KR102046532B1 - Multilayer laser marking film and method for manufacturing the same - Google Patents

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

Info

Publication number
KR102046532B1
KR102046532B1 KR1020160045165A KR20160045165A KR102046532B1 KR 102046532 B1 KR102046532 B1 KR 102046532B1 KR 1020160045165 A KR1020160045165 A KR 1020160045165A KR 20160045165 A KR20160045165 A KR 20160045165A KR 102046532 B1 KR102046532 B1 KR 102046532B1
Authority
KR
South Korea
Prior art keywords
meth
acrylate
laser marking
layer
colored
Prior art date
Application number
KR1020160045165A
Other languages
Korean (ko)
Other versions
KR20170116902A (en
Inventor
조명현
김장순
조홍관
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to KR1020160045165A priority Critical patent/KR102046532B1/en
Publication of KR20170116902A publication Critical patent/KR20170116902A/en
Application granted granted Critical
Publication of KR102046532B1 publication Critical patent/KR102046532B1/en

Links

Images

Classifications

    • 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]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/10—Removing layers, or parts of layers, mechanically or chemically
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0843—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Theoretical Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laser Beam Processing (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Adhesive Tapes (AREA)

Abstract

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 includes a urethane (meth) acrylate oligomer and a (meth) acrylate monomer; And a cured product of the base composition comprising a pigment, wherein the adhesive layer is a first alkyl (meth) acrylate having a linear or branched alkyl group of 1 to 3 carbon atoms; Second alkyl (meth) acrylates having linear or branched alkyl groups of 4 to 16 carbon atoms; And a cured product of the pressure-sensitive adhesive composition comprising a copolymerized resin of a mixed monomer component containing a (meth) acrylate having a carboxyl group.

Description

Multilayer Laser Marking Film and Manufacturing Method Thereof {MULTILAYER LASER MARKING FILM AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a multilayer film capable of marking with a laser and a method of manufacturing the same.

Various articles have labels for unique identification functions. These labels contain a variety of information about the item and may also perform unique identification functions. Labels used in the automotive industry, for example, may be used to display information about various parts of a vehicle, such as tire pressure or fuel type, or to display unique security information such as, for example, chassis number and vehicle identification number. It is used. In case of theft or accident, these labels allow tracking of the vehicle.

As one kind of method of manufacturing such a label, a method of writing information with a laser is used. Lasers are easy to be used for machining as high power light sources. For example, Korean Patent Publication No. 10-2006-0027501 includes an adhesive label sheet capable of marking a large amount of barcodes in a short time using a laser. Japanese Laid-Open Patent Publication No. 1990-120042 discloses a heat resistant display material having a marked layer having an etching pattern formed by a laser beam on a heat resistant base layer.

Such a label should have physical properties that can be precisely processed by a laser, have excellent adhesion to adherends, and simultaneously implement various physical properties corresponding to a purpose and purpose. Therefore, there is a need for a study to control the properties of the label according to each use and purpose.

One embodiment of the present invention is capable of precise punching and marking through a laser, and provides a multi-layer laser marking film having excellent reprocessability due to physical properties that are easily detachable and reattached within a short time after attachment. In addition, the multilayer laser marking film may implement excellent protection against desorption, forgery, and modulation after a predetermined time has elapsed after attachment.

In addition, another embodiment of the present invention is a method of manufacturing a multilayer laser marking film having excellent physical properties as described above, to provide a method of manufacturing a multilayer laser marking film that can be implemented to excellently implement the durability of the multilayer structure of the film itself. do.

In one embodiment of the invention, the 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 includes a urethane (meth) acrylate oligomer and a (meth) acrylate monomer; And a cured product of the base composition comprising a pigment, wherein the adhesive layer is a first alkyl (meth) acrylate having a linear or branched alkyl group of 1 to 3 carbon atoms; Second alkyl (meth) acrylates having linear or branched alkyl groups of 4 to 16 carbon atoms; And it provides the multilayer laser marking film containing the hardened | cured material of the adhesive composition containing the copolymerization resin of the mixed monomer component containing the (meth) acrylate which has a carboxyl group.

In another embodiment of the present invention, a urethane (meth) acrylate oligomer, (meth) acrylate monomer on top of one release film; And applying a base composition comprising the pigment, and laminating another release film thereon; Curing the substrate composition to form a laminate in which a colored substrate layer having a first color is disposed between 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 surface of the colored substrate layer; And a first alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms on the other side of the colored substrate layer after removing another release film from the laminate; Second alkyl (meth) acrylates having linear or branched alkyl groups of 4 to 16 carbon atoms; And forming a pressure-sensitive adhesive layer comprising a cured product of the pressure-sensitive adhesive composition comprising a copolymerization resin of a mixed monomer component including a (meth) acrylate having a carboxyl group.

The multi-layer laser marking film is capable of precise punching and marking through a laser, and has an excellent reprocessing property due to easy physical property detachment within a short time after attachment. In addition, the multilayer laser marking film may implement excellent protection against desorption, forgery, and modulation after a predetermined time has elapsed after attachment.

