KR102153287B1 - Multilayer marking film - Google Patents

Abstract

The present specification relates to a multilayer marking film.

Description

Multilayer Marking Film {MULTILAYER MARKING FILM}

The present invention relates to a multilayer marking film.

Various articles have labels for their unique identification function. These labels contain a variety of information about the item and also perform a unique identification function. Labels used in the automotive industry, for example, to display information about various parts of the vehicle, such as tire pressure or fuel type, or to display unique security information such as, for example, vehicle identification numbers and vehicle identification numbers. Is being used. In the case of theft or accident, these labels enable the vehicle to be tracked.

As a type of method for manufacturing such a label, information can be written using a light irradiation means such as a laser. The laser is a high-power light source and is easily used for machining. For example, Korean Patent Laid-Open Publication No. 10-2006-0027501 has an adhesive label sheet capable of marking a large amount of barcodes in a short time using a laser. Japanese Patent Application Laid-Open No. 1990-120042 discloses a heat-resistant display material having a marked layer on which an etching pattern is formed by a laser beam on a heat-resistant base layer.

In order for such a label to be used for anti-theft, it is necessary to retain the friability of being shredded when the label is detached after a certain period of time has elapsed from the time the label is attached. In addition, excellent long-term reliability, cold resistance, and adhesion are required for an adhesive for attaching a label to an adherend. However, in the case of securing long-term reliability of the conventional pressure-sensitive adhesive, cold resistance and adhesion are deteriorated, and in the case of securing cold resistance and adhesion, long-term reliability is deteriorated. Therefore, even after the label is attached to the adherend, research on an adhesive having excellent long-term reliability, cold resistance, and adhesion is required.

The present invention relates to a multilayer marking film.

An embodiment of the present invention is an adhesive layer; A colored substrate layer having a first color; And a colored coating layer having a second color, wherein the first color and the second color are different colors, the colored coating layer, the colored base layer, and the adhesive layer are sequentially provided, and the adhesive layer includes an adhesive material. A first monomer comprising a thermosetting product of the pressure-sensitive adhesive composition, wherein the pressure-sensitive adhesive material includes a (meth)acrylate having a linear or branched alkyl group having 4 or more and 20 or less carbon atoms; Including one or more selected from the group consisting of (meth)acrylate having a straight or branched chain alkyl group having 1 to 3 carbon atoms, (meth)acrylate having an epoxy group, and (meth)acrylate having an alicyclic alkyl group A second monomer; And a third monomer comprising a (meth)acrylate having a polar functional group; and a weight average molecular weight of the polymer is 500,000 g/mol or more and 800,000 g/mol or less, and the colored coating layer is irradiated with laser. It provides a multi-layered marking film that is etched.

According to an embodiment of the present invention, theft, forgery, and tampering may be prevented due to excellent crushability.

According to an embodiment of the present invention, an adhesive layer for attaching the multilayer marking film to an adherend may implement excellent long-term reliability, cold resistance, and adhesion.

1 is a schematic view showing a multilayer marking film according to an embodiment of the present invention.
2A and 2B are views schematically showing a multilayer marking film on which marking by laser irradiation is performed according to an embodiment of the present invention.

When a member is referred to herein as being “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members. In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In addition, in the present invention, "(meth)acrylate" is used as a collective term for acrylate and methacrylate.

Hereinafter, the present specification will be described in more detail.

An embodiment of the present invention is an adhesive layer; A colored substrate layer having a first color; And a colored coating layer having a second color, wherein the first color and the second color are different colors, the colored coating layer, the colored base layer, and the adhesive layer are sequentially provided, and the adhesive layer includes an adhesive material. A first monomer comprising a thermosetting product of the pressure-sensitive adhesive composition, wherein the pressure-sensitive adhesive material includes a (meth)acrylate having a linear or branched alkyl group having 4 or more and 20 or less carbon atoms; Including one or more selected from the group consisting of (meth)acrylate having a straight or branched chain alkyl group having 1 to 3 carbon atoms, (meth)acrylate having an epoxy group, and (meth)acrylate having an alicyclic alkyl group A second monomer; And a third monomer comprising a (meth)acrylate having a polar functional group; and a weight average molecular weight of the polymer is 500,000 g/mol or more and 800,000 g/mol or less, and the colored coating layer is irradiated with laser. It provides a multi-layered marking film that is etched.

According to an embodiment of the present invention, an adhesive layer for attaching the multilayer marking film to an adherend may implement excellent long-term reliability, cold resistance, and adhesion.

1 is a schematic view showing a multilayer marking film according to an embodiment of the present invention. Referring to FIG. 1, a multilayer marking film 100 according to an embodiment of the present invention includes an adhesive layer 10, a colored substrate layer 20 and a colored coating layer 30, and the colored coating layer 30, The colored substrate layer 20 and the adhesive layer 10 are sequentially provided. Specifically, the colored base layer 20 may be provided under the colored coating layer 30, and the adhesive layer 10 may be provided under the colored base layer 20.

According to an embodiment of the present invention, the colored coating layer may be etched by laser irradiation, and may have a marking property by laser irradiation in which the etched portion is removed. The multilayer marking film is a film in which various information can be written through laser irradiation, and'marking' means writing information on the film by etching by laser irradiation. Specifically, marking by laser irradiation may be performed on the colored coating layer included in the multilayer marking film. Specifically, the laser-irradiated portion of the colored coating layer is etched and removed, and at the same time, it is possible to write various letters and designs by interacting with the colored substrate layer.

