13) 및 탑코팅층(15) 사이에 형성되는 경우, 가시광이 통과하는 매질의 거리가 짧아진다. 하지만, 기재층인 열가소성 폴리우레탄 층(13) 상에 열경화성 폴리우레탄 층(11)을 코팅한 이후 탑코팅층(15)을 열경화성 폴리우레탄 층(11) 상에 코팅하는 제조과정 상에서, 탑코팅층(15) 용액에 포함된 용제와 열경화성 폴리우레탄 층(11)의 일부 사이의 스웰링 현상이 발생하여 가시광 반사율 및 광택도 상에서 불리한 단점이 있다.In another embodiment of the present invention, as shown in Figure 8, a thermosetting polyurethane layer 11 as a first layer containing pearl and color pigment is composed of a thermoplastic polyurethane layer 13 as a second layer and a top coating layer as a third layer. It may be formed between (15). When the thermosetting polyurethane layer 11 containing pearl and color pigment is formed between the thermoplastic polyurethane layer 13 and the top coating layer 15, the distance through which visible light passes through the medium is shortened. However, in the manufacturing process of coating the thermosetting polyurethane layer 11 on the thermoplastic polyurethane layer 13, which is a base layer, and then coating the top coating layer 15 on the thermosetting polyurethane layer 11, the top coating layer 15 ) A swelling phenomenon occurs between the solvent contained in the solution and a portion of the thermosetting polyurethane layer 11, resulting in disadvantages in terms of visible light reflectance and gloss.
(실시예 31)(Example 31)
본 발명의 바람직한 일 실시예 중 하나인 실시예 11과 같이 열경화성 폴리우레탄 층(11)을 구성하되, 각 층의 구조를 도 8에 도시된 바와 같이 제1층으로서의 열경화성 폴리우레탄 층(11)이 제2층으로서의 열가소성 폴리우레탄 층(13)과 제3층으로서의 탑코팅층(15) 사이에 형성되도록 하였다.A thermosetting polyurethane layer 11 is formed as in Example 11, which is one of the preferred embodiments of the present invention, but the structure of each layer is as shown in FIG. 8, and the thermosetting polyurethane layer 11 as the first layer is It was formed between the thermoplastic polyurethane layer 13 as the second layer and the top coating layer 15 as the third layer.
실시예 11에 따른 페인트 보호용 색상필름의 외관이 도 9에 표시되며, 실시예 31에 따른 페인트 보호용 색상필름의 외관이 도 10에 표시된다. 페인트 보호용 색상필름의 광택도 측정을 위하여, ISO2813에 따라 광택도 측정 각도에 따른 광원 대비 glossmeter로 들어온 빛의 양을 측정하여 표 7에 개시하였다. 이와 같이 실시예 11에 따른 페인트 보호용 색상필름이 실시예 31의 경우보다 우수하며, 외관상으로도 실시예 31은 난반사로 인해 매트한 표면이 관찰된다.The appearance of the color film for paint protection according to Example 11 is shown in Figure 9, and the appearance of the color film for paint protection according to Example 31 is shown in Figure 10. To measure the gloss of the paint protection color film, the amount of light entering the glossmeter was measured compared to the light source according to the gloss measurement angle according to ISO2813, and is listed in Table 7. In this way, the paint protection color film according to Example 11 is superior to that of Example 31, and in appearance, Example 31 has a matte surface due to diffuse reflection.
측정각도에 따른 광택도Glossiness according to measurement angle 2020 6060 8585
실시예11Example 11 8383 9292 9999
실시예31Example 31 5050 8888 9191
이상의 상세한 설명은 본 발명을 예시하는 것이다. 또한 전술한 내용은 본 발명의 바람직한 실시 형태를 나타내어 설명하는 것이며, 본 발명은 다양한 다른 조합, 변경 및 환경에서 사용할 수 있다. 즉 본 명세서에 개시된 발명의 개념의 범위, 저술한 개시 내용과 균등한 범위 및/또는 당업계의 기술 또는 지식의 범위 내에서 변경 또는 수정이 가능하다. 전술한 실시예는 본 발명의 기술적 사상을 구현하기 위한 최선의 상태를 설명하는 것이며, 본 발명의 구체적인 적용 분야 및 용도에서 요구되는 다양한 변경도 가능하다. 따라서 이상의 발명의 상세한 설명은 개시된 실시 상태로 본 발명을 제한하려는 의도가 아니다. 또한 첨부된 청구범위는 다른 실시 상태도 포함하는 것으로 해석되어야 한다. The above detailed description is illustrative of the present invention. Additionally, the foregoing is intended to illustrate preferred embodiments of the present invention, and the present invention can be used in various other combinations, modifications, and environments. That is, changes or modifications are possible within the scope of the inventive concept disclosed in this specification, the scope equivalent to the written disclosure, and/or the skill or knowledge in the art. The above-described embodiments illustrate the best state for implementing the technical idea of the present invention, and various changes required for specific application fields and uses of the present invention are also possible. Accordingly, the detailed description of the invention above is not intended to limit the invention to the disclosed embodiments. Additionally, the appended claims should be construed to include other embodiments as well.

