KR102012683B1 - Multilayer laser marking film - Google Patents
Multilayer laser marking film Download PDFInfo
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- KR102012683B1 KR102012683B1 KR1020160028137A KR20160028137A KR102012683B1 KR 102012683 B1 KR102012683 B1 KR 102012683B1 KR 1020160028137 A KR1020160028137 A KR 1020160028137A KR 20160028137 A KR20160028137 A KR 20160028137A KR 102012683 B1 KR102012683 B1 KR 102012683B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
- B41M5/446—Fluorine-containing polymers
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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
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/34—Both sides of a layer or material are treated, e.g. coated
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- Engineering & Computer Science (AREA)
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
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Abstract
Adhesive layer; A colored base layer having a first color; A colored coating layer having a second color; And a self restoring layer, wherein the first color and the second color are different colors from each other,
The self-healing layer comprises a cured product of a photocurable composition comprising a photocurable urethane acrylate resin, a photocurable acrylate monomer and inorganic nanoparticles, wherein the inorganic nanoparticles have an alkyl group having 1 to 20 carbon atoms on the surface thereof. The multilayer laser marking film which is the surface modified particle which introduce | transduced is provided.
Description
A multilayer laser marking film.
Various articles have labels for unique identification functions. These labels contain a variety of information about the item and may also perform unique identification functions. Labels used in the automotive industry, for example, may be used to display information about various parts of a vehicle, such as tire pressure or fuel type, or to display unique security information such as, for example, chassis number and vehicle identification number. It is used. In case of theft or accident, these labels allow tracking of the vehicle. As one kind of method of manufacturing such a label, a method of writing information with a laser is used.
In addition, the self-recovering layer is scratch-resistant and self-resilient, and by coating various resin compositions on the surfaces of electrical and electronic home appliances, automobiles, high-grade musical instruments and furniture to form a coating film, mechanical, physical and chemical effects from the outside It protects the damage of the product and keeps long-term durability and reliability.
Therefore, scratches such as scratches due to scratches on the surface of the label significantly degrade the information and unique identification function of the article, and thus, a study on the improvement method using the self-recovering layer is necessary.
One embodiment of the present invention provides a multi-layer laser marking film capable of precise processing through a laser, including a self-restoration layer and improved scratch resistance.
In one embodiment of the invention, the adhesive layer; A colored base layer having a first color; A colored coating layer having a second color; And a self restoring layer, wherein the first color and the second color are different colors from each other, and the self restoring layer includes a photocurable urethane acrylate resin, a photocurable acrylate monomer, and inorganic nanoparticles. Comprising a cured product of the chemical composition, the inorganic nanoparticles provide a multilayer laser marking film which is surface-modified particles introduced with an alkyl group having 1 to 20 carbon atoms on the surface.
The multilayer laser marking film may have a laser marking property in which a colored coating layer is etched by laser irradiation and an etched portion is removed.
The photocurable urethane acrylate-based resin may include one selected from the group consisting of urethane silicone acrylate resin, urethane methacrylate resin, urethane acrylate resin, bisphenol F-urethane diacrylate, and combinations thereof.
The photocurable urethane acrylate-based resin may have a glass transition temperature of 10 ℃ to 30 ℃.
The photocurable acrylate monomers are methacrylate, acrylate, dipentaerythritol hexaacrylate, dicyclopentadiene acrylate, trimethylpropane triacrylate, glycidyl methacrylate, taerythritol triacrylate and these It may include one selected from the group consisting of a combination of.
The glass transition temperature (Tg) of the photocurable acrylate monomer may be about 35 ℃ to about 70 ℃.
The inorganic nanoparticles may include one selected from the group consisting of silica, alumina, zirconia, zeolite, titanium oxide, and combinations thereof.
The alkyl group having 1 to 20 carbon atoms includes one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, octyl acrylate, heptadecafluorodecyl acrylate, and combinations thereof. can do.
The photocurable composition may include 10 parts by weight to 20 parts by weight of the photocurable acrylate monomer and 5 parts by weight to 20 parts by weight of the inorganic nanoparticles based on 100 parts by weight of the photocurable urethane acrylate resin.