According to an embodiment of the present invention, a fiber laser using an optical fiber as a resonator, a carbon dioxide laser (CO ₂ laser) or the like may be used as a laser for etching the colored coating layer. In addition, the colored coating layer may be etched by a laser having a wavelength value of 900 nm or more and 1,100 nm or less. Specifically, a laser having a wavelength value of 900 nm or more and 1,100 nm or less and an average power of 10 W or more and 50 W or less is irradiated to the colored coating layer at a draw speed of 100 mm/s or more and 4,000 mm/s or less. I can. By irradiating the colored coating layer with the laser under the above-described conditions, the colored coating layer can be easily etched.

2A and 2B are views schematically showing a multilayer marking film on which marking by laser irradiation is performed according to an embodiment of the present invention.

As shown in FIG. 2A, marking by laser may be performed as much as the thickness of the colored coating layer 30, and marking by laser may be performed on a part of the thickness of the colored coating layer 30 as shown in FIG. 2B.

According to an embodiment of the present invention, the colored substrate layer and the colored coating layer are both layers having a color, and the meaning of'colored' means that the substrate layer or the coating layer is not transparent, and colors such as white, black, blue, etc. To have. Specifically, the colored substrate layer has a first color, the colored coating layer has a second color, and the first color and the second color are different colors.

When the colored substrate layer and the colored coating layer have different colors from each other and the colored coating layer is etched through a laser, various colors may be displayed according to the etching depth of the etched portion.

Referring to FIG. 2A, when etching using a laser as much as the thickness of the colored coating layer 30, the user visually perceives only the first color of the colored base layer 20 with respect to the etched portion of the colored coating layer 30. can do. In addition, as shown in FIG. 2B, when a part of the thickness of the colored coating layer 30 is etched with a laser, the user does not etch with the first color of the colored substrate layer 20 with respect to the portion where the colored coating layer 30 is etched. The color expressed by overlapping the second color of the remaining colored coating layer 30 can be visually recognized. Accordingly, a color that can be perceived by a user may be adjusted according to the thickness at which the colored coating layer 30 is etched.

According to an embodiment of the present invention, in the multilayer marking film, it is possible to write characters or designs of various colors by laser irradiation on the colored coating layer. Specifically, the multilayer marking film may be used for automobiles, and the colored coating layer is laser irradiated to display information on various parts of the vehicle such as tire pressure or fuel type, or unique vehicle identification number and vehicle identification number. Security information can be displayed.

When important information is written on the multilayer marking film, it is necessary to prevent forgery or falsification thereof. Specifically, the multilayer marking film may have'crushability'. 'Freshability' means physical properties that cannot be recycled because the original shape is destroyed when an attempt is made to detach or remove the multilayer marking film after it is attached to an adherend. Accordingly, according to an embodiment of the present invention, since the multilayer marking film has crushability, unique information written on the multilayer marking film cannot be arbitrarily changed, and characteristics that cannot be forged or altered can be secured.

According to an embodiment of the present invention, by controlling the composition of the pressure-sensitive adhesive composition, it is possible to implement an adhesive layer having excellent long-term reliability, cold resistance, and adhesion.

According to an embodiment of the present invention, the pressure-sensitive adhesive composition includes an adhesive material, and the adhesive material may include a polymer of a first monomer, a second monomer, and a third monomer. In addition, the weight average molecular weight of the polymer may be 500,000 g/mol or more and 800,000 g/mol or less.

Specifically, the weight average molecular weight of the polymer may be 550,000 g/mol or more and 750,000 g/mol or less, 550,000 g/mol or more and 600,000 g/mol or less, and 650,000 g/mol or more and 700,000 g/mol or less. By controlling the weight average molecular weight of the polymer within the above-described range, it is possible to prevent deterioration of the adhesion and long-term reliability of the adhesive layer, and easily implement the crushability characteristics of the multilayer marking film.

When the weight average molecular weight of the polymer included in the pressure-sensitive adhesive composition is less than 500,000 g/mol, a problem of deteriorating the long-term reliability of the pressure-sensitive adhesive layer may occur. In addition, when the weight average molecular weight of the polymer exceeds 800,000 g/mol, the adhesiveness of the adhesive layer may decrease.

According to an embodiment of the present invention, the glass transition temperature of the thermosetting product of the pressure-sensitive adhesive composition may be -30 °C or more and -10 °C or less. Specifically, the glass transition temperature of the thermosetting product of the pressure-sensitive adhesive composition may be -25°C or more and -15°C or less. The pressure-sensitive adhesive layer including the thermosetting product of the pressure-sensitive adhesive composition having a glass transition temperature in the above-described range may have excellent cold resistance. When the glass transition temperature of the thermosetting product of the adhesive composition is less than -30 °C, the durability of the adhesive layer may be deteriorated, resulting in a problem of lowering reliability at a high temperature of room temperature or higher. When the glass transition temperature exceeds -10 °C There may be a problem in that the cold resistance of the adhesive layer is deteriorated, making it difficult to attach the adhesive layer to the adherend under low temperature conditions.

According to an embodiment of the present invention, the adhesive material may include a first monomer comprising a (meth)acrylate having a straight or branched alkyl group having 4 to 20 carbon atoms; Including one or more selected from the group consisting of (meth)acrylate having a straight or branched chain alkyl group having 1 to 3 carbon atoms, (meth)acrylate having an epoxy group, and (meth)acrylate having an alicyclic alkyl group A second monomer; And a third monomer including a (meth)acrylate having a polar functional group.

According to an embodiment of the present invention, the adhesive layer formed by using the adhesive composition including the adhesive material containing the second monomer can secure excellent cold resistance, adhesion, and long-term reliability.

According to an embodiment of the present invention, the adhesive material may be formed of a polymer of a first monomer, a second monomer, and a third monomer. The first monomer may be used as a base material for the adhesive material.

The first monomer includes a (meth)acrylate having a linear or branched alkyl group having 4 or more and 20 or less carbon atoms. Specifically, the (meth)acrylate having a straight-chain or branched-chain alkyl group having 4 to 20 carbon atoms is n-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl ( Meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, iso It may include at least one selected from the group consisting of nonyl (meth) acrylate, lauryl (meth) acrylate, and tetradecyl (meth) acrylate.