The method of manufacturing the multi-layer laser marking film can produce a multi-layer laser marking film having the above-described advantages with high process efficiency, and the multi-layer laser marking film produced through this has excellent interlayer interface adhesion and excellent durability of the multi-layer structure Can have

1 is a schematic cross-sectional view of a multilayer laser marking film according to an embodiment of the present invention.
FIG. 2 schematically illustrates a cross section when laser marking is performed on the multilayer laser marking film of FIG. 1.
3 is a schematic cross-sectional view of a multilayer laser marking film according to another embodiment of the present invention.

Advantages and features of the present invention, and methods for achieving the same will be apparent with reference to the following embodiments. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms. The present embodiments are merely provided to make the disclosure of the present invention complete, and to fully convey the scope of the invention to those skilled in the art, and the present invention is defined by the scope of the claims. It will be. Like reference numerals refer to like elements throughout.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.

In addition, in this specification, when a part such as a layer, film, region, plate, etc. is said to be "on" or "upper" another part, it is not only when the other part is "directly over" but also another part in the middle. Also includes. On the contrary, when a part is "just above" another part, there is no other part in the middle. In addition, when a part such as a layer, a film, an area, or a plate is "below" or "below" another part, it is not only when the part is "below" but also another part in the middle. Include. In contrast, when a part is "just below" another part, there is no other part in the middle.

In one embodiment of the present invention, a multi-layer laser marking film comprising 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. to provide.

 At this time, the colored base layer is a urethane (meth) acrylate oligomer, (meth) acrylate monomer; And a cured product of the base composition comprising a pigment, wherein the adhesive layer is a first alkyl (meth) acrylate having a linear or branched alkyl group of 1 to 3 carbon atoms; Second alkyl (meth) acrylates having linear or branched alkyl groups of 4 to 16 carbon atoms; And hardened | cured material of the adhesive composition containing the copolymerization resin of the mixed monomer component containing the (meth) acrylate which has a carboxyl group. It is characterized by the above-mentioned.

1 schematically illustrates a multilayer laser marking film 100 according to an embodiment of the present invention, and specifically, schematically illustrates a cross section thereof.

Referring to FIG. 1, the multilayer laser marking film 100 includes an adhesive layer 10, a colored substrate layer 20, and a colored coating layer 30. For example, the multilayer laser marking film 100 may be formed directly on the adhesive layer 10. A colored substrate layer 20 may be formed on the colored substrate layer 20, and the colored substrate layer 20 may include a multi-layered structure on which the colored coating layer 30 is formed.

The multilayer laser marking film is a film which can be etched by a laser to write various information, and the 'laser marking' means to write information on the film by etching by a laser. Specifically, in the multilayer laser marking film, laser marking may be performed on the colored coating layer.

That is, the multilayer laser marking film has laser marking property, and the laser marking property means a physical property that the colored coating layer is etched by laser irradiation, and the etched portion is removed. As such, the laser irradiated portion of the colored coating layer is etched and removed to interact with the colored substrate layer to write various letters, patterns, and the like.

The colored base layer 20 and the colored coating layer 30 are both colored layers, meaning 'colored' indicates that the base layer or coating layer is not transparent and has a color such as white, black, blue, or the like. . Specifically, the colored base 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 from each other.

As such, when the colored substrate layer and the colored coating layer have different colors from each other, when the colored coating layer is etched by laser marking, the etched portion may exhibit various colors according to the etching depth.

Specifically, referring to FIG. 2 (a), only the first color of the colored substrate layer 20 may be visually recognized when all of the colored coating layers 30 are etched by laser marking. . In addition, referring to FIG. 2B, when a part of the thickness of the colored coating layer 30 is etched, the colored coating layer 30 remaining without being etched with the first color of the colored base layer 20 is etched. The color in which the second color overlaps may be visually recognized.

The multilayer laser marking film can be written characters or patterns of various colors through the laser marking in this way. For example, the multilayer laser marking film may be used in automobiles, and specifically, may display information about various parts of the vehicle such as tire pressure or fuel type, or may provide unique security information such as chassis number and vehicle identification number. Can be used to indicate.

When the multilayer laser marking film according to an embodiment of the present invention is applied to the final position in this way, it may be wrongly attached to a position other than the position to be attached. In this case, the reworking may be easily carried out within a short time after attachment. It may have a possible advantage.

In addition, the multilayer laser marking film needs to prevent forgery or modulation when important information is written. Specifically, the multilayer laser marking film may have 'fragability'. "Fragmentable" refers to physical properties that cannot be recycled because the original shape is destroyed when an attempt is made to detach or remove the multilayer laser marking film after it is attached to the adherend. Since the multilayer laser marking film has self-destructive property, it is impossible to arbitrarily change the unique information written therein, and it is possible to secure a property that cannot be forged or modulated.

The multilayer laser marking film may implement such physical properties and advantages by appropriately controlling the composition and structure of the colored substrate layer and the adhesive layer.

Specifically, in the multilayer laser marking film according to the embodiment of the present invention, the colored substrate layer is a substrate composition comprising a (meth) acrylate oligomer and (meth) acrylate monomer as a matrix (matrix) constituting it It contains the hardened | cured material of.