The photocurable composition further includes a fluorine-based compound, and the fluorine-based compound may include one selected from the group consisting of fluorinated acrylate, fluorinated methacrylate, fluorinated epoxy acrylate, and combinations thereof.
The photocurable composition may include 5 parts by weight or less of the fluorine compound based on 100 parts by weight of the photocurable urethane acrylate resin.
The photocurable composition may further include one selected from the group consisting of photoinitiators, stabilizers, steels, flame retardants, plasticizers, lubricants, dispersants, flow regulators, leveling agents, antifoaming agents, and combinations thereof.
The viscosity at 25 ° C. of the photocurable composition may be 1cp to 20cp.
The haze value of the self-healing layer may be 0.1% to 1%.
The thickness of the self restoring layer may be 5um to 30um.
The colored coating layer may include a photocurable product of a composition including a photocurable urethane acrylate resin and a pigment.
The multilayer laser marking film provides a multilayer laser marking film having an effect of preventing or restoring scratches caused by external friction.
Specifically, the multi-layer laser marking film is capable of precise processing through a laser, has a property that does not break when evaluating physical properties, and when applied to the actual article, it is suitable as a label film because it is excellent in preventing forgery and tampering In addition, even if scratches occur on the surface of the label due to physical deformation and friction, the surface is restored by the self-resilience of the self-recovery layer, so that scratch resistance and scratch resistance are improved.
1 is a schematic cross-sectional view of a multilayer laser marking film according to an embodiment of the present invention.
Advantages and features of the present invention, and methods for achieving the same will be apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms. The present embodiments are merely provided to make the disclosure of the present invention complete, and to fully convey the scope of the invention to those skilled in the art, and the present invention is defined by the scope of the claims. It will be. Like reference numerals refer to like elements throughout.
In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.
In addition, in this specification, when a part such as a layer, film, region, plate, or the like is said to be "on" or "upper" another part, it is not only when the other part is "right over" but also when there is another part in the middle. Also includes. On the contrary, when a part is "just above" another part, there is no other part in the middle. In addition, when a part such as a layer, a film, an area, or a plate is "below" or "below" another part, it is not only when the part is "below" but also another part in the middle. Include. In contrast, when a part is "just below" another part, there is no other part in the middle.
In one embodiment of the invention, the adhesive layer; A colored base layer having a first color; A colored coating layer having a second color; And a self restoring layer, wherein the first color and the second color are different colors from each other, and the self restoring layer includes a photocurable urethane acrylate resin, a photocurable acrylate monomer, and inorganic nanoparticles. Comprising a cured product of the chemical composition, the inorganic nanoparticles provide a multilayer laser marking film which is surface-modified particles introduced with an alkyl group having 1 to 20 carbon atoms on the surface.
1 schematically illustrates a multilayer
Referring to FIG. 1, the multilayer
The multilayer laser marking film may have a laser marking property in which a colored coating layer is etched by laser irradiation and an etched portion is removed. The multilayer laser marking film is a film which can be etched by a laser to write various information, and the 'laser marking' means to write information on the film by etching by a laser. For example, in the multilayer laser marking film, laser marking may be performed on the colored coating layer by passing through the transparent self restoring layer.
Specifically, the transparent self-restoring layer has no deterioration or damage and no deterioration in physical properties such as durability and visibility even if the laser transmits, thereby realizing optimized properties as the multilayer laser marking film.
In addition, when the colored substrate layer and the colored coating layer have different colors from each other, when the colored coating layer is etched by laser marking, the etched portion may exhibit various colors according to the etching depth.
The multilayer laser marking film can be written characters or patterns of various colors through the laser marking in this way. For example, the multilayer laser marking film may be used in automobiles, and specifically, may display information about various parts of the vehicle such as tire pressure or fuel type, or may provide unique security information such as chassis number and vehicle identification number. Can be used to indicate.
In addition, the multi-layered laser marking film includes a magnetic restoring layer having a self restoring property on the outermost surface while displaying information by laser marking, thereby simultaneously implementing excellent self restoring, scratch prevention and scratch resistance. The self-resilience means that the scratches are removed within a predetermined time after leaving scratches or the like on the self-restoring layer and returning to the original clean self-restoration layer.