According to an embodiment of the present invention, the content of the first monomer may be 60 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. A polymer of the first monomer, the second monomer, and the third monomer may be included in the pressure-sensitive adhesive composition, and in addition to the polymerized material, a liquid such as a solvent may be included in the pressure-sensitive adhesive composition. In the present invention, the solid content of the pressure-sensitive adhesive composition may refer to a pressure-sensitive adhesive material including a polymer of the first monomer, the second monomer, and the third monomer, and the weight of the solid content of the pressure-sensitive adhesive composition is the first monomer, the second It may be substantially the same as the weight of the polymer of the monomer and the third monomer. In addition, the solid content of the pressure-sensitive adhesive composition may mean excluding a liquid such as a solvent contained in the pressure-sensitive adhesive composition.

Specifically, the content of the first monomer may be 65 parts by weight or more and 75 parts by weight or less, based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. By adjusting the content of the first monomer within the above-described range, durability of the adhesive layer and adhesion to an adherend may be improved.

According to an embodiment of the present invention, the third monomer includes a (meth)acrylate having a polar functional group. The polar functional group may be a hydroxy group, a carboxyl group, or an amino group. Specifically, the third monomer includes a (meth)acrylate having a carboxyl group among the polar functional groups, thereby improving the adhesion and cohesiveness of the adhesive layer, and further improving the long-term reliability of the adhesive layer.

Specifically, the (meth)acrylate having a carboxyl group may include at least one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and cinnamic acid.

According to an embodiment of the present invention, the content of the third monomer may be 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. Specifically, the content of the third monomer may be 5 parts by weight or more and 8 parts by weight or less, based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. By adjusting the content of the third monomer within the above-described range, adhesion of the adhesive layer to the adherend can be improved, and interfacial adhesion between the adhesive layer and the colored substrate layer can be effectively maintained.

According to an embodiment of the present invention, by including the second monomer in the adhesive material, cold resistance, adhesion, and long-term reliability of the adhesive layer may be improved. In addition, excellent interfacial adhesion between the adhesive layer and the colored substrate layer may be implemented.

According to an embodiment of the present invention, the content of the second monomer may be 15 parts by weight or more and 35 parts by weight or less based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. Specifically, the content of the second monomer may be 20 parts by weight or more and 30 parts by weight or less, based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. By adjusting the content of the second monomer within the above-described range, cold resistance, adhesion, and long-term reliability of the adhesive layer may be improved.

According to an embodiment of the present invention, the second monomer is methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobornyl acrylate, glycidyl methacrylate. It may include one or more selected from the group consisting of acrylate, isobornyl methacrylate, benzyl acrylate, cyclohexyl acrylate, and 1-hexadecyl methacrylate. The second monomer is selected from the group consisting of (meth)acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms, (meth)acrylate having an epoxy group, and (meth)acrylate having an alicyclic alkyl group. Includes one or more.

Specifically, the (meth)acrylate having a straight or branched chain alkyl group having 1 to 3 carbon atoms is methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and isopropyl methacrylate. It may include one or more selected from the group consisting of a rate. In addition, glycidyl methacrylate may be used as the (meth)acrylate having an epoxy group, and the (meth)acrylate having an alicyclic alkyl group is a group consisting of isobornyl acrylate and isobornyl methacrylate. It may include at least one selected.

According to an embodiment of the present invention, a polymer having a weight average molecular weight of 500,000 g/mol or more and 800,000 g/mol or less is easily prepared by adjusting the content of the first monomer, the second monomer, and the third monomer within the above range. Can be manufactured.

According to an embodiment of the present invention, the adhesive layer includes a thermosetting product of the adhesive composition. By thermally curing the pressure-sensitive adhesive composition, a cured product of a higher molecular weight pressure-sensitive adhesive composition can be easily prepared.

According to an embodiment of the present invention, the pressure-sensitive adhesive composition further includes a curing agent, and the content of the curing agent may be 0.01 parts by weight or more and 1 part by weight or less based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. A thermal curing agent may be used as the curing agent, and specifically, the curing agent may include at least one selected from the group consisting of an aziridine-based curing agent, a peroxide-based curing agent, and an isocyanate-based curing agent. By adjusting the content of the curing agent in the above-described range, the weight average molecular weight of the polymer contained in the pressure-sensitive adhesive composition can be easily controlled to 500,000 g/mol or more and 800,000 g/mol or less.

According to an embodiment of the present invention, the pressure-sensitive adhesive composition may include a solvent and a tackifier. The solvent may include at least one selected from the group consisting of toluene, acetone, ethyl acetate, and methyl ethyl ketone. By controlling the amount of the solvent contained in the pressure-sensitive adhesive composition, the viscosity of the pressure-sensitive adhesive composition may be controlled to improve coating properties and processability.

According to an embodiment of the present invention, the pressure-sensitive adhesive composition may have a viscosity of 1,000 cps or more and 5,000 cps or less at 25° C. or more and 30° C. or less. Specifically, the viscosity of the pressure-sensitive adhesive composition may be 1,500 cps or more and 3,000 cps or less at 25° C. or more and 30° C. or less. By controlling the viscosity of the pressure-sensitive adhesive composition within the above range, it is possible to improve the coatability and processability of the pressure-sensitive adhesive composition.

According to an embodiment of the present invention, the pressure-sensitive adhesive composition may further include a tackifier. By adding the tackifier to the pressure-sensitive adhesive composition, the adhesion of the pressure-sensitive adhesive layer to an adherend can be improved. Specifically, the tackifier includes at least one selected from the group consisting of rosin-based resins, terpene-based resins, terpenephenol-based resins, coumarone-indene-based resins, styrene-based resins, xylene-based resins, phenolic resins, and petroleum resins. can do.