Claims (10)

  1. 열경화성 폴리우레탄계 수지, 경화제, 상기 폴리우레탄계 수지에 혼입되는 펄과 색상안료를 포함하는 제1층을 포함하며, It includes a first layer containing a thermosetting polyurethane-based resin, a curing agent, pearl and color pigment mixed in the polyurethane-based resin,
    상기 펄과 색상안료는 평균입자직경이 상이한 것을 특징으로 하는 페인트 보호용 색상필름.A color film for paint protection, wherein the pearl and the color pigment have different average particle diameters.
  2. 제1항에 있어서, 상기 열경화성 폴리우레탄계 수지는 중량평균분자량이 40,000 이상 60,000 이하, 유리전이온도가 20℃ 이상 60℃ 이하이며,The method of claim 1, wherein the thermosetting polyurethane resin has a weight average molecular weight of 40,000 to 60,000 and a glass transition temperature of 20°C to 60°C,
    상기 제1층에 혼입되는 펄의 입자직경은 5㎛ 이상 100㎛ 이하이고, 상기 제1층에 혼입되는 색상안료의 입자직경은 1㎛ 이상 10㎛ 이하인 것을 특징으로 하는 것을 특징으로 하는 페인트 보호용 색상필름.A paint protection color, characterized in that the particle diameter of the pearl mixed in the first layer is 5 ㎛ or more and 100 ㎛ or less, and the particle diameter of the color pigment mixed in the first layer is 1 ㎛ or more and 10 ㎛ or less. film.
  3. 제2항에 있어서, 상기 제1층에 혼입되는 펄의 입자직경은 5㎛ 이상 45㎛ 이하이고, 상기 제1층에 혼입되는 색상안료의 입자직경은 1㎛ 이상 5㎛ 이하인 것을 특징으로 하는 것을 특징으로 하는 페인트 보호용 색상필름.The method of claim 2, wherein the particle diameter of the pearl mixed in the first layer is 5 ㎛ or more and 45 ㎛ or less, and the particle diameter of the color pigment mixed in the first layer is 1 ㎛ or more and 5 ㎛ or less. Features a color film for paint protection.
  4. 제3항에 있어서, 상기 제1층은 폴리우레탄 수지와 함께 상기 제1층의 중량 기준 펄 1 내지 3 중량부, 색상안료 5 내지 20 중량부를 포함하는 것을 특징으로 하는 페인트 보호용 색상필름.The color film for paint protection according to claim 3, wherein the first layer includes a polyurethane resin and 1 to 3 parts by weight of pearl and 5 to 20 parts by weight of color pigment based on the weight of the first layer.
  5. 제4항에 있어서, 상기 제1층은 상기 색상안료를 바람직하게는 상기 제1층의 중량 기준 10 내지 15중량부 포함하는 것을 특징으로 하는 페인트 보호용 색상필름.The color film for paint protection according to claim 4, wherein the first layer contains the color pigment, preferably 10 to 15 parts by weight based on the weight of the first layer.
  6. 제5항에 있어서, 상기 제1층은 상기 제1층에 혼입된 펄에 의해 각도에 따라 색상이 변화하도록 구비되는 것을 특징으로 하는 페인트 보호용 색상필름.The color film for paint protection according to claim 5, wherein the first layer is provided so that its color changes depending on the angle due to pearls incorporated into the first layer.
  7. 제1항 내지 제6항 중 어느 한 항에 있어서, 상기 제1층의 일면에 형성되며 열가소성 폴리우레탄을 포함하는 제2층, 상기 제2층의 일면에 형성되어 제2층을 보호하는 제3층, 상기 제1층의 다른 일측에 형성되는 점착층을 포함하고, 상기 제1층은 제2층과 점착층 사이에 형성되는 것을 특징으로 하는 페인트 보호용 색상필름.The method of any one of claims 1 to 6, wherein a second layer is formed on one side of the first layer and includes thermoplastic polyurethane, and a third layer is formed on one side of the second layer and protects the second layer. A color film for paint protection, comprising a layer and an adhesive layer formed on the other side of the first layer, wherein the first layer is formed between the second layer and the adhesive layer.
  8. 제7항에 있어서, 상기 페인트 보호용 색상필름은 380 내지 780nm 파장의 가시광선 영역에서 투과율이 3% 이하, 반사율이 5 내지 15%인 것을 특징으로 하는 페인트 보호용 색상필름.The color film for paint protection according to claim 7, wherein the color film for paint protection has a transmittance of 3% or less and a reflectance of 5 to 15% in the visible light region with a wavelength of 380 to 780 nm.
  9. 제1항 내지 제6항 중 어느 한 항에 있어서, 상기 제1층의 일면에 형성되며 열가소성 폴리우레탄을 포함하는 제2층, 상기 제1층의 다른 일면에 형성되어 상기 제1층을 보호하는 제3층, 상기 제2층의 일측에 형성되는 점착층을 포함하고, 상기 제2층은 제1층과 점착층 사이에 형성되는 것을 특징으로 하는 페인트 보호용 색상필름.The method of any one of claims 1 to 6, wherein a second layer is formed on one side of the first layer and includes thermoplastic polyurethane, and is formed on the other side of the first layer to protect the first layer. A color film for paint protection, comprising a third layer and an adhesive layer formed on one side of the second layer, wherein the second layer is formed between the first layer and the adhesive layer.
  10. 제9항에 있어서, 상기 페인트 보호용 색상필름은 380 내지 780nm 파장의 가시광선 영역에서 투과율이 3% 이하, 반사율이 5 내지 15%인 것을 특징으로 하는 페인트 보호용 색상필름.The color film for paint protection according to claim 9, wherein the color film for paint protection has a transmittance of 3% or less and a reflectance of 5 to 15% in the visible light region with a wavelength of 380 to 780 nm.
PCT/KR2023/008975 2022-06-29 2023-06-27 Color film for paint protection WO2024005517A1 (en)

