KR20170114688A - Multilayer laser marking film and method for manufacturing the same - Google Patents

Multilayer laser marking film and method for manufacturing the same Download PDF

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Publication number
KR20170114688A
KR20170114688A KR1020160042077A KR20160042077A KR20170114688A KR 20170114688 A KR20170114688 A KR 20170114688A KR 1020160042077 A KR1020160042077 A KR 1020160042077A KR 20160042077 A KR20160042077 A KR 20160042077A KR 20170114688 A KR20170114688 A KR 20170114688A
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South Korea
Prior art keywords
laser marking
meth
colored
layer
acrylate oligomer
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KR1020160042077A
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Korean (ko)
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KR102046529B1 (en
Inventor
조홍관
홍주희
조명현
김장순
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주식회사 엘지화학
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    • C09J7/0278—
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J7/0296—
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/08—Fastening or securing by means not forming part of the material of the label itself
    • G09F3/10—Fastening or securing by means not forming part of the material of the label itself by an adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label

Abstract

An adhesive layer; A colored base 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 from each other, and the colored base layer comprises a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer , A multi-functional epoxy (meth) acrylate oligomer, and a pigment.
In addition, a base composition comprising a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment is applied onto one release film, Laminating the other release film; Curing the base composition to produce a laminate in which a colored base layer having a first color is disposed between the two release films; Removing one release film from the laminate and forming a colored coating layer having a second color different from the first color on one side of the colored substrate layer; And removing the other release film from the laminate and forming an adhesive layer on the back surface of the colored substrate layer.

Description

TECHNICAL FIELD [0001] The present invention relates to a multilayer laser marking film,

The present invention relates to a multi-layer laser marking film which is excellent in security and which can exhibit high adhesion, and a method for producing the same.

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

As a kind of a method of manufacturing such a label, a method of writing information with a laser is used. For example, Korean Patent Laid-Open No. 10-2006-0027501 discloses an adhesive label sheet capable of marking a large amount of bar codes in a short time using a laser. And JP-A-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.

Such a label should have properties that can be precisely processed by a laser, have excellent adherence to an adherend, and realize various physical properties corresponding to the purpose and purpose at the same time. Therefore, research is needed to control the physical properties of the label according to each application and purpose.

One embodiment of the present invention provides a multilayer laser marking film which is capable of precise processing through a laser, has properties that are not broken at the time of evaluation of physical properties, and is excellent in prevention against forgery and modulation when applied to an actual product .

Another embodiment of the present invention is a method for producing the above-mentioned multilayer laser marking film, whereby the multilayer laser marking film having excellent physical properties can be produced.

In one embodiment of the present invention, an adhesive layer; A colored base 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 from each other, and the colored base layer comprises a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer , A multi-functional epoxy (meth) acrylate oligomer, and a pigment.

In another embodiment of the present invention, a base composition comprising a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment, And laminating another release film on top of the release film; Curing the base composition to produce a laminate in which a colored base layer having a first color is disposed between the two release films; Removing one release film from the laminate and forming a colored coating layer having a second color different from the first color on one side of the colored substrate layer; And removing the other release film from the laminate and forming an adhesive layer on the back surface of the colored substrate layer.

The multi-layer laser marking film has properties that can measure the adhesion force without being broken at the time of physical property evaluation, and at the same time, after being applied to an actual article, it is shredded when it is done to remove it, It is possible to realize the anti-modulation performance.

The multi-layer laser marking film can simultaneously produce the multilayer laser marking film.

1 schematically shows a cross section of a multilayer laser marking film according to an embodiment of the present invention.
Fig. 2 schematically shows a cross section of the multilayer laser marking film of Fig. 1 when laser marking is performed.
3 schematically shows a cross-section of a multilayer laser marking film according to another embodiment of the present invention.
4 schematically shows a method of manufacturing a multilayer laser marking film according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art to which the invention pertains. Only. Like reference numerals refer to like elements throughout the specification.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. In the drawings, for the convenience of explanation, the thicknesses of some layers and regions are exaggerated.

It will also be understood that when a layer, film, region, plate, or the like is referred to as being "on" or "over" another portion, . Conversely, when a part is "directly over" another part, it means that there is no other part in the middle. In addition, when a layer, film, region, plate, or the like is referred to as being "under" or "under" another portion, . Conversely, when a part is "directly underneath" another part, it means that there is no other part in the middle.