According to an embodiment of the present invention, the content of the tackifier may be 1 part by weight or more and 20 parts by weight or less based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. By adjusting the content of the tackifier in the above-described range, the adhesion of the adhesive layer can be effectively improved.

According to an embodiment of the present invention, the colored base layer may include a cured product of a base composition including a urethane (meth)acrylate oligomer, a (meth)acrylate monomer, and a pigment.

According to an embodiment of the present invention, the urethane (meth)acrylate oligomer is an oligomer including a urethane structure (-CONH-) in a chemical structure, and the weight average molecular weight may be easily adjusted. In addition, the base composition includes the urethane (meth)acrylate oligomer, thereby improving the crushability of the multilayer marking film and controlling elongation, and the colored base layer and the upper and lower adhesive layers and colored It may be advantageous to secure excellent interfacial adhesion between coating layers.

According to an embodiment of the present invention, the urethane (meth)acrylate oligomer includes an isocyanate compound containing 3 or more and 6 or less isocyanate groups, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc. It can be obtained from a compound containing a hydroxy group and an acrylate group.

According to an embodiment of the present invention, the weight average molecular weight of the urethane (meth)acrylate oligomer may be 2,000 g/mol or more and 10,000 g/mol or less. Specifically, the weight average molecular weight of the urethane (meth)acrylate oligomer may be 2,500 g/mol or more and 8,000 g/mol or less, and 4,000 g/mol or more and 7,500 g/mol or less. By using a urethane (meth)acrylate oligomer having a weight average molecular weight of 2,000 g/mol or more and 10,000 g/mol or less, the cured product of the base composition including the urethane (meth)acrylate oligomer may have a dense cured structure, It is possible to secure excellent interfacial adhesion between the colored substrate layer, the adhesive layer, and the colored coating layer. In addition, by controlling the weight average molecular weight of the urethane (meth)acrylate oligomer, it is possible to control the crushability, tensile strength and elongation of the colored substrate layer including the cured product of the substrate composition. Mechanical properties can be effectively controlled.

According to an embodiment of the present invention, the urethane (meth)acrylate oligomer may include 3 or more and 6 or less (meth)acrylate groups. Specifically, the urethane (meth)acrylate oligomer is a trifunctional urethane (meth)acrylate oligomer containing three (meth)acrylate groups or a tetrafunctional urethane (meth)acrylate containing four (meth)acrylate groups Oligomer; A 5-functional urethane (meth)acrylate oligomer containing five (meth)acrylate groups or a six-functional urethane (meth)acrylate oligomer containing six (meth)acrylate groups; Or it may include a mixture of all of them.

The trifunctional urethane (meth)acrylate oligomer or the tetrafunctional urethane (meth)acrylate oligomer undergoes a curing reaction with the (meth)acrylate monomer to impart excellent friability to the colored substrate layer. In addition, the 5-functional urethane (meth)acrylate oligomer or the six-functional urethane (meth)acrylate oligomer undergoes a curing reaction in the oligomer itself, thereby imparting excellent crushability and mechanical properties to the colored substrate layer.

According to an embodiment of the present invention, the (meth)acrylate monomer is an alicyclic (meth)acrylate monomer, an epoxy (meth)acrylate monomer, a chain aliphatic (meth)acrylate monomer, and a polyol-based (meth)acrylate monomer. ) It may include at least one monomer selected from the group consisting of acrylate monomers. When the (meth)acrylate monomer includes a monomer having a chemical structure of the above-described kind, it interacts with the urethane (meth)acrylate oligomer, thereby greatly improving the crushability of the multilayer marking film.

According to an embodiment of the present invention, the molecular weight of the (meth)acrylate monomer included in the base composition may be 200 g/mol or more and 500 g/mol or less. Specifically, the molecular weight of the (meth)acrylate monomer may be 200 g/mol or more and 400 g/mol or less. The (meth)acrylate monomer includes at least one of an alicyclic (meth)acrylate monomer, an epoxy-based (meth)acrylate monomer, a chain aliphatic (meth)acrylate monomer, and a polyol-based (meth)acrylate monomer. Each of the monomers included in the (meth)acrylate monomer may independently have a molecular weight of 200 g/mol or more and 500 g/mol or less. For example, when the (meth)acrylate monomer includes an alicyclic (meth)acrylate monomer and a chain aliphatic (meth)acrylate monomer, the alicyclic (meth)acrylate monomer and a chain aliphatic monomer The molecular weight of each of the (meth)acrylate monomers may be 200 g/mol or more and 500 g/mol or less.

According to an embodiment of the present invention, a (meth)acrylate monomer having a molecular weight of 200 g/mol or more and 500 g/mol or less is crosslinked through a curing reaction between the urethane (meth)acrylate oligomers serving as a matrix. As a result, it is possible to implement a colored substrate layer having a high density and high hardness.

According to an embodiment of the present invention, the (meth)acrylate monomer may include 2 or more and 4 or less (meth)acrylate groups. The (meth)acrylate monomer includes at least one of an alicyclic (meth)acrylate monomer, an epoxy-based (meth)acrylate monomer, a chain aliphatic (meth)acrylate monomer, and a polyol-based (meth)acrylate monomer. Each of the monomers included in the (meth)acrylate monomer may independently include 2 or more and 4 or less (meth)acrylate groups. In addition, the (meth)acrylate group included in the monomer may be a photoreactive functional group.

According to an embodiment of the present invention, a (meth)acrylate monomer containing 2 or more and 4 or less (meth)acrylate groups is cured together with the urethane (meth)acrylate oligomer, effectively improving the crushability of the colored substrate layer. I can make it.