In order to simultaneously realize the information transfer function by the laser marking while the multilayer laser marking film has a scratch prevention and a scratch resistance effect, excellent self adhesiveness and durability that the self-recovery layer does not peel off from the multilayer laser marking film are required. Such durability and adhesion improving effect can be implemented by controlling the photocurable composition for forming the self-recovering layer.
The self-healing layer may include a photocurable material of the photocurable composition, and the photocurable composition may include a photocurable urethane acrylate resin, a photocurable acrylate monomer, and inorganic nanoparticles.
The photocurable urethane acrylate-based resin may include one selected from the group consisting of urethane silicone acrylate resin, urethane methacrylate resin, urethane acrylate resin, bisphenol F-urethane diacrylate, and combinations thereof. The photocurable urethane acrylate-based resin may play a role of constituting the basic structure of the self-restored layer during photocuring.
For example, when the photocurable urethane acrylate-based resin contains urethane silicone acrylate, it forms a dense crosslinked structure during photocuring and maintains an appropriate surface hardness while improving chemical resistance, and self-recovering including silicone The effect is greatly improved.
The photocurable urethane acrylate resin may include a polyfunctional urethane acrylate resin. Specifically, the multifunctional urethane acrylate resin may include at least two functional groups, and for example, may include about 2 to 15 functional groups. By the polyfunctional urethane acrylate resin includes a functional group in the above range, it is possible to implement the effect of preventing the wrinkles and hardness of the surface. When the functional group of the multifunctional urethane acrylate-based resin is less than the above range, the effect of preventing wrinkles and improving hardness may be lowered. When the functional group of the polyfunctional urethane acrylate resin is more than the above range, surface wrinkles may occur.
delete
The photocurable urethane acrylate resin may have a glass transition temperature of about 10 ° C to about 30 ° C or less. Since the photocurable urethane acrylate-based resin maintains the glass transition temperature range, the magnetic restoring layer may have improved flexibility, and as a result, the self restoring effect may be greatly improved.
The photocurable composition may include the photocurable acrylate monomer, and the photocurable acrylate monomer may serve to adjust surface hardness.
Specifically, the photocurable acrylate monomer is methacrylate, acrylate, dipentaerythritol hexaacrylate, dicyclopentadiene acrylate, trimethylpropane triacrylate, glycidyl methacrylate, taerythritol triacrylate And combinations thereof.
By using the above-mentioned photocurable acrylate monomer, the hardness of the said self restoring layer can be improved significantly.
The glass transition temperature (Tg) of the photocurable acrylate monomer may be about 35 ℃ to about 70 ℃. By maintaining the glass transition temperature of the acrylate monomer in the above range, the hardness of the self-recovering layer can be improved.
The photocurable composition includes the inorganic nanoparticles. The inorganic nanoparticles refer to inorganic particles having a nano size, and are intended to prevent excellent hardness and wrinkles. The inorganic nanoparticles may be one selected from the group consisting of silica, alumina, zirconia, zeolite, titanium oxide, and combinations thereof, but is not limited thereto.
For example, when the inorganic nanoparticles are silica, it is economically advantageous and at the same time, excellent hardness and curl implementation of the self restoring layer are possible.
In addition, the inorganic nanoparticles may be surface modified particles having an alkyl group having 1 to 20 carbon atoms on the surface thereof.
When the inorganic nanoparticles are surface modified particles under the above conditions, the surface energy of the inorganic nanoparticles may be sufficiently lowered, and a relatively high level of hydrophobicity may be realized. Therefore, when the inorganic nanoparticles are surface modified particles having an alkyl group having 1 to 20 carbon atoms on the surface, the inorganic nanoparticles may be disposed between crosslinked structures in the composition to improve curl prevention and crosslinking density to achieve excellent hardness. Can be.
Specifically, the alkyl group having 1 to 20 carbon atoms is one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, octyl acrylate, heptadecafluorodecyl acrylate and combinations thereof It may include, but is not limited thereto.