The urethane (meth) acrylate oligomer is an oligomer comprising a urethane structure (-CONH-) in a chemical structure, and is easier to control the molecular weight than an oligomer including other chemical structures, and improves the crushability of the colored substrate layer. It is advantageous to control the elongation at the same time, it may be advantageous to properly secure the interfacial adhesion between the colored substrate layer and the upper and lower adhesive layers and the colored coating layer.

The urethane (meth) acrylate oligomer may have a weight average molecular weight (Mw) of about 2,000 to about 10,000, for example, about 2,000 to about 4,000. Since the urethane (meth) acrylate oligomer has a weight average molecular weight (Mw) in the above-mentioned range, the cured product of the base composition may have an appropriate cured structure, and between the colored substrate layer, the adhesive layer, and the colored coating layer Appropriate interface adhesion of each can be ensured. In addition, the colored substrate layer can greatly contribute to improving the fracture properties of the multi-layer laser marking film, it is possible to easily perform the role of implementing the basic durability by configuring a basic matrix (matrix) of the colored substrate layer.

In addition, the urethane (meth) acrylate oligomer may be a trifunctional to six-functional oligomer. That is, the urethane (meth) acrylate oligomer may contain 3 to 6 (meth) acrylate groups in one molecule.

In one embodiment, the urethane (meth) acrylate oligomer is tri- to 4-functional oligomer; 5- or 6-functional oligomers; Or it may be a mixture of both. The trifunctional to tetrafunctional oligomers may impart excellent crushability by performing a curing reaction with the (meth) acrylate monomer, and the 5-functional to six-functional oligomers perform excellent crushing by performing a curing reaction in the oligomer itself. You can give it a surname.

The base composition comprises a (meth) acrylate monomer together with the urethane (meth) acrylate oligomer.

Specifically, the (meth) acrylate monomers are cyclo-aliphatic (meth) acrylate monomers, epoxy (epoxy) (meth) acrylate monomers, aliphatic (aliphatic) (meth) acrylate monomers, It may include one selected from the group consisting of polyol-based (meth) acrylate monomers and combinations thereof.

By including the (meth) acrylate monomer having a chemical structure of the kind described above, the monomer can interact with the urethane (meth) acrylate oligomer to greatly improve the fractureability of the multilayer laser marking film.

In addition, the weight average molecular weight (Mw) of the (meth) acrylate monomer may be about 200 to about 500, for example, may be about 200 to about 300, for example may be about 300 to about 400. . By satisfying the above-mentioned range, the weight average molecular weight of the (meth) acrylate monomer can be appropriately crosslinked through a curing reaction between the oligomers acting as a matrix, and as a result, a dense, hard colored pigment It is possible to implement a coating layer.

In addition, the oligomer and the monomer of the base composition satisfy each weight average molecular weight (Mw) in the above-mentioned range at the same time can be expected to have a high density and high reliability, and at the same time excellent reliability, thereby providing high tensile strength and appropriate elongation This ensures excellent crushability and workability.

The (meth) acrylate monomer may be a bifunctional or higher monomer, for example, a bifunctional to tetrafunctional monomer. That is, the (meth) acrylate monomer may have two or more photoreactive functional groups, for example, two to four in one molecule. In addition, the photoreactive functional group may be a (meth) acrylate group.

Specifically, the cycloaliphatic (meth) acrylate monomer includes an alicyclic functional group in a chemical structure, for example, a cycloalkyl group having 3 to 25 carbon atoms and a heterocycloalkyl group having 2 to 25 carbon atoms. It may include at least one selected from the group consisting of. More specifically, the cycloaliphatic (meth) acrylate monomer may include one selected from the group consisting of cyclohexanedimethanol diacrylate, tricyclodecanedimethanol diacrylate, and combinations thereof. have.

The epoxy-based (meth) acrylate monomers may include novolak-type epoxy (meth) acrylates, bisphenol-A type epoxy (meth) acrylates, bisphenol-S type epoxy (meth) acrylates, Bisphenol-F type epoxy (meth) acrylate, phenol type epoxy (meth) acrylate, cresol novolak type epoxy (meth) acrylate, and combinations thereof.

In addition, the aliphatic (meth) acrylate monomer may be a compound having a (meth) acrylate group at each end of the main chain consisting of alkylene structural units having 1 to 16 carbon atoms. More specifically, the aliphatic (meth) acrylate monomers are 1,6-hexanedioldi (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,4-butanedioldi (meth) ) Acrylates and combinations thereof.

In addition, the polyol (meth) acrylate monomer is 1,6-hexanediol (ethoxylate) diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene It may include one selected from the group consisting of glycol diacrylate and combinations thereof.

The multilayer laser marking film is remarkably excellent in crushability. In addition, the interface between the colored substrate layer and the colored coating layer has an interface adhesion suitable for allowing the colored coating layer to be removed from the colored substrate layer by laser marking to enable writing of fine characters and designs. In addition, the interface between the colored substrate layer and the adhesive layer has an interface adhesion suitable for applying the multilayer laser marking film to the final article to be firmly attached to achieve long-term durability.

The colored base layer is an intermediate layer in contact with both the colored coating layer and the adhesive layer, it is possible to implement the above-described physical properties and advantages by appropriately controlling the composition thereof.