According to an embodiment of the present invention, the alicyclic (meth)acrylate monomer may mean a (meth)acrylate monomer including a cyclic hydrocarbon in an aliphatic hydrocarbon. Specifically, the alicyclic (cyclo-aliphatic)-based (meth)acrylate monomer may include at least one substituent of a cycloalkyl group having 3 or more and 25 or less carbon atoms and a heterocycloalkyl group having 2 or more and 25 or less carbon atoms. The heterocycloalkyl group having 2 or more and 25 or less carbon atoms may include at least one heteroelement of nitrogen, sulfur, and oxygen. By using an alicyclic (meth)acrylate monomer containing a heterocycloalkyl group, the crushability of the colored substrate layer can be further improved. In addition, the base composition may increase the curing reaction rate of the base composition by including an alicyclic (meth)acrylate monomer containing the heterocycloalkyl group.

Specifically, the alicyclic (cyclo-aliphatic)-based (meth)acrylate monomer may include at least one of cyclohexanedimethanol diacrylate, tricyclodecanedimethanol diacrylate, and adamantanediol diacrylate. I can.

According to an embodiment of the present invention, the epoxy-based (meth)acrylate monomer is a novolac type epoxy (meth)acrylate, a bisphenol-A type epoxy (meth)acrylate, a bisphenol-S type Including at least one selected from the group consisting of epoxy (meth)acrylate, bisphenol-F type epoxy (meth)acrylate, phenol type epoxy (meth)acrylate, and cresol novolac type epoxy (meth)acrylate. I can.

According to an embodiment of the present invention, the chain aliphatic (meth)acrylate monomer may mean a (meth)acrylate monomer that does not include a cyclic hydrocarbon in the aliphatic hydrocarbon and includes a chain hydrocarbon. Specifically, the chain-type aliphatic (meth)acrylate monomer may be a compound having (meth)acrylate groups at both ends of the main chain consisting of an alkylene structural unit having 1 to 16 carbon atoms. More specifically, the chain-type aliphatic (meth)acrylate monomer is 1,6-hexanedioldi(meth)acrylate, 1,3-butanedioldi(meth)acrylate, and 1,4-butanedioldi It may include at least one selected from the group consisting of (meth)acrylate.

According to an embodiment of the present invention, the polyol-based (meth)acrylate monomer is 1,6-hexanediol (ethoxylate) diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene It may include at least one selected from the group consisting of glycol diacrylate and tetraethylene glycol diacrylate.

According to an embodiment of the present invention, by adjusting the number of functional groups and the weight average molecular weight of the urethane (meth)acrylate oligomer and the number of functional groups and molecular weight of the (meth)acrylate monomer to an appropriate range, the crushability of the multilayer marking film And mechanical properties such as tensile strength and elongation can be improved.

According to an embodiment of the present invention, the content of the (meth)acrylate monomer may be greater than 0 parts by weight and less than 66 parts by weight based on 100 parts by weight of the urethane (meth)acrylate oligomer. Specifically, the content of the (meth)acrylate monomer is 5 parts by weight or more and 40 parts by weight or less, 5 parts by weight or more and 30 parts by weight or less, 25 parts by weight or more, based on 100 parts by weight of the urethane (meth)acrylate oligomer. It may be less than or equal to parts by weight.

According to an embodiment of the present invention, by using the (meth)acrylate monomer in an amount in the above-described range, the colored base layer may have excellent crushability, and the hardness of the cured product of the base composition and By improving the elongation, it is possible to form a colored substrate layer with improved durability and workability.

Therefore, according to an embodiment of the present invention, by adjusting the content of the (meth)acrylate monomer, by improving the crushability, durability and workability of the multilayer marking film, it is applied to various types of adherends, While performing the identification function, the theft and counterfeiting prevention functions can be performed.

According to an embodiment of the present invention, the base composition includes a pigment as a component for imparting color to the colored base layer. The kind of the pigment is not particularly limited, and various pigments may be used alone or appropriately mixed according to the color of the colored substrate layer.

According to an embodiment of the present invention, the pigment is titanium dioxide (TiO ₂ ), carbon black, iron stone, azo pigment, cobalt violet, cadmium sulfide, chromium ferrocyanide, silicate, It may include one selected from the group consisting of phosphate, phthalocyanine-based compounds, dioxazine compounds, and combinations thereof, but is not limited thereto.

According to an embodiment of the present invention, the content of the pigment may be 50 parts by weight or more and 135 parts by weight or less based on 100 parts by weight of the urethane (meth)acrylate oligomer. Specifically, the content of the pigment may be 70 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the urethane (meth)acrylate oligomer.

When the content of the pigment is less than 50 parts by weight based on 100 parts by weight of the urethane (meth)acrylate oligomer, the effect may be reduced in terms of color contrast with the colored coating layer, and the crushability of the colored substrate layer may be reduced. Problems can arise. In addition, when the content of the pigment exceeds 135 parts by weight, the reaction efficiency of the curing process of the base composition may be reduced, and the colored base layer may interfere with securing appropriate interfacial adhesion and crushability.

Therefore, according to an embodiment of the present invention, by adjusting the content of the pigment contained in the base composition to 50 parts by weight or more and 135 parts by weight or less based on 100 parts by weight of the urethane (meth) acrylate oligomer, Without deteriorating mechanical properties, the color of the colored substrate layer can be effectively expressed.

According to an embodiment of the present invention, the base composition may be cured by an electron beam or ultraviolet light. That is, the cured product of the base composition may be an electron beam cured product or an ultraviolet cured product. When the substrate composition is cured using heat or other curing means, curing proceeds slowly with little energy, so that the crushability of the colored substrate layer is lowered and the elongation becomes too large, resulting in a problem that the desired physical properties cannot be realized. Can be. On the other hand, according to an embodiment of the present invention, by curing the base composition using an electron beam or ultraviolet rays capable of instantaneously applying a lot of energy, the crushability of the colored base layer to be prepared may be easily secured.

According to an embodiment of the present invention, when the base composition is cured by ultraviolet rays, the base composition may further include a photoinitiator. A material known as the photoinitiator may be used, and there is no limitation as long as it is a material capable of initiating photocuring of the base composition by irradiation with ultraviolet rays. On the other hand, when the base composition is cured by an electron beam, a separate photoinitiator may not be added to the base composition.

According to an embodiment of the present invention, the base composition may be cured using an electron beam having an energy of 20 kGy or more and 80 kGy or less. In addition, the base composition may be cured by irradiating ultraviolet rays having a wavelength value of 200 nm or more and 450 nm or less.

By curing the base composition using an electron beam having an energy in the above range or an ultraviolet ray having a wavelength in the above range, the colored base layer can easily implement a desired level of crushability.

According to an embodiment of the present invention, the interface between the colored substrate layer and the colored coating layer is marked by laser irradiation so that the colored coating layer is removed from the colored substrate layer to enable writing of fine characters and designs. It can have an interfacial adhesion suitable for doing it. In addition, the interface between the colored substrate layer and the adhesive layer may have an interface adhesion suitable for realizing long-term durability by applying the multilayer marking film to the final article and attaching it firmly.

According to an embodiment of the present invention, the colored coating layer may include an ultraviolet curable oligomer or an electron beam curable oligomer; And it may include a cured product of the coating composition containing the pigment.

According to an embodiment of the present invention, the colored coating layer may be cured by ultraviolet rays or electron beams, and thus superior reliability of the colored coating layer may be realized compared to other curing means such as thermal curing.

The ultraviolet curable oligomer or electron beam curable oligomer may each independently include at least one selected from the group consisting of a bifunctional bisphenol A epoxy acrylate oligomer and a trifunctional urethane acrylate oligomer.

The ultraviolet curable oligomer or electron beam curable oligomer may each independently have a weight average molecular weight of 500 g/mol or more and 3,000 g/mol or less. Specifically, the weight average molecular weight of the ultraviolet curable oligomer or electron beam curable oligomer may be 500 g/mol or more and 2,000 g/mol or less. By using the UV-curable oligomer or electron-beam curable oligomer having a weight average molecular weight of 500 g/mol or more and 3,000 g/mol or less, durability of the colored coating layer and marking precision by laser irradiation can be improved.

According to an embodiment of the present invention, the coating composition includes a pigment for implementing a color, and the pigment may be variously selected within a range in which the colored base layer and the colored coating layer implement different colors. Specifically, as the pigment, titanium dioxide (TiO ₂ ), carbon black, iron stone, azo pigment, cobalt violet, cadmium sulfide, chromium ferrocyanide, silicate, phosphate, phthalocyanine compound And it may include at least one selected from the group consisting of dioxazine compounds.

According to an embodiment of the present invention, the colored substrate layer and the colored coating layer may implement different colors by including different pigments. Specifically, the colored substrate layer may contain titanium dioxide (TiO ₂ ) as a pigment and exhibit white color, and the colored coating layer may exhibit black as a pigment, including carbon black. In addition, the colored base layer and the colored coating layer may contain the same pigments and adjust their content to implement different colors.

According to an embodiment of the present invention, the content of the pigment may be 1 part by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the ultraviolet curable oligomer or electron beam curable oligomer. By adjusting the content of the pigment within the above range, it is possible to easily secure adhesion of the colored coating layer to the colored substrate layer, and appropriately implement the color of the colored substrate layer, thereby improving the marking performance by laser irradiation. have.

According to an embodiment of the present invention, the multi-layer marking film includes the colored coating layer, the colored substrate layer, and the adhesive layer together to implement improved crushability, and the interfacial adhesion between each layer is properly controlled, and thus laser The precision of marking by irradiation and durability of the final product can be secured at the same time.

The multi-layer marking film secures the property to accurately perform marking by laser irradiation by properly designing the thickness of the layer, implements crushability, and does not cause damage or tearing when measuring adhesion despite high adhesion. Characteristics can be secured.

According to an embodiment of the present invention, the thickness of the colored coating layer may be 2 μm or more and 4 μm or less. By adjusting the thickness of the colored coating layer to 2 µm or more and 4 µm or less, the efficiency of marking by laser irradiation can be improved, and the colored coating layer etched from the colored base layer can be neatly removed. After marking by, the effect of excellent visibility can be easily implemented.

Further, according to an embodiment of the present invention, the thickness of the colored substrate layer may be 50 μm or more and 150 μm or less. By forming a colored base layer having a thickness of 50 µm or more and 150 µm or less on a colored coating layer having a thickness of 2 µm or more and 4 µm or less, the colored base layer can realize excellent durability when marking by laser irradiation, and the multilayer It can greatly contribute to improving the crushability of the marking film. In addition, the distribution or handling of the multilayer marking film is easy, and punchability by laser irradiation can be improved when the multilayer marking film is processed to a desired size.

According to an embodiment of the present invention, the thickness of the adhesive layer may be 20 μm or more and 50 μm or less. By adjusting the thickness of the adhesive layer to 20 µm or more and 50 µm or less, while securing the adhesion to the final article of the multilayer marking film, it is possible to greatly improve the crushability at the same time, and facilitate the adhesion performance of the multilayer marking film Can be implemented.

The present invention will be described in more detail through the following examples. These examples are for illustrative purposes only and do not limit the invention.

Preparation of base composition

Urethane (meth)acrylate oligomer with a weight average molecular weight of 2,400 g/mol and trifunctional MIRAMER PU340 (Miwon Specialty Chemical), a chain aliphatic (meth)acrylate monomer with a molecular weight of 226 g/mol and a bifunctional Titanium dioxide (TiO ₂ ) was prepared as 1,6-hexanediol di(meth)acrylate and a pigment.