The photocurable composition may include about 10 parts by weight to about 20 parts by weight of the photocurable acrylate monomer and about 5 parts by weight to about 20 parts by weight of the inorganic nanoparticles based on 100 parts by weight of the photocurable urethane acrylate resin. Can be.
Since the photocurable composition includes the photocurable acrylate monomer in the above weight part range, an appropriate surface hardness can be maintained even at a thin thickness. When the weight part of the photocurable acrylate monomer is more than the above range, the self-restoring performance can be reduced.
When the inorganic nanoparticles included in the photocurable composition are within the weight part range, it is possible to maximize the effect of reducing the occurrence of curls in the self-healing layer.
The photocurable composition may further include the fluorine-based compound, wherein the fluorine-based compound is a structure in which fluorine is substituted in a carbon-carbon main skeleton, and the fluorine-based compound is disposed near the surface of the self-restored layer to control slip property. It can play a role in preventing scratches.
Specifically, the fluorine-based compound may include one selected from the group consisting of fluorinated acrylate, fluorinated methacrylate, fluorinated epoxy acrylate, and combinations thereof, but is not limited thereto. By using the fluorine-based compound described above it is possible to maximize the resulting self-restoration performance by improving the slip properties of the self-restoration layer.
As described above, the photocurable composition includes a photocurable urethane acrylate-based resin, inorganic nanoparticles, and a fluorine compound, and may maximize the aforementioned effects by controlling the weight parts of the respective compositions.
The photocurable composition may include about 5 parts by weight or less of the fluorine compound based on 100 parts by weight of the photocurable urethane acrylate resin.
Since the photocurable composition includes a fluorine-based compound in the above weight part range, it is possible to maximize the self-restoring performance by maintaining appropriate slip property.
The photocurable composition may include photoinitiators, dyes, fillers, reinforcing agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers), mold release agents, antistatic agents, surfactants, dispersants, flow regulators, leveling agents, antifoaming agents, surfaces The modifier may further include one selected from the group consisting of a low stress agent (silicone oil), a silicone rubber, a heat resistance improver, and a combination thereof, but is not limited thereto.
The photocurable composition may have a viscosity of about 1cp to about 20cp at about 25 ℃. By maintaining the viscosity range of the photocurable composition, the workability at the time of manufacturing the self-recovering layer may be increased, and the time required for curing may be shortened.
Since the multilayer laser marking film has a function of transmitting unique information of a product described by laser marking, the self restoring layer should be clear and clear.
The haze value of the self-healing layer may be about 0.1% to about 1%. The self-healing layer maintains the haze value, thereby maintaining excellent cyanity of the multilayer laser marking film.
The thickness of the self restoring layer may be about 5um to about 30um. By maintaining the thickness range of the magnetic restoring layer, it is possible to simultaneously maintain an excellent laser marking efficiency and a self restoring effect and to realize an appropriate surface hardness. When the thickness of the self-recovery layer is less than the above range, mechanical properties and self-recovery effects may be lowered. When the thickness of the self-recovery layer is greater than the above range, the laser marking efficiency and the cyanity of the multilayer laser marking film may be reduced. Can be.
As described above, the self restoring layer may be formed on the colored coating layer, and since the self restoring layer is located on the outermost surface of the multilayer laser marking film, adhesion to the colored coating layer should be excellent for excellent durability.
Specifically, the self restoring layer should not be easily peeled from the colored coating layer by external impact or friction, and should have excellent adhesion at the interface between the self restoring layer and the colored coating layer. It can be implemented by controlling the composition with good compatibility with the self-recovering layer.
The colored coating layer may include a photocured product of a composition including a urethane acrylate-based resin and a pigment. The urethane acrylate resin may serve to provide a basic structure for forming the colored coating layer.
In addition, the urethane acrylate-based resin is excellent in interactivity with the photocurable urethane acrylate-based resin contained in the self-restored layer can be maximized the adhesion of the self-recovered layer to the colored coating layer is the self-restored layer Not only does it easily peel off, but also the interface adhesion to the colored coating layer can be improved.
The urethane acrylate resin may include one selected from the group consisting of urethane methacrylate resin, urethane acrylate resin, bisphenol F-urethane diacrylate, and combinations thereof.