Specifically, the substrate composition for forming the colored substrate layer may include more than about 0 parts by weight and about 66 parts by weight or less of the (meth) acrylate monomer based on 100 parts by weight of the urethane (meth) acrylate oligomer. May, for example, comprise about 25 to about 40 parts by weight. As the (meth) acrylate monomer is used in the above-described content of the oligomer, the effect of improving the crushability of the colored base layer is further improved, and the composition is cured to have an appropriate hard and elongation, so that durability and workability Can improve.

  The substrate composition includes a pigment as a component for imparting color to the colored substrate layer. The type of the pigment is not particularly limited, and various pigments may be used alone or as appropriate, depending on the color of the colored substrate layer.

The pigment may be, for example, titanium dioxide (TiO 2 ), carbon black, iron, azo pigments, cobalt violet, cadmium sulfide, chromium salts ferrocyanide, silicates, phosphates, phthalocyanine compounds, It may include one selected from the group consisting of dioxazine compounds and combinations thereof, but is not limited thereto.

The base composition may include about 50 to about 135 parts by weight of the pigment, for example, about 80 to about 120 parts by weight based on 100 parts by weight of the urethane (meth) acrylate oligomer. When the pigment is contained too little, the effect may be reduced in terms of contrast of the color with the colored coating layer, and the crushability may also be reduced. In addition, laser processing may not be performed properly. On the contrary, when the pigment is excessively contained, it may give a negative tendency to the curing process of the substrate composition, and may prevent the colored substrate layer from securing appropriate interfacial adhesion and crushability. Therefore, the pigment may be used in the above-described content of content to exhibit a suitable color without lowering the required physical properties of the colored substrate layer.

The colored substrate layer may include a cured product of the substrate composition, and the cured product may be an electron beam cured product or an ultraviolet (UV) cured product. In the case of curing by heat or other curing means, since curing proceeds slowly with little energy, the fracture property of the base layer is lowered and the elongation is excessively large, so that the desired physical properties cannot be realized. Therefore, since the colored base layer is made of an electron beam cured product or an ultraviolet cured product, a large amount of energy is instantaneously applied during curing, thereby facilitating securing fracture properties.

Referring to FIG. 1, the multilayer laser marking film 100 includes an adhesive layer 10 disposed on one surface of the colored substrate layer 20, and the adhesive layer 10 is colored as described above. Together with the base layer serves to improve the crushability and reworkability.

Specifically, the pressure-sensitive adhesive layer is a first alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms; Second alkyl (meth) acrylates having linear or branched alkyl groups of 4 to 16 carbon atoms; And hardened | cured material of the adhesive composition containing the copolymerization resin of the mixed monomer component containing the (meth) acrylate which has a carboxyl group.

The copolymer resin of the pressure-sensitive adhesive composition may have a weight average molecular weight (Mw) of about 1 million to about 1.5 million, for example, about 1.2 million to about 1.3 million. By controlling the weight average molecular weight of the copolymer resin in the above range, the build-up process of the adhesive layer and the adherend may occur at an appropriate speed, and as a result, the multilayer laser marking film may realize improved reworkability. have. In addition, the pressure-sensitive adhesive layer may be easy to implement appropriate fracture properties with the colored substrate layer.

 Specifically, the first alkyl (meth) acrylate has a linear or branched alkyl group having 1 to 3 carbon atoms, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) ) Acrylate, isopropyl (meth) acrylate, and combinations thereof.

In addition, the second alkyl (meth) acrylate has a linear or branched alkyl group having 4 to 16 carbon atoms, for example, 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 ( Meta) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, and combinations thereof.

In addition, the (meth) acrylate having a carboxyl group may include one selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, and combinations thereof.

The mixed monomer component is a weight average molecular weight (Mw) in the above-mentioned range by using (meth) acrylate having the first alkyl (meth) acrylate, the second alkyl (meth) acrylate and the carboxyl group in an appropriate content ratio It is possible to easily prepare a copolymer resin having, and further, by the chemical structure derived from each monomer, the adhesive layer can implement an appropriate interfacial adhesion with the colored substrate layer, the multilayer laser marking film has excellent fracture properties and Good reworkability can be achieved simultaneously.

Specifically, the mixed monomer component is a weight ratio of the first alkyl (meth) acrylate: the second alkyl (meth) acrylate: (meth) acrylate having the carboxyl group is 20 to 30: 60 to 70: 5 to May be 15.

The adhesive composition may further include a solvent and a curing agent together with the copolymer resin.

The solvent is not particularly limited in kind, but may include toluene. The adhesive composition can secure an appropriate viscosity range through the solvent, it is possible to improve the coating properties and processability.

The adhesive composition may have a viscosity of about 1000 cps to about 5000 cps at room temperature of about 20 ° C to about 30 ° C, for example, about 1500 cps to about 3000 cps. By controlling the viscosity of the pressure-sensitive adhesive composition in the above range it can be implemented excellent coating properties and processability.

The curing agent may include one selected from the group consisting of aziridine-based curing agents, peroxide-based curing agents, isocyanate-based curing agents, and combinations thereof. In one embodiment, the curing agent may include an aziridine-based curing agent. In addition, the pressure-sensitive adhesive composition may include 0.01 to 1 parts by weight of the curing agent, relative to 100 parts by weight of the copolymer resin.