Thereafter, a base composition comprising 25 parts by weight of a chain aliphatic (meth)acrylate monomer and 87.5 parts by weight of a pigment was prepared based on 100 parts by weight of the urethane (meth)acrylate oligomer.

Preparation of coating composition

A mixture of a trifunctional urethane acrylate oligomer (Miwonspe oT Chemical Co., MIRAMER PU3200) and a bifunctional bisphenol A-based epoxy acrylate oligomer (SARTOMER, CN120C80) having a weight average molecular weight of 1,900 g/mol as a UV-curable oligomer 100 A coating composition including 5 parts by weight and 5 parts by weight of carbon black was prepared.

Preparation of adhesive composition

Manufacturing example One

Butyl acrylate as a first monomer, benzyl acrylate as a second monomer, and acrylic acid as a third monomer were prepared, toluene as an organic solvent, and isophthaloylbis (2-methylaziridine) as an aziridine curing agent as a curing agent.

Thereafter, butyl acrylate, benzyl acrylate, and acrylic acid were added to toluene, followed by stirring, and heated to 60°C. Thereafter, the mixture was stirred at 70° C. for 8 hours to synthesize a polymer of butyl acrylate, benzyl acrylate, and acrylic acid. Thereafter, the polymer was diluted in toluene, an organic solvent, to prepare a pressure-sensitive adhesive composition. The first monomer, the second monomer, and the third monomer were each adjusted to be added so that 75 parts by weight of butyl acrylate, 20 parts by weight of benzyl acrylate, and 5 parts by weight of acrylic acid based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition.

Thereafter, isophthaloylbis (2-methylaziridine) was dissolved in toluene by adjusting the content of the curing agent to 0.1 parts by weight based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition.

Manufacturing example 2 to 3

A pressure-sensitive adhesive composition was prepared in the same manner as in Preparation Example 1, except that the first monomer, the second monomer, the third monomer, and the curing agent were prepared as shown in Table 1 below.

Manufacturing example 4 to 5

A pressure-sensitive adhesive composition was prepared in the same manner as in Preparation Example 1, except that the first monomer, the second monomer, the third monomer, and the curing agent were prepared as shown in Table 1 below.

Example One

The prepared base composition was applied to one side of a polyethylene terephthalate (PET) release film, and the same PET release film was laminated on top of the base composition applied to the release film. Thereafter, an electron beam having an energy of 40 kGy was irradiated to the base composition, and the base composition was cured with an electron beam to prepare a laminate in which a release film, a colored base layer, and a release film were stacked. Then, one release film was peeled from the laminate, and the coating composition was applied to one side of the colored substrate layer from which the release film was peeled off, followed by UV curing to form a colored coating layer.

Subsequently, the other release film of the laminate was peeled off, and the other side of the colored substrate layer from which the other release film was peeled was subjected to corona treatment, and then the pressure-sensitive adhesive composition prepared in Preparation Example 1 was applied, and at 110° C. 3 The adhesive layer was prepared by heat curing for minutes. The weight average molecular weight of the polymer contained in the pressure-sensitive adhesive composition prepared in Preparation Example 1 is 680,000 g/mol, and the glass transition temperature of the thermosetting product of the pressure-sensitive adhesive composition is -23°C. As a result, a multilayer marking film including a colored coating layer having a thickness of 2 μm, a colored substrate layer having a thickness of 100 μm, and an adhesive layer having a thickness of 25 μm was prepared.

Example 2

A multilayer marking film was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared in Preparation Example 2 was used. The weight average molecular weight of the polymer contained in the pressure-sensitive adhesive composition prepared in Preparation Example 2 is 700,000 g/mol, and the glass transition temperature of the thermosetting product of the pressure-sensitive adhesive composition prepared in Preparation Example 2 is -21°C.

Example 3

A multilayer marking film was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared in Preparation Example 3 was used. The weight average molecular weight of the polymer contained in the pressure-sensitive adhesive composition prepared in Preparation Example 3 is 580,000 g/mol, and the glass transition temperature of the thermosetting product of the pressure-sensitive adhesive composition prepared in Preparation Example 3 is -29°C.

Comparative example One

A multilayer marking film was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared in Preparation Example 4 was used. The weight average molecular weight of the polymer included in the pressure-sensitive adhesive composition prepared in Preparation Example 4 is 350,000 g/mol, and the glass transition temperature of the thermosetting product of the pressure-sensitive adhesive composition prepared in Preparation Example 4 is -8°C.

Comparative example 2

A multilayer marking film was prepared in the same manner as in Example 1, except that the pressure-sensitive adhesive composition prepared in Preparation Example 5 was used. The weight average molecular weight of the polymer included in the pressure-sensitive adhesive composition prepared in Preparation Example 5 is 900,000 g/mol, and the glass transition temperature of the thermosetting product of the pressure-sensitive adhesive composition prepared in Preparation Example 5 is -34°C.

Fragility evaluation

For the multilayer marking film according to the above Examples and Comparative Examples, after attaching a sample of 75 mm × 150 mm size to an aluminum coating plate, 1 hour after exposure to isopropyl alcohol (IPA) having a concentration of 100% The crushability was evaluated according to whether a broken shape was seen when attempting to detach it forcibly using a knife, and whether detachment was possible as it was in the form attached at the beginning, and the results are shown in Table 2 below. When the initial attachment and detachment is possible, the crushability is'NG', and when a breakable shape is seen during the detachment attempt, the crushability is described as'OK'.