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KR1020220079946A KR102657310B1 (en) 2022-06-29 Color Film for Paint Protection

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100200419B1 (en) * 1996-08-23 1999-06-15 한형수 Light transmittance and reflex film
US20080199704A1 (en) * 2005-04-29 2008-08-21 Ho Charlie C Multilayer Polyurethane Protective Films
US20140302308A1 (en) * 2011-11-21 2014-10-09 3M Innovative Properties Company Paint protective film comprising nanoparticles
KR20150086664A (en) * 2014-01-20 2015-07-29 주식회사 넥센 Composition for Color Golf Ball Cover Using the Thermoplastic Polyurethane Resin and Method for Maufacturing Color Golf Ball
KR101877782B1 (en) * 2016-04-28 2018-07-16 (주)필링크 A Paint Protection Film
CN114539841A (en) * 2020-11-24 2022-05-27 高丽大学校产学协力团 Radiation-cooled element comprising a coating with nano-or micro-particles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100200419B1 (en) * 1996-08-23 1999-06-15 한형수 Light transmittance and reflex film
US20080199704A1 (en) * 2005-04-29 2008-08-21 Ho Charlie C Multilayer Polyurethane Protective Films
US20140302308A1 (en) * 2011-11-21 2014-10-09 3M Innovative Properties Company Paint protective film comprising nanoparticles
KR20150086664A (en) * 2014-01-20 2015-07-29 주식회사 넥센 Composition for Color Golf Ball Cover Using the Thermoplastic Polyurethane Resin and Method for Maufacturing Color Golf Ball
KR101877782B1 (en) * 2016-04-28 2018-07-16 (주)필링크 A Paint Protection Film
CN114539841A (en) * 2020-11-24 2022-05-27 高丽大学校产学协力团 Radiation-cooled element comprising a coating with nano-or micro-particles

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