The multilayer laser marking film is used by attaching the adhesive layer to abut the adherend. In this case, the multilayer laser marking film may have an adhesive force of about 1000 gf / inch or less after about 1 minute to about 10 minutes after attaching the adhesive layer to a metal adherend, for example, greater than about 0 gf / inch. , About 1000 gf / inch or less. As a result, the multilayer laser marking film can be detached again within a short time after being attached, and as a result, it can exhibit improved reworkability.

Referring to FIG. 1, the multilayer laser marking film 100 includes a colored coating layer 30 disposed on one surface of the colored substrate layer 20. The colored coating layer 30 is a layer to be laser marking, and is etched by laser irradiation to be separated and removed from the colored substrate layer 20.

The colored coating layer 30 may include an ultraviolet (UV) cured product or an electron beam cured product of the coating composition, thereby realizing excellent reliability as compared with the case of manufacturing by other curing means such as thermosetting.

Specifically, the coating composition may be an ultraviolet curable oligomer or an electron beam curable oligomer; And pigments.

The ultraviolet curable oligomer or the electron beam curable oligomer may include a bifunctional bisphenol A-based epoxy acrylate oligomer, a trifunctional urethane acrylate oligomer, or a mixture thereof.

Each of the ultraviolet curable oligomer or the electron beam curable oligomer may have a weight average molecular weight (Mw) of about 500 to about 3,000, for example, about 500 to about 2,000. As a result, the colored coating layer may have excellent durability, and the precision of laser marking may be improved.

As described above, the colored coating layer has a different color from the colored substrate layer. In such a range that satisfies conditions having different colors, the coating composition includes a pigment.

For example, the pigment is titanium dioxide (TiO 2 ), carbon black, iron, azo pigments, cobalt violet, cadmium sulfide, chromium salts ferrocyanide, silicate, phosphate, phthalocyanine Compounds, dioxazine compounds may include one selected from the group consisting of, and combinations thereof, but is not limited thereto.

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

On the other hand, the colored base layer and the colored coating layer may include the same pigments while adjusting the content thereof to implement different colors.

The coating composition may include about 1 to about 20 parts by weight of the pigment based on 100 parts by weight of the ultraviolet curable oligomer or the electron beam curable oligomer. As a result, the colored coating layer can easily secure proper adhesion to the colored substrate layer, and at the same time can realize precise laser marking performance while exhibiting an appropriate color.

The multilayer laser marking film may include the colored coating layer, the colored substrate layer, and the adhesive layer together to implement improved crushability, and the interface adhesion between the layers is properly controlled, so that the precision of the laser marking and the durability of the final article may be achieved. Can be secured at the same time.

The multi-layer laser marking film can be designed to ensure the characteristics of precise laser marking by easily designing the thickness of the layer, to realize the crushability, and to ensure the property of no breakage or tearing when the adhesion is measured despite the high adhesion. have.

The colored coating layer may have, for example, about 2 μm to about 4 μm. Since the thickness range of the colored coating layer satisfies this, the efficiency of laser marking is improved, and the colored coating layer etched from the colored substrate layer can be neatly removed, and thus the effect of excellent visibility after laser marking can be easily realized. .

In addition, the colored substrate layer may have, for example, about 50 μm to about 150 μm. The thickness of the colored substrate layer together with the thickness of the colored coating layer satisfies such a range, thereby achieving excellent durability of the colored substrate layer at the time of laser marking, and greatly contributing to improving the crushability of the multilayer laser marking film. The distribution or handling of the multilayer laser marking film is easy, and the punchability by the laser may be excellent when the multilayer laser marking film is processed to a desired size.

In addition, the adhesive layer may have a thickness of about 20 μm to about 50 μm. When the thickness of the adhesive layer satisfies the above range, the multilayer laser marking film secures adhesion to the final article and at the same time greatly improves crushability, and the multilayer laser marking film smoothly functions as an adhesive tape. You can get the effect.

As described above, referring to FIG. 1, the multilayer laser marking film 100 may include a multilayer structure of the adhesive layer 10, the colored substrate layer 20, and the colored coating layer 30. In this case, referring to FIG. 3, the multilayer laser marking film 100 may further include a release layer 40 on one or both surfaces of the outermost shell.

As shown in FIG. 3A, the release layer 40 may be formed only on one surface of the adhesive layer 10, and as shown in FIG. 3B, one surface of the adhesive layer 10 and the colored coating layer ( 30 may be formed together.

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

In another embodiment of the present invention, a method of manufacturing the multilayer laser marking film is provided. The multilayer laser marking film is a method of manufacturing a colored substrate layer including a cured product of the substrate composition, manufacturing a colored coating layer on one surface of the colored substrate layer, and manufacturing an adhesive layer on the other surface of the colored substrate layer. Can be prepared.

Specifically, the multilayer laser marking film is the step of applying the substrate composition on one release film, and laminating another release film thereon; Curing the substrate composition to form a laminate in which a colored substrate layer having a first color is disposed between 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 surface of the colored substrate layer; And forming an adhesive layer on the other surface of the colored base layer after removing the other release film from the laminate.