Cold resistance evaluation

For the multilayer marking film according to the Examples and Comparative Examples, a sample having a size of 75 mm × 150 mm was prepared, and the sample and an aluminum coating plate were allowed to stand at a temperature of 0° C. or more and 10° C. or less for 24 hours. . Thereafter, only the 75 mm × 75 mm portion of the sample portion was attached to the coating plate and left at a temperature of 0° C. or more and 10° C. or less for 48 hours. Thereafter, in the case of peeling the sample from the painted plate by grabbing the part of the sample that is not attached to the coating plate, the case where peeling is easy is set as'NG', and the case where peeling is not easy is set as'OK', and the cold resistance evaluation result is as follows. It is described in Table 2.

Adherence evaluation

For the multilayer marking film according to the Examples and Comparative Examples, a sample having a size of 25 mm × 150 mm was prepared, and only a 25 mm × 80 mm part of the sample part was attached to an aluminum coating plate and left for 48 hours. Thereafter, a 90° peeling evaluation was performed in which a portion of the sample not attached to the painted plate was held and peeled at a rate of 300 mm/min, and the results are shown in Table 2 below. The case where peeling of the sample is easy is described as'NG', and the case where peeling is not easy is described as'OK'.

Long-term reliability evaluation

With respect to the multilayer marking film according to the Examples and Comparative Examples, a 75 mm × 150 mm sample was attached to an aluminum coating plate and 48 hours passed, and the sample was placed in engine oil at a temperature of 120° C. for 4 hours. Long-term reliability was evaluated according to the state after exposure, and the results are shown in Table 2 below. In the case of the initial attachment, it was indicated as'OK', and in the case of a change in the appearance of the sample, it was indicated as'NG'.

Polymer of adhesive composition
Mw(g/mol) Thermosetting product of adhesive composition
Tg(℃) Fragility Cold resistance Adherence long time
responsibility Example 1 680,000 -23 OK OK OK OK Example 2 700,000 -21 OK OK OK OK Example 3 580,000 -29 OK OK OK OK Comparative Example 1 350,000 -8 OK NG OK NG Comparative Example 2 900,000 -34 OK OK NG OK

Referring to Table 2, it can be seen that the multilayer marking film according to Examples 1 to 3 of the present invention has crushability, excellent cold resistance, adhesion, and long-term reliability. On the other hand, it can be seen that the multilayer marking film according to Comparative Example 1 is inferior to the multilayer marking film according to the embodiment of the present invention in cold resistance and long-term reliability, and the multilayer marking film according to Comparative Example 2 is It can be seen that the adhesion is inferior to the marking film.

100: multilayer marking film
10: adhesive layer
20: colored substrate layer
30: colored coating layer

Claims (16)

Adhesive layer; A colored substrate layer having a first color; And a colored coating layer having a second color, wherein the first color and the second color are different colors,
The colored coating layer, the colored substrate layer, and the adhesive layer are sequentially provided,
The adhesive layer includes a thermosetting product of an adhesive composition containing an adhesive material,
The adhesive material may include a first monomer including a (meth)acrylate having a linear or branched alkyl group having 4 or more and 20 or less carbon atoms; 1 selected from the group consisting of (meth)acrylate having a straight or branched chain alkyl group having 1 to 3 carbon atoms, (meth)acrylate having an epoxy group, (meth)acrylate having an alicyclic alkyl group, and benzyl acrylate A second monomer containing more than one species; And a third monomer comprising a (meth)acrylate having a polar functional group;
The content of the second monomer is 15 parts by weight or more and 35 parts by weight or less, based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition,
The weight average molecular weight of the polymer is 500,000 g/mol or more and 800,000 g/mol or less,
The colored coating layer is a multilayer marking film etched by laser irradiation. The method according to claim 1,
The glass transition temperature of the thermosetting product of the pressure-sensitive adhesive composition is -30 °C or more and -10 °C or less. delete The method according to claim 1,
The second monomer is methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobornyl acrylate, glycidyl methacrylate, isobornyl methacrylate, A multilayer marking film comprising at least one selected from the group consisting of benzyl acrylate, cyclohexyl acrylate and 1-hexadecyl methacrylate. The method according to claim 1,
The content of the first monomer is 60 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. The method according to claim 1,
The polar functional group is a hydroxy group, a carboxyl group or an amino group, the multilayer marking film. The method according to claim 1,
The content of the third monomer is 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. The method according to claim 1,
The pressure-sensitive adhesive composition further comprises a curing agent,
The content of the curing agent is 0.01 parts by weight or more and 1 part by weight or less, based on 100 parts by weight of the total solid content of the pressure-sensitive adhesive composition. The method according to claim 1,
The colored base layer is a multilayer marking film comprising a cured product of a base composition comprising a urethane (meth)acrylate oligomer, a (meth)acrylate monomer, and a pigment. The method of claim 9,
The weight average molecular weight of the urethane (meth) acrylate oligomer is 2,000 g/mol or more and 10,000 g/mol or less. The method of claim 9,
The urethane (meth) acrylate oligomer is a multilayer marking film containing 3 or more and 6 or less (meth) acrylate groups. The method of claim 9,
The (meth)acrylate monomer is selected from the group consisting of an alicyclic (meth)acrylate monomer, an epoxy-based (meth)acrylate monomer, a chain aliphatic (meth)acrylate monomer, and a polyol-based (meth)acrylate monomer The multilayer marking film comprising at least one of which is. The method of claim 9,
The molecular weight of the (meth)acrylate monomer is 200 g/mol or more and 500 g/mol or less. The method of claim 9,
The (meth)acrylate monomer is a multilayer marking film containing 2 or more and 4 or less (meth)acrylate groups. The method of claim 9,
The content of the (meth)acrylate monomer is more than 0 parts by weight and less than 66 parts by weight based on 100 parts by weight of the urethane (meth)acrylate oligomer multilayer marking film. The method according to claim 1,
The colored coating layer may be an ultraviolet curable oligomer or an electron beam curable oligomer; And a cured product of a coating composition comprising a pigment.

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