The pigment may implement the color of the colored coating layer, it may be variously selected according to the color to be implemented.
For example, the pigment may include one selected from the group consisting of titanium dioxide (TiO 2 ), carbon black, and a combination thereof, but is not limited thereto.
The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.
< Example And Comparative example >
Example One
Forming a pressure-sensitive adhesive layer and a white colored substrate layer on one surface of a polyethylene terephthalate (PET) release film, and a colored coating layer composition comprising a urethane acrylate resin (Miwon, PU3200) and carbon black (Colombia Chemical, no.1200) After coating, photocuring and laminating a colored coating layer having a thickness of 3㎛.
Then, the components and contents shown in Table 1 below, and specifically, the inorganic nanoparticles are self-restored with a thickness of 20 μm by applying a photocurable composition, which is a surface-modified particle having methyl methacrylate introduced thereon, and photocuring the surface. The layers were laminated.
Comparative example One
Forming a pressure-sensitive adhesive layer and a white colored substrate layer on one surface of a polyethylene terephthalate (PET) release film, and a colored coating layer composition comprising a urethane acrylate resin (Miwon, PU3200) and carbon black (Colombia Chemical, no.1200) After coating, photocuring and laminating a colored coating layer having a thickness of 3㎛.
Comparative example 2
Forming a pressure-sensitive adhesive layer and a white colored substrate layer on one surface of a polyethylene terephthalate (PET) release film, and a colored coating layer composition comprising a urethane acrylate resin (Miwon, PU3200) and carbon black (Colombia Chemical, no.1200) After coating, photocuring and laminating a colored coating layer having a thickness of 3㎛.
Then, the photocurable composition was applied to the components and contents shown in Table 1 below and photocured to laminate a self-healing layer having a thickness of 20 μm.
Comparative example 3
Forming a pressure-sensitive adhesive layer and a white colored substrate layer on one surface of a polyethylene terephthalate (PET) release film, and a colored coating layer composition comprising a urethane acrylate resin (Miwon, PU3200) and carbon black (Colombia Chemical, no.1200) After coating, photocuring and laminating a colored coating layer having a thickness of 3㎛.
Then, the components and contents shown in Table 1 below, and specifically, the inorganic nanoparticles were coated with a photocurable composition that was not surface-modified and photocured to laminate a self-healing layer having a thickness of 20 μm.
[Parts by weight]
(Taerythritol triacrylate, PETIA)
[Parts by weight]
Fluoroacrylate
, DIC, RS-75)
[Parts by weight]
(BASF, IRG 184)
[Parts by weight]
<Evaluation>
Experimental Example 1: Self-resilience measurement
For the multilayer laser marking films of Examples and Comparative Examples, a time was measured after recovering the scratch on the outermost surface of the multilayer laser marking film with a brass brush using a video recorder, and the results are shown in Table 2 below. Indicated.
Experimental Example 4: Curling test
After cutting the multilayer laser marking films of the Examples and Comparative Examples to a length of 10 cm in length and length, and then to measure the height of the vertex of the rectangle and to report the highest value of the measured four values as the curling (curling) value is shown in Table 2 It was.
Experimental Example 4: pencil hardness test
The hardness of the pencil hardness tester manufactured by Toyoseki by the test method of ASTM D3502 is shown in Table 1 below. A total of five experiments were performed with the pencil hardness meter, and the number of times the scratches were not visible to the naked eye compared to the total number of experiments was measured.
(mm)
The multilayer laser marking film prepared according to Example 1 may implement excellent self-resilience, interlayer adhesion, surface hardness and at the same time effective anti-curling property.
In particular, it is excellent in anti-curling, it is possible to maintain a smooth surface of the laser marking film, it can be seen that the laser marking film can maximize the visibility.
On the other hand, Comparative Example 1 does not include the self-recovery layer, it can be confirmed that no restoration is made when an external scratch or impact is applied. In addition, Comparative Example 2 does not include the inorganic nanoparticles, the curling occurs significantly, so that the function can be reduced as a laser marking film, Comparative Example 3 includes inorganic nanoparticles without surface modification, curling is Example 1 It can be seen that the role may be lowered as a laser marking film occurs more.