As such, after the multilayer laser marking film preferentially forms a laminate having a structure in which a colored substrate layer is interposed between two release films, both surfaces of the colored substrate layer are subsequently removed while sequentially removing the two release films. By forming the colored coating layer and the pressure-sensitive adhesive layer in each, it is possible to secure the interface adhesion between the layers. In addition, the thickness uniformity of the colored substrate layer can be improved.

Specifically, the colored coating layer is the step of applying the coating composition on one surface of the colored substrate layer; And curing the coating composition to form a colored coating layer.

Alternatively, the colored coating layer comprises the steps of preparing a transfer film comprising a cured product of the coating composition; And transferring the cured product of the coating composition through the transfer film to one surface of the colored substrate layer to prepare a colored coating layer.

The adhesive layer may be prepared by directly coating the adhesive composition on one surface of the colored substrate layer, followed by thermosetting, or after preparing the adhesive layer including the thermoset of the adhesive composition in advance. It can be prepared by laminating on one side of.

In this case, the method of manufacturing the multilayer laser marking film may further include corona treatment before forming an adhesive layer on one surface of the colored substrate layer. That is, before the adhesive composition is directly coated; Alternatively, a corona treatment may be performed on one surface of the colored substrate layer before the adhesive layer is laminated.

In one embodiment, the method of manufacturing the multilayer laser marking film is subjected to a corona treatment on one surface of the colored substrate layer, and then heat-cured after direct coating the adhesive composition on one surface of the corona treatment. An adhesive layer can be manufactured by the method of making it. In this case, it may be advantageous to improve the adhesion between the colored substrate layer and the adhesive layer.

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

< Production Example >

Production Example  1: Preparation of Substrate Composition

To 100 parts by weight of the trifunctional urethane acrylate oligomer having a weight average molecular weight (Mw) of 2,500, 25 parts by weight of an alicyclic acrylate monomer having a weight average molecular weight (Mw) of 304, and 70 parts by weight of titanium dioxide (TiO 2 ) The base composition containing was prepared.

Production Example  2-4: Preparation of Adhesive Composition

A pressure-sensitive adhesive composition comprising a copolymer resin and an aziridine-based curing agent as described in Table 1 was prepared, respectively. In Table 1, the content is described in parts by weight.

Adhesive composition Copolymer resin Aziridine Curing Agent Creation costs Mw content Kinds content Preparation Example 2 MA: EHA: AA = 25: 65: 10 1.25 million 100 Isophthaloylbis (2-Methylaziridine) 0.04 Preparation Example 3 MA: EHA: AA = 30: 65: 5 1.3 million 100 Isophthaloylbis (2-Methylaziridine) 0.04 Preparation Example 4 MA: EHA: AA = 25: 70: 5 1.1 million 100 Isophthaloylbis (2-Methylaziridine) 0.04 Preparation Example 5 GMA: EHA: AA = 25: 65: 10 1 million 100 Isophthaloylbis (2-Methylaziridine) 0.04 Preparation Example 6 GMA: BA: AA = 10: 80: 10 520,000 100 Isophthaloylbis (2-Methylaziridine) 0.04 Preparation Example 7 MA: HBA: AA = 25: 65: 10 340,000 100 Isophthaloylbis (2-Methylaziridine) 0.04

* MA: methyl acrylate

* EHA: ethylhexyl acrylate

* AA: acrylic acid

* GMA: glycidyl methacrylate

* BA: Butylacrylate

* HBA: hydroxybutyl acrylate

< Example  And Comparative example >

Example  One

The base composition of Preparation Example 1 was applied to one surface of a polyethylene terephthalate (PET) release film, and the same PET release film was laminated thereon.

Subsequently, a laminate in which a release film, a colored substrate layer, and a release film was laminated was cured by curing the substrate composition through electron beam curing. Subsequently, one release film of the laminate was peeled off, and a trifunctional urethane acrylate oligomer having a weight average molecular weight (Mw) of 1900 as an ultraviolet curable oligomer was formed on one surface of the colored substrate layer on which the release film was peeled off. 100 parts by weight of a mixture of Chemical, MIRAMER PU3200) and a bifunctional bisphenol A-based epoxy acrylate oligomer (SARTOMER, CN120C80); And a coating composition including 5 parts by weight of carbon black, followed by UV curing to prepare a colored coating layer.

Subsequently, another release film of the laminate was peeled off, the back surface of the colored substrate layer was subjected to corona treatment, and then the pressure-sensitive adhesive composition of Preparation Example 2 was applied, followed by thermosetting at 110 ° C. for 3 minutes. Prepared.

Thus, a multilayer laser marking film including a 2 μm thick colored coating layer, a 100 μm thick colored substrate layer, and a 25 μm thick adhesive layer was prepared.

Example  2

A multilayer laser marking film was prepared in the same manner as in Example 1, except that the adhesive composition of Preparation Example 3 was used.

Example  3

A multilayer laser marking film was prepared in the same manner as in Example 1, except that the adhesive composition of Preparation Example 4 was used.

Comparative example  One

A multilayer laser marking film was prepared in the same manner as in Example 1, except that the adhesive composition of Preparation Example 5 was used.