In one embodiment of the present invention, an adhesive layer; A colored base 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 from each other, and the colored base layer comprises a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer , A multi-functional epoxy (meth) acrylate oligomer, and a pigment.

FIG. 1 schematically shows a multilayer laser marking film 100 according to an embodiment of the present invention, and specifically shows a cross section of the multilayer laser marking film 100 in detail.

1, the multilayer laser marking film 100 includes an adhesive layer 10, a colored base layer 20, and a colored coating layer 30. The multilayer laser marking film 100 includes, for example, Layer structure in which the colored substrate layer 20 is formed on the colored substrate layer 20 and the colored coating layer 30 is formed directly on the colored substrate layer 20.

The multilayer laser marking film is a film that can be etched by a laser to write various information. In this specification, 'laser marking' means writing information to a film by laser etching. Specifically, in the multilayer laser marking film, laser marking can be performed on the colored coating layer.

That is, the multilayer laser marking film has laser markability, and the 'laser markability' means the property that the colored coating layer is etched by laser irradiation and the etched portion is removed. As described above, the laser-irradiated portion of the colored coating layer is etched and removed, thereby interacting with the colored substrate layer and writing various characters, drawings, and the like.

The colored substrate layer 20 and the colored coating layer 30 all have a color, and the term 'colored' means that the substrate layer or the coating layer is not transparent and has a color such as white, black, or blue . Specifically, the colored substrate layer 20 has a first color, the colored coating layer 30 has a second color, and the first color and the second color are different colors.

As described above, 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 portions can exhibit various colors depending on the etching depth.

2 is a schematic cross-sectional view of a multilayer laser marking film 100 according to an embodiment of the present invention when laser marking is performed.

Referring to FIG. 2 (a), only the first color of the colored substrate layer 20 can be visually recognized when the entirety of the colored coating layer 30 is etched by laser marking. Referring to FIG. 2B, when a part of the thickness of the colored coating layer 30 is etched, the first color of the colored substrate layer 20 and the color of the remaining colored coating layer 30 The color in which the second color appears superimposed can be visually recognized.

The multilayer laser marking film is capable of writing letters or patterns of various colors through laser marking. For example, the multilayer laser marking film can be used in automobiles and specifically displays information about various parts of the vehicle such as tire pressure or fuel type, unique security information such as vehicle identification number and vehicle identification number Lt; / RTI >

The multilayer laser marking film needs to be prevented from forging or modulating important information when it is written. Specifically, the multilayer laser marking film may have a self-destructive property. The term "self-destructive property" means a property in which an original shape is broken and can not be recycled when an attempt is made to detach or remove the multilayer laser marking film after it has adhered to an adherend. Since the multilayer laser marking film has self-crushing property, unique information written thereon can not be arbitrarily changed, and characteristics that can not be falsified or modulated can be secured.

In addition, the multilayer laser marking film has excellent self-destructiveness after being applied to a final product, and evaluates physical properties such as adhesion before being applied to a final product, or in the process of producing a multilayer laser marking film. Or the multilayer laser marking film may have a property of being not broken during the flow of the multilayer laser marking film, that is, resistance to self-fracturing and stability. Generally, a self-destructive film has a problem that the film tears or breaks due to self-fracturing property when evaluating physical properties such as adhesion. Particularly, in the case of a film having a pressure sensitive adhesive layer with high adhesion, there is a problem that the measurement of the adhesion force becomes more difficult.

However, the multilayer laser marking film may include a pressure-sensitive adhesive layer having a high adherence property, but may not be torn or broken at the time of evaluating properties such as adhesion, and at the same time, . ≪ / RTI >

Specifically, this advantage of the multilayer laser marking film can be achieved through the colored base layer and the adhesive layer.

The colored substrate layer may comprise a cured product of a base composition comprising a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment.

The base composition is a composition for forming the colored base layer, which contains a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer, It is possible to impart favorable physical properties to the multilayer laser marking film as described above.

Specifically, the monofunctional (meth) acrylate oligomer is an oligomer having one (meth) acrylate group as a functional group in one molecule, and more specifically may include a (meth) acrylate group at the terminal.

The weight average molecular weight (Mw) of the monofunctional (meth) acrylate oligomer may be about 30,000 to about 50,000. In this case, the modulus of the colored substrate layer may be reduced to provide flexibility, Deformation due to shrinkage can be effectively prevented.