100: multilayer laser marking film
110: adhesive layer
120: colored substrate layer
130: colored coating layer
140: self-healing
Claims (16)
The self-healing layer includes a cured product of a photocurable composition comprising a photocurable urethane acrylate resin, a photocurable acrylate monomer and inorganic nanoparticles,
The photocurable composition comprises 10 parts by weight to 20 parts by weight of the photocurable acrylate monomer and 5 parts by weight to 20 parts by weight of the inorganic nanoparticles based on 100 parts by weight of the photocurable urethane acrylate resin,
The inorganic nanoparticles are surface modified particles having an alkyl group having 1 to 20 carbon atoms on its surface.
Multilayer Laser Marking Film.
The colored coating layer is etched by laser irradiation, and the laser marking property that the etched portion is removed
Multilayer Laser Marking Film.
The photocurable urethane acrylate resin includes one selected from the group consisting of urethane silicone acrylate resin, urethane methacrylate resin, urethane acrylate resin, bisphenol F-urethane diacrylate, and combinations thereof
Multilayer Laser Marking Film.
The photocurable urethane acrylate resin has a glass transition temperature of 10 ℃ to 30 ℃
Multilayer Laser Marking Film.
The photocurable acrylate monomers include methacrylate, acrylate, dipentaerythritol hexaacrylate, dicyclopentadiene acrylate, trimethylpropane triacrylate, glycidyl methacrylate, taerythritol triacrylate and these Containing one selected from the group consisting of
Multilayer Laser Marking Film.
The glass transition temperature (Tg) of the photocurable acrylate monomer is 35 ℃ to 70 ℃
Multilayer Laser Marking Film.
The inorganic nanoparticles include one selected from the group consisting of silica, alumina, zirconia, zeolite, titanium oxide, and combinations thereof.
Multilayer Laser Marking Film.
The alkyl group having 1 to 20 carbon atoms includes one selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, octyl acrylate, heptadecafluorodecyl acrylate, and combinations thereof. doing
Multilayer Laser Marking Film.
The photocurable composition further comprises a fluorine-based compound,
The fluorine-based compound includes one selected from the group consisting of fluorinated acrylate, fluorinated methacrylate, fluorinated epoxy acrylate, and combinations thereof
Multilayer Laser Marking Film.
The photocurable composition may include 5 parts by weight or less of the fluorine compound based on 100 parts by weight of the photocurable urethane acrylate resin.
Multilayer Laser Marking Film.
The photocurable composition further comprises one selected from the group consisting of photoinitiators, stabilizers, steels, flame retardants, plasticizers, lubricants, dispersants, flow regulators, leveling agents, antifoaming agents, and combinations thereof.
Multilayer Laser Marking Film.
The viscosity of 1cp to 20cp at 25 ° C of the photocurable composition
Multilayer Laser Marking Film.
Haze value of the self-healing layer is 0.1% to 1%
Multilayer Laser Marking Film.
The thickness of the self restoring layer is 5um to 30um
Multilayer Laser Marking Film.
The colored coating layer comprises a photocurable composition of the composition comprising a photocurable urethane acrylate resin and a pigment
Multilayer Laser Marking Film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101470462B1 (en) | 2011-02-14 | 2014-12-08 | 주식회사 엘지화학 | Uv curable coating composition having self-healing property, coating film, and preparation method of coating film |
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| US5688573A (en) * | 1991-12-18 | 1997-11-18 | Minnesota Mining And Manufacturing Company | Halogen-free acrylic urethane sheet material |
| US6573011B1 (en) * | 2001-12-21 | 2003-06-03 | Eastman Kodak Company | Label with curl and moisture resistant protective layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101470462B1 (en) | 2011-02-14 | 2014-12-08 | 주식회사 엘지화학 | Uv curable coating composition having self-healing property, coating film, and preparation method of coating film |
Non-Patent Citations (1)
| Title |
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| 'Self-healing polymeric materials', Y. Yang 등, Chem. Soc. Rev., 2013, 42, 7446-7467 |
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| KR20170105669A (en) | 2017-09-20 |
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