Comparative example  2

A multilayer laser marking film was manufactured in the same manner as in Example 1, except that the adhesive composition of Preparation Example 6 was used.

Comparative example  3

A multilayer laser marking film was prepared in the same manner as in Example 1, except that the adhesive composition of Preparation Example 7 was used.

<Evaluation>

Experimental Example  1: within a short time Reprocessable  evaluation

With respect to the multilayer laser marking films of Examples 1-3 and Comparative Examples 1-3, after fabrication of 2.54 cm x 10 cm (width x length) specimens, each adhesive layer abuts on an aluminum plate. 2kg rollers are reciprocated five times so that the end 2cm of the longitudinal direction is not attached. After 10 minutes have elapsed from the time of attachment, desorption is attempted from the portion not attached to the terminal in the longitudinal direction, and the desorption is observed. In addition, when detachable, it is observed whether it is attached again.

The results are as described in Table 2 below. Specifically, the case where the multilayer laser film can be detached and can be reattached is described as 'OK', and the case where the multilayer laser film is damaged without being detached or a peeling residue remains is described as 'NG'.

Experimental Example  2: Crushable  evaluation

For the multilayer laser marking films of Examples 1-3 and Comparative Examples 1-3, a 75 mm × 150 mm size sample was attached to an aluminum coating plate, and then exposed to 100% isopropyl alcohol (IPA). After 1 hour of use, the fracture was evaluated according to whether or not a broken form was seen when forcibly desorption was attempted using a knife, and the results are shown in Table 2 below. The case of crushing at the desorption attempt was described as 'OK', and the case of desorption without crushing at the desorption attempt was described as 'NG'.

Short reworkability Crushable Removability after 10 minutes Reattachment after detachment Example 1 OK OK OK Example 2 OK OK OK Example 3 OK OK OK Comparative Example 1 OK NG OK Comparative Example 2 NG NG OK Comparative Example 3 NG NG OK

When referring to Table 1 and Table 2, the multilayer laser marking film of Examples 1 to 3 according to an embodiment of the present invention through the colored base layer and the adhesive layer as described above, of the Comparative Examples 1 to 3 Compared with the multilayer laser marking film, it can be seen that the short reworkability and the crushability are realized at the same time.

Specifically, in the case of Comparative Example 1 it can be seen that the desorption is possible within a short time after the attachment, but it is impossible to reattach, so that it does not implement the required level of short-term reprocessing.

In addition, in the case of Comparative Examples 2 to 3, since it is impossible to detach and reattach within a short time after the attachment, it can be seen that the reprocessing is significantly inferior to Examples 1 to 3.

100, 100 ': multilayer laser marking film
10: adhesive layer
20: colored base material layer
30: colored coating layer
40: release layer

Claims (17)

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 is a urethane (meth) acrylate oligomer; (Meth) acrylate monomers; And a cured product of the base composition comprising the pigment,
The adhesive layer may include a first alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms; Second alkyl (meth) acrylates having linear or branched alkyl groups of 4 to 16 carbon atoms; And a cured product of the pressure-sensitive adhesive composition comprising a copolymerized resin of a mixed monomer component containing a (meth) acrylate having a carboxyl group,
The mixed monomer component is a weight ratio of the first alkyl (meth) acrylate: second alkyl (meth) acrylate: (meth) acrylate having a carboxyl group is 20 to 30:60 to 70: 5 to 15
Multilayer Laser Marking Film.
The method of claim 1,
The colored coating layer has a laser marking property that is etched by laser irradiation and the etched portion is removed.
Multilayer Laser Marking Film.
The method of claim 1,
The weight average molecular weight (Mw) of the copolymer resin is 1 million to 1.5 million
Multilayer Laser Marking Film.
delete The method of claim 1,
The weight average molecular weight (Mw) of the urethane (meth) acrylate oligomer is 2,000 to 10,000
Multilayer Laser Marking Film.
The method of claim 1,
The urethane (meth) acrylate oligomer is trifunctional to six functional
Multilayer Laser Marking Film.
The method of claim 1,
The molecular weight of the (meth) acrylate monomer is 200 to 500
Multilayer Laser Marking Film.
The method of claim 1,
The (meth) acrylate monomer is bifunctional to tetrafunctional
Multilayer Laser Marking Film.
The method of claim 1,
The (meth) acrylate monomers include cyclo-aliphatic (meth) acrylate monomers, epoxy (epoxy) (meth) acrylate monomers, aliphatic (meth) acrylate monomers, and polyols. ) -Containing (meth) acrylate monomers and combinations thereof
Multilayer Laser Marking Film.
The method of claim 1,
The base composition comprises more than 0 parts by weight and 66 parts by weight or less of the (meth) acrylate monomer, based on 100 parts by weight of the urethane (meth) acrylate oligomer.
Multilayer Laser Marking Film.
The method of claim 1,
The base composition comprises 50 to 135 parts by weight of the pigment based on 100 parts by weight of the urethane (meth) acrylate oligomer.
Multilayer Laser Marking Film.
The method of claim 1,
After the adhesive layer is attached to the adherend of the metal material, the adhesion after 1 minute to 10 minutes is less than 1000gf / inch
Multilayer Laser Marking Film.
The method of claim 1,
The colored coating layer may be an ultraviolet curable oligomer or an electron beam curable oligomer; And a cured product of the coating composition comprising the pigment.
Multilayer Laser Marking Film.
The method of claim 13,
The ultraviolet curable oligomers or electron beam curable oligomers each include a bifunctional bisphenol A-based epoxy acrylate oligomer, a trifunctional urethane acrylate oligomer, or a mixture thereof.
Multilayer Laser Marking Film.
Urethane (meth) acrylate oligomer, (meth) acrylate monomer on one release film; And applying a base composition comprising the pigment, and laminating another release film thereon;
Curing the substrate composition to form a laminate in which a colored substrate layer having a first color is disposed between 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 surface of the colored substrate layer; And
A first alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 3 carbon atoms on the other side of the colored substrate layer after removing another release film from the laminate; Second alkyl (meth) acrylates having linear or branched alkyl groups of 4 to 16 carbon atoms; And forming a pressure-sensitive adhesive layer comprising a cured product of the pressure-sensitive adhesive composition comprising a copolymerized resin of a mixed monomer component comprising a (meth) acrylate having a carboxyl group.
The mixed monomer component is a weight ratio of the first alkyl (meth) acrylate: second alkyl (meth) acrylate: (meth) acrylate having a carboxyl group is 20 to 30: 60 to 70: 5 to 15
The method for producing a multilayer laser marking film according to any one of claims 1 to 3 and 5 to 14.
The method of claim 15,
Forming the adhesive layer,
Forming the adhesive composition on the other side of the colored substrate layer by direct coating and then curing;
Forming a pressure-sensitive adhesive layer including the cured product of the pressure-sensitive adhesive composition on the other side of the colored substrate layer;
Method for producing a multilayer laser marking film.
The method of claim 15,
Forming the adhesive layer,
Further comprising corona treatment before forming an adhesive layer on the other side of the colored substrate layer.
Method for producing a multilayer laser marking film.
KR1020160045165A 2016-04-12 2016-04-12 Multilayer laser marking film and method for manufacturing the same KR102046532B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020160045165A KR102046532B1 (en) 2016-04-12 2016-04-12 Multilayer laser marking film and method for manufacturing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020160045165A KR102046532B1 (en) 2016-04-12 2016-04-12 Multilayer laser marking film and method for manufacturing the same