The polyfunctional urethane (meth) acrylate oligomer is a urethane oligomer having two or more (meth) acrylate groups in one molecule, and examples thereof include trifunctional urethane (meth) acrylate oligomer or hexafunctional Lt; / RTI > oligomers.

In one embodiment, the polyfunctional urethane (meth) acrylate oligomer may comprise a trifunctional urethane (meth) acrylate oligomer and a hexafunctional urethane (meth) acrylate oligomer, Rigidity and surface hardness of the colored substrate layer, and it is possible to effectively enhance the tensile strength of the colored substrate layer to ensure the ability to resist self-fracturing during evaluation of process, distribution and physical property data, It is possible to effectively realize a characteristic exhibiting excellent self-destructiveness.

The trifunctional urethane (meth) acrylate oligomer may be an aliphatic urethane (meth) acrylate oligomer. Through such a chemical structure, rigidity and tensile strength of the colored base layer are strengthened, and process, It may be advantageous to impart stability to self-fracturing during evaluation.

In addition, the hexafunctional urethane (meth) acrylate oligomer may be an aliphatic urethane (meth) acrylate oligomer, thereby securing rapid curing characteristics to increase the degree of surface hardening of the colored base layer, May be advantageous to the following.

The polyfunctional urethane (meth) acrylate oligomer may have a weight average molecular weight (Mw) of from about 2,000 to about 5,000 and, in this case, while ensuring the required self-destructive performance, at the same time, It may be advantageous to secure.

Also, the polyfunctional epoxy (meth) acrylate oligomer is an epoxy oligomer having two or more (meth) acrylate groups in one molecule and may include, for example, a bifunctional epoxy (meth) acrylate oligomer. When the polyfunctional epoxy (meth) acrylate oligomer includes a bifunctional epoxy (meth) acrylate oligomer, the effect of reducing the curling due to shrinkage after curing by increasing the hardness of the substrate while imparting flexibility to the substrate Can be more advantageous.

Further, the bifunctional epoxy (meth) acrylate oligomer may be advantageous to simultaneously impart an effect of raising the base strength and a base shrinkage lowering effect after curing by using a bisphenol A (bisphenol A) structure.

The polyfunctional epoxy (meth) acrylate oligomer may have a weight average molecular weight (Mw) of from about 500 to about 1,500, which may be advantageous in securing substrate flexibility effects.

The base composition can control the modulus of the colored base layer by controlling the components contained therein in an appropriate amount so that the problem of breakage or tearing during the measurement of the adhesion of the multilayer laser marking film is effectively prevented The multilayer laser marking film can be made to exhibit improved self-destructiveness when a predetermined time has elapsed after application of the multilayer laser marking film to the final product.

Specifically, the base composition comprises about 5 wt% to about 20 wt% of the monofunctional (meth) acrylate oligomer and about 10 wt% to about 35 wt% of the polyfunctional urethane (meth) acrylate oligomer About 5 wt% to about 30 wt% of the polyfunctional epoxy (meth) acrylate oligomer, and about 45 wt% to about 55 wt% of the pigment.

The base composition can ensure the self-destructiveness by incorporating each component in the content within the above-mentioned range, thereby realizing a function of preventing forgery and tampering. At the same time, the multilayer laser marking film comprising the colored base layer, It is possible to maximize the property of not tearing or breaking when evaluating physical properties.

The base composition can achieve a clear color by including the pigment in the above range of contents. In general, when the content of the pigment is increased, there is a problem that the viscosity is excessively increased or the workability is lowered. However, although the base composition contains a comparatively large amount of pigment, It is possible to secure the self-fracturing property and the workability at the same level.

The multilayer laser marking film is applied to an article related to information contained in laser marking and includes an adhesive layer to be attached to the article. The multilayer laser marking film can exhibit a high adhesive force to an article to be finally applied through the adhesive layer. By including both the adhesive layer and the colored substrate layer, breakage and tearing Can be effectively prevented. Furthermore, it can exhibit improved self-destructiveness when a predetermined time has elapsed after application to the final product through the adhesive layer.

Specifically, the adhesive layer may have an adhesive force of about 1400 gf / cm or more to the adherend, and may be, for example, about 1400 gf / cm to about 4000 gf / cm. Although the multilayer laser marking film includes the pressure-sensitive adhesive layer exhibiting the adhesive force within the above range, the pressure-sensitive adhesive layer and the colored substrate layer may be included together so that the measurement can be performed without any breakage or tearing in measuring the physical properties of the adhesive force. In addition, the multilayer laser marking film can improve long term adhesion when applied to a final product through an adhesive layer exhibiting an adhesive force in the above range. The multilayer laser marking film has a variety of uses and can be used, for example, as a label attached to an automobile. In this case, the adherend may be a metal automobile coating plate, It is possible to secure long-term adherence thereto.

The adhesive layer may be formed from a pressure-sensitive adhesive composition comprising a thermosetting acrylic resin and a curing agent, and may specifically include a cured product of the pressure-sensitive adhesive composition.

The thermosetting acrylic resin may be a copolymer of ethylhexyl acrylate (EHA), methyl acrylate (MA), and acrylic acid (AA), although it is not particularly limited as long as it can achieve the above- , Whereby the adhesive layer can excellently realize the effect of improving adhesion to the colored base layer and heat resistance.

The thermosetting acrylic resin may have a weight average molecular weight (Mw) of about 100,000 to about 1,000, for example, about 500,000 to about 500. When the weight average molecular weight (Mw) of the resin satisfies the above range, the pressure-sensitive adhesive layer can exhibit high adhesiveness, easy adhesion to the colored base layer can be ensured, and heat resistance can be secured.

The adhesive composition comprises a curing agent together with the thermosetting acrylic resin, wherein the curing agent has an appropriate gel content in the adhesive layer comprising the cured product of the adhesive composition to impart enhanced adhesion to the multilayer laser marking film , The multilayer laser marking film can have a self-destructive property at a required level.

The curing agent may include one selected from the group consisting of an aziridine curing agent, a peroxide type curing agent, an isocyanate type curing agent, and combinations thereof. For example, the curing agent may include an aziridine-based curing agent. In this case, the curing agent interacts with the thermosetting acrylic resin to realize an excellent curing efficiency, heat resistance, chemical resistance, Can be more advantageous.

 The adhesive composition may include from about 90 wt% to about 99.999 wt% of the thermosetting acrylic resin, and from about 0.001 wt% to about 10 wt% of the curing agent. By using the resin and the curing agent in the above-mentioned ranges, the adhesive layer formed from the adhesive composition can have a proper gel content, and adhesion to the colored base layer and high adhesion to the final product can be secured at the same time. Further, the multilayer laser marking film can be provided with an improved long-term attachment holding performance.

The multilayer laser marking film further comprises a colored coating layer together with the adhesive layer and the colored substrate layer. As described above, the colored coating layer is a layer to be subjected to laser marking, and must be capable of precise etching by a laser, and the adhesion with the colored base layer must be ensured. Further, the colored coating layer has a second color different from the first color of the colored substrate layer.

Wherein the colored coating layer comprises a photo-curable oligomer or a thermosetting oligomer; And a pigment, and may specifically comprise a cured product of the coating composition.

In one embodiment, the colored coating layer may comprise a photo-cured product of a coating composition comprising a photo-curable oligomer and a pigment.

In another embodiment, the colored coating layer may comprise a coating composition comprising a mixture of a photo-curable oligomer and a thermosetting oligomer and a pigment, or a dual cure, i.e., a cure applying both photo-curing and thermosetting.

That is, the coating composition may include only a photo-curable oligomer and may have dual curability including both the photo-curable oligomer and the thermosetting oligomer.

The photocurable oligomer may be, for example, a bifunctional bisphenol A epoxy acrylate oligomer, a trifunctional urethane acrylate oligomer, or a mixture of the two.

Also, the photo-curable oligomer may have a weight average molecular weight (Mw) of from about 500 to about 3,000, for example, from about 500 to about 2,000.

The thermoset oligomer may include, for example, an isocyanate oligomer or an isocyanate acrylate oligomer.

More specifically, the thermosetting oligomer is selected from the group consisting of Biuret type hexamethylene diisocyanate (HDI) oligomer, isocyanurate type hexamethylene diisocyanate (HDI) oligomer, adduct type hexamethylene But are not limited to, diisocyanate (HDI) oligomers, biuret type isophorone diisocyanate (IPDI) oligomers, isocyanurate type isophorone diisocyanate (IPDI) oligomers, adduct type isophorone di Isocyanate (IPDI) oligomer, adduct type xylene diisocyanate (XDI) oligomer, adduct type 1,4-bis (isocyanate methyl) cyclohexane (H6XDI) oligomer, adduct type Of 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI) oligomers, and combinations thereof. .

When the coating composition has dual curability including both photo-curable oligomers and thermoset oligomers, the weight ratio of the photo-curable oligomer to the thermoset oligomer may range from about 75:25 to about 98: 2.

The coating composition comprises from about 80% to about 98% by weight of the photo-curable oligomer or thermoset oligomer and from about 2% to about 20% by weight of the pigment. It is easy to secure the adhesion between the colored base layer and the colored coating layer in the content of each component in the above range, and the precise shape can be precisely etched by laser marking.

When the coating composition contains a photocurable oligomer, it may further include a photoinitiator for photocuring, and the kind thereof is not particularly limited.

In the multilayer laser marking film, 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 from each other. In order to obtain such a hue, the colored base layer and the colored coating layer each include a pigment, and the pigment may be variously selected depending on the color to be implemented.

For example, the pigment may include one selected from titanium dioxide (TiO 2), carbon black, silicon dioxide (SiO2), zinc oxide and combinations thereof.

The colored substrate layer and the colored coating layer may contain different pigments to realize different colors. For example, the colored substrate layer may include white pigment including titanium dioxide (TiO 2 ) as a pigment, and the colored coating layer may include black as a pigment including carbon black.

On the other hand, the colored base layer and the colored coating layer may contain different pigments and different colors may be realized by adjusting their contents.

1, the multi-layer laser marking film 100 may include a multi-layer structure of an adhesive layer 10, a colored base layer 20, and a colored coating layer 30. As shown in FIG. Referring to FIG. 3, the multi-layer laser marking film 100 may further include a release layer 40 on one or both sides of the outermost edge.

3 (a), the release layer 40 may be formed on only one side of the adhesive layer 10, and the side of the adhesive layer 10 and the side of the colored coating layer 10 30 may be formed together.

The release layer 40 is removed when the multilayer laser marking film is applied to a final product. The release layer 40 formed on one side of the colored coating layer 30 may be removed before laser marking, It may be removed later. When the release layer 40 is removed after the laser marking, the release layer 40 may be formed of a material having transparency to the laser.

In the multilayer laser marking film, the thickness of the layer is appropriately designed so that the laser marking is easily performed, the self-destructive property is realized, and even when the adhesion is measured, the laser marking film is free from breakage or ripping .

For example, the thickness of the colored substrate layer may be from about 60 占 퐉 to about 150 占 퐉, and the thickness of the colored coating layer may be from about 1 占 퐉 to about 5 占 퐉. When the thickness of the colored base layer and the thickness of the colored coating layer respectively satisfy the above ranges, it is possible to realize accurate design and character by laser marking of the colored coating layer, and the multilayer laser marking film It is possible to effectively prevent breakage or ripping of the hour.

Also, the thickness of the adhesive layer may be about 10 탆 to about 50 탆. The thickness of the adhesive layer satisfies the above range, it is possible to realize a level of adhesion capable of securing a physical property capable of measuring the adhesive force without breakage or tearing, and it can be applied to a final product, .

As described above, the multilayer laser marking film includes the colored base layer, the colored coating layer, and the adhesive layer, and by properly designing the components and the thickness of each layer, it is possible to secure physical properties capable of measuring the adhesive force without breakage or tearing And, at the same time, improved self-destructive and adherence performance can be achieved after application to the final article.

In another embodiment of the present invention, there is provided a method of producing the multilayer laser marking film, wherein the method comprises, on one release film, a monofunctional (meth) acrylate oligomer, a polyfunctional urethane Applying a base composition comprising an oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment, and laminating another release film on top of the base composition; Curing the base composition to produce a laminate in which a colored base layer having a first color is disposed between the two release films; Removing one release film from the laminate and forming a colored coating layer having a second color different from the first color on one side of the colored substrate layer; And removing the other release film from the laminate and forming an adhesive layer on the back surface of the colored substrate layer.

The multi-layer laser marking film produced by the above-described method can ensure physical properties capable of measuring the adhesive force without breaking or tearing, and at the same time, it can achieve improved self-destructiveness and adhesion maintenance performance after being applied to a final product. That is, the above-described manufacturing method can be an optimal method for producing a multilayer laser marking film having such advantages.

4 schematically shows a method of manufacturing a multilayer laser marking film according to an embodiment of the present invention.

4, the manufacturing method includes a step (S100) of applying a base composition (A) on one release film (50) and laminating another release film (50) on the base composition . The base composition (A) comprises a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment, .

The method of applying the base composition (A) on one release film (50) is not particularly limited. For example, a spin coating method, a bar coating method, a comma coating method, A gravure coating method, a roll coating method, or the like can be used.

Then, the manufacturing method may include a step (S200) of curing the base composition (A) to form a laminate in which a colored base layer (20) having a first color is disposed between the two release films have. That is, by curing the base composition (A) applied between the two release films 50, it is possible to produce a laminate in which the release film 50, the colored base layer 20 and the release film 50 are sequentially laminated have.

Curing of the base composition may be performed by a method of electron beam curing. As described above, the base composition comprises a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment and is cured . As a result, the colored base layer can impart physical properties to the multilayer laser marking film without causing breakage or tearing, and at the same time, after a predetermined period of time after application to the final product, . ≪ / RTI >

As described above, in the method for producing a multilayer laser marking film, a laminate having a structure in which a colored substrate layer is interposed between two release films is preferentially formed, thereby improving the adhesion force in the subsequent process of producing the colored coating layer and the adhesive layer It may be more advantageous in terms of securing the physical property for improving the self-fracturing property after a predetermined time has elapsed after being applied to the final article while preventing the breakage or tearing in the measurement of the adhesive force.

After one release film 50 is removed from the laminate having the colored substrate layer 20 interposed between the two release films 50, the first release film 50 is removed from the first release film 50, (S300, S400) of forming a colored coating layer (30) having a second color which is a different color from the color.

The colored coating layer 30 is formed from the coating composition as described above. For example, referring to FIG. 4, a coating composition (B) is coated on one side of the colored substrate layer by a direct coating method and cured to form can do. When the coating composition (B) is coated by a direct coating method, there is an advantage that the adhesion of the colored coating layer and the colored substrate layer can be easily secured compared with other coating methods such as transfer coating.

The coating composition may comprise a photo-curable oligomer or a thermoset oligomer; And a pigment, and the details thereof are as described above.

When the step of forming the colored coating layer is a direct coating method, the method of coating the coating composition is not particularly limited. For example, a spin coating, a bar coating, a gravure coating, a microgravure coating, Comma coating, slot die coating, spray coating and the like can be used. The curing method of the coating composition may be a thermal curing method, a light curing method or a dual curing method depending on the components of the colored coating layer.

In one embodiment, the coating composition may be advantageous from the viewpoint of chemical resistance and abrasion resistance to have dual curing properties including both photo-curable oligomers and thermosetting oligomers.

When the coating composition has dual curability including both a photo-curable oligomer and a thermosetting oligomer, the weight ratio of the photo-curable oligomer and the thermosetting oligomer may be 75:25 to 98: 2.

At this time, in addition to the photoinitiator for photo-curing, the coating composition may use a Tin-based catalyst as a thermosetting catalyst.

The method of manufacturing the multilayer laser marking film includes the steps of forming an adhesive layer 10 on the back surface of the colored substrate layer 20 after removing the other release film 50 (S500 and S600).

The adhesive layer 10 may include a cured product of a pressure-sensitive adhesive composition comprising a thermosetting acrylic resin and a curing agent, as described above.

Referring to FIG. 4, the step of forming the pressure-sensitive adhesive layer 10 may be a step of applying the pressure-sensitive adhesive composition (C) on the back surface of the colored base material layer 20 and thermally curing the same.

The multilayer laser marking film can be manufactured through the method of producing the multilayer laser marking film, and the thickness of each layer can be manufactured to satisfy the above-mentioned range.

The method of manufacturing the multilayer laser marking film may further include forming a release layer 40 on one or both sides of the outermost layer, and the release layer 40 is as described above .

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

< Example  And Comparative Example >

Example  1-7

On one side of the polyethylene terephthalate (PET) release film, the components and the contents of the base compositions as shown in Table 1 below were applied, and the same PET release film was laminated on the top. Subsequently, the base composition was cured through electron beam curing to produce a laminate having a structure in which a release film, a colored base layer having a thickness of 90 占 퐉 and a release film were laminated.

Next, one of the release films of the laminate is peeled off, and a bifunctional bisphenol A epoxy acrylate oligomer and a trifunctional urethane acrylate oligomer as photo-curable oligomers are peeled off from the colored base layer from which the release film is peeled. A coating composition containing an isocyanate oligomer as an oligomer and containing carbon black was prepared in the contents shown in Table 1 below and coated with a coating solution diluted in a solvent (MEK, MIBK). Then, the coating solution was photo-cured by UV of 300 mJ and then thermally cured at 100 ° C for 30 minutes to prepare a 3-μm-thick colored coating layer.

Next, another release film of the laminate was peeled off, and a thermosetting acrylic resin and an aziridine curing agent having a weight average molecular weight (Mw) of 500,000 to 5,000,000 were included in the contents shown in the following Table 1 on the back surface of the colored base layer And then thermally cured at 120 캜 for 3 minutes to 5 minutes to prepare a pressure-sensitive adhesive layer having a thickness of 25 탆. Thus, a multilayer laser marking film comprising a colored coating layer, a colored base layer and an adhesive layer was produced.

Comparative Example  1-3

A multilayer laser marking film was prepared in the same manner as in the above Examples except that each of the base composition, coating composition and adhesive composition was used in the components and contents shown in Table 1 below.

Base composition
[weight%] Coating composition
[Chan%] Adhesive composition
[weight%] 1-sensory UAO Trifunctional UAO 6-sensory UAO Bifunctional EAO TiO 2 Photo-curable oligomer Thermosetting
Oligomer Carbon black Suzy Hardener room
city
Yes One 5 15 12 20 48 86 5 9 99 One 2 10 15 5 15 55 86 5 9 99 One 3 20 20 10 5 45 86 5 9 99 One 4 10 25 5 15 45 86 5 9 99 One 5 5 15 12 20 48 89 2 9 99 One 6 5 15 12 20 48 81 10 9 99 One 7 5 15 12 20 48 73 18 9 99 One ratio
School
Yes One - 20 12 20 48 86 5 9 99 One 2 22 - - 30 48 86 5 9 99 One 3 5 15 32 - 48 86 5 9 99 One

* UAO: Urethane acrylate oligomer

* EAO: Epoxy acrylate oligomer

<Evaluation>

Experimental Example  1: Measurement of change of adhesion force with time

The multilayer laser marking films of Example 1-7 and Comparative Example 1-3 were adhered such that the respective adhesive layers were in contact with automotive coating plates made of stainless steel, The adhesion after the elapse of time was measured. The adhesive force was measured by applying a load in a direction of 90 degrees at a rate of 300 mm / min at room temperature using a tensile tester based on the method based on ASTM D3330. In addition, it was observed whether or not each multilayer laser marking film had self-fracturing property after a predetermined time had elapsed since its attachment.

Adhesion over time [gf / cm] After 1 hour After 24 hours After 48 hours 3 days later Example 1 1200 2610 3200 Shredding Example 2 1100 2470 3000 Shredding Example 3 1080 2810 3150 Shredding Example 4 990 2380 3210 Shredding Example 5 1010 2480 3030 Shredding Example 6 1080 2570 3120 Shredding Example 7 1190 2320 3060 Shredding Comparative Example 1 Curl Generation NG - - - Comparative Example 2 870 Shredding - - Comparative Example 3 Curl Generation NG - - -

Referring to the results of Tables 1 and 2, the multilayer laser marking films of Examples 1 to 7 were prepared by mixing monofunctional (meth) acrylate oligomer, polyfunctional urethane (meth) acrylate oligomer, polyfunctional epoxy Acrylate oligomer and a pigment, wherein the colored coating layer and the adhesive layer formed on one side of the colored substrate layer are provided with an adhesion force equal to or higher than a certain level and at the same time, It shows self-destructiveness and realizes excellent security performance.

In addition, the multilayer laser marking films of Comparative Examples 1 to 3 include a colored base layer composed of a component lacking at least one of the components of the base compositions of Examples 1 to 7, and curl It is not possible to secure a basic adhesion performance because it can not realize a certain level of adhesion force or more, and there is a problem that the resistance against fracture or damage can not be realized during the time required for distribution, manufacturing process and physical property evaluation.

100: multilayer laser marking film
10: Adhesive layer
20: colored substrate layer
30: colored coating layer
40:
50: release film
A: base composition
B: Coating composition
C: adhesive composition

Claims (16)

An adhesive layer; A colored base 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 from each other,
The colored base layer comprises a cured product of a base composition comprising a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment
Multilayer laser marking film.
The method according to claim 1,
The polyfunctional urethane (meth) acrylate oligomer includes a trifunctional urethane (meth) acrylate oligomer or a hexafunctional urethane (meth) acrylate oligomer
Multilayer laser marking film.
The method according to claim 1,
The polyfunctional epoxy (meth) acrylate oligomer comprises a bifunctional epoxy (meth) acrylate oligomer
Multilayer laser marking film.
The method according to claim 1,
The base composition comprises 5% to 20% by weight of the monofunctional (meth) acrylate oligomer; 10% to 35% by weight of the polyfunctional urethane (meth) acrylate oligomer; 5 to 30% by weight of the polyfunctional epoxy (meth) acrylate oligomer; And from 45% to 55% by weight of the pigment
Multilayer laser marking film.
The method according to claim 1,
The adhesive layer has an adhesive force of not less than 1400 gf / cm
Multilayer laser marking film.
The method according to claim 1,
Wherein the adhesive layer comprises a cured product of a pressure-sensitive adhesive composition comprising a thermosetting acrylic resin and a curing agent
Multilayer laser marking film.
The method according to claim 6,
The thermosetting acrylic resin has a weight average molecular weight (Mw) of 100,000 to 10,000,000
Multilayer laser marking film.
The method according to claim 6,
The thermosetting acrylic resin is a copolymer of ethylhexyl acrylate (EHA), methyl acrylate (MA) and acrylic acid (AA)
Multilayer laser marking film.
The method according to claim 6,
Wherein the curing agent comprises one selected from the group consisting of an aziridine-based curing agent, a peroxide-based curing agent, an isocyanate-based curing agent,
Multilayer laser marking film.
The method according to claim 6,
Wherein the adhesive composition comprises 90% by weight to 99.999% by weight of the thermosetting acrylic resin; And 0.001 wt% to 10 wt% of the hardener
Multilayer laser marking film.
The method according to claim 1,
Wherein the colored coating layer comprises a photocurable oligomer, a thermosetting oligomer or a mixed oligomer thereof; And a cure of a coating composition comprising a pigment
Multilayer laser marking film.
12. The method of claim 11,
Wherein the coating composition comprises 80 wt% to 98 wt% of the photocurable oligomer, the thermosetting oligomer, or a mixed oligomer thereof, and the coating composition comprises 2 wt% to 20 wt%
Multilayer laser marking film.
The method according to claim 1,
The method for manufacturing a semiconductor device according to any one of claims 1 to 3,
Multilayer laser marking film.
A base composition comprising a monofunctional (meth) acrylate oligomer, a polyfunctional urethane (meth) acrylate oligomer, a polyfunctional epoxy (meth) acrylate oligomer and a pigment is applied on top of one release film, Laminating a release film of
Curing the base composition to produce a laminate in which a colored base layer having a first color is disposed between the two release films;
Removing one release film from the laminate and forming a colored coating layer having a second color different from the first color on one side of the colored substrate layer; And
Removing the other release film from the laminate and forming an adhesive layer on the back surface of the colored base layer
A method for producing a multilayer laser marking film.
15. The method of claim 14,
The base composition is cured by electron beam curing
A method for producing a multilayer laser marking film.
15. The method of claim 14,
The step of forming a colored coating layer on one side of the colored base layer includes:
Coating the coating composition on one surface of the colored substrate layer by a direct coating method and curing the coating composition
A method for producing a multilayer laser marking film.
KR1020160042077A 2016-04-06 2016-04-06 Multilayer laser marking film and method for manufacturing the same KR102046529B1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003114621A (en) * 2001-08-11 2003-04-18 Tesa Ag Label having increased protecting property for prevention of forgery
KR20130018625A (en) * 2011-08-12 2013-02-25 테사 소시에타스 유로파에아 Heat-resistant laser-inscribable film
JP2014189563A (en) * 2013-03-26 2014-10-06 Lintec Corp Tacky sheet, film for forming protective film, composite sheet for forming protective film, and marking method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003114621A (en) * 2001-08-11 2003-04-18 Tesa Ag Label having increased protecting property for prevention of forgery
KR20130018625A (en) * 2011-08-12 2013-02-25 테사 소시에타스 유로파에아 Heat-resistant laser-inscribable film
JP2014189563A (en) * 2013-03-26 2014-10-06 Lintec Corp Tacky sheet, film for forming protective film, composite sheet for forming protective film, and marking method

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