Publications (2)

Publication Number Publication Date
KR20170116902A KR20170116902A (en) 2017-10-20
KR102046532B1 true KR102046532B1 (en) 2019-12-02

Family

ID=60299349

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020160045165A KR102046532B1 (en) 2016-04-12 2016-04-12 Multilayer laser marking film and method for manufacturing the same

Country Status (1)

Country Link
KR (1) KR102046532B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102165099B1 (en) * 2017-06-01 2020-10-13 주식회사 엘지화학 Multilayer marking film

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003132319A (en) * 2001-10-19 2003-05-09 Oji Paper Co Ltd Ic card, its manufacturing method, and ultraviolet curing ink
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

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011080883A1 (en) * 2011-08-12 2013-02-14 Tesa Se Temperature-resistant laser-inscribable film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003132319A (en) * 2001-10-19 2003-05-09 Oji Paper Co Ltd Ic card, its manufacturing method, and ultraviolet curing ink
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

Also Published As

Publication number Publication date
KR20170116902A (en) 2017-10-20

Similar Documents

Publication Publication Date Title
TWI546366B (en) And a method for manufacturing a dicing film and a wafer having a protective film forming layer
CN110092937B (en) Protective film forming film, protective film forming sheet, and method for producing processed product
JP6557912B2 (en) Composite sheet for protective film formation
EP2710084B1 (en) Processing tapes for preparing laminate articles
WO2015016063A1 (en) Protective film formation-use composite sheet
TW201422757A (en) Dicing sheet with protective film formation layer and method for producing chip
CN114266334B (en) Holographic anti-counterfeiting PC film, PC card and preparation method
KR20230035012A (en) Pattered Adhesive tape, Release film for forming the same and Method of producing Release film
KR102046530B1 (en) Multilayer laser marking film and method for manufacturing the same
KR102046532B1 (en) Multilayer laser marking film and method for manufacturing the same
US11795344B2 (en) Multilayer marking film
US11142670B2 (en) Multilayer marking film and manufacturing method for multilayer marking film
KR102063543B1 (en) Multilayer laser marking film and method for manufacturing the same
KR102153287B1 (en) Multilayer marking film
KR102046528B1 (en) Multilayer laser marking film and method for manufacturing the same
KR102155493B1 (en) Multilayer marking film
KR102063538B1 (en) Multilayer laser marking film and method for manufacturing the same
KR102046529B1 (en) Multilayer laser marking film and method for manufacturing the same
KR102060804B1 (en) Multilayer laser marking film and method for manufacturing the same
JP2021155624A (en) Release film and manufacturing method of laminate
CN115820168A (en) Protective film forming film, composite sheet for protective film formation, and method for producing workpiece with protective film
KR20170114691A (en) Multilayer laser marking film and method for manufacturing the same

Legal Events

Date Code Title Description
N231 Notification of change of applicant
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant