JP5717690B2 - Transparent laser marking sheet, laminate, and laser marking method - Google Patents

Description

  The present invention relates to a transparent laser marking sheet, a laminate, and a laser marking method.

  As international exchange is progressing, the movement of human resources has become active. As a means of identifying individuals and identifying their identities and identities, ID cards that record personal information or so-called identification cards such as passports (identifications) ) Etc. are used. In particular, the importance of ID cards issued by public institutions and highly reliable organizations is increasing.

  Since the September 2001 global terrorist attacks in September 2001, various countries have taken measures such as stricter immigration control. For example, the United Nations specialized organization ICAO (International Civic Aviation Organization) has established a standard, and efforts to introduce it into electronic passports have been started in each country. In this approach, forgery prevention is important, and for that purpose, a technique for laser marking personal names, symbols, characters, photographs or the like on electronic passports has attracted attention.

  The electronic passport can identify and prove an individual. Therefore, if a third party other than the country (or a national agency) can easily tamper or forge personal information, the reliability of identification is lowered. And it may hinder the progress of international exchange and the global movement of human resources.

  Therefore, how to prevent tampering and counterfeiting is an important problem in the aforementioned electronic passport. Furthermore, since the electronic passport is composed of a light, thin, and short standard, it is important how the personal name, symbol, character, photograph, or the like can be displayed clearly with high contrast. In particular, whether a display with high contrast and clearness can be realized leads to prevention of tampering and counterfeiting, and therefore the market is highly expected.

  For such a problem, a technique for laser marking an individual name, a symbol, a character, a photograph, or the like, specifically a laser marking sheet, has attracted attention. For example, there are the following Patent Documents 1 and 2.

  Patent Document 1 discloses a technique related to the production of a flexible data sheet in a security document such as a passport. Specifically, it is a technique related to a data sheet of a security document including a data portion and an attachment portion. The data portion is configured to include a data area in which at least some data in the data sheet is recorded using a laser inscription technique. The attachment portion is configured to be flexible and bend resistant to secure the data sheet to the security document.

  Patent Document 2 discloses a technique related to a laser marking multilayer sheet used for an electronic passport and an electronic passport using the multilayer sheet. Specifically, the technology of Patent Document 2 is configured as a laser marking multilayer sheet for electronic passports in which five layers of multilayer sheet A / multilayer sheet B / film C / multilayer sheet B / multilayer sheet A are laminated. . Furthermore, the multilayer sheet A is a transparent laser marking multilayer sheet having a skin layer and a core layer and formed from at least three sheets. The multilayer sheet B is a colored laser marking multilayer sheet having a skin layer and a core layer and formed from at least three layers. Further, the film C is a resin film or a film made of cloth.

JP-T-2006-527670 JP 2009-279906 A

  By the way, in the technique of Patent Document 1, two sheets are partially separated from one, and an adhesive is applied between the two sheets and a part thereof is further disposed. The data sheet is then laminated at a high temperature. Furthermore, in the technique of Patent Document 1, a data sheet is also disclosed in which a filling layer made of the same material or the like as the sheet is disposed between two sheets.

  However, the technique disclosed in Patent Document 1 is not limited to laminating a sheet printed by the laser inscription technique. That is, a sufficient integration effect cannot be obtained for a data sheet composed of a combination of a sheet printed by laser inscription and a sheet printed by another method.

  For example, combining a sheet printed by UV offset printing or UV silk printing and a sheet printed by laser inscription technology as a data sheet is effective from the viewpoint of design and prevention of counterfeiting. It becomes. On the other hand, in this combination, integration with a sheet printed by different methods as described above is important. In this regard, in the technique of the cited document 1, when lamination or the like is performed on a sheet on which UV offset printing or UV silk printing has been performed, the lamination can be easily taken and cannot be integrated.

  Furthermore, in patent document 1, it is comprised so that it may isolate | separate partially from one. Therefore, a combination of a plurality of sheets constitutes a complicated design and is not suitable for counterfeiting.

  Moreover, in the technique of patent document 2, it integrates by heating or pressurization. Therefore, there is room for improvement in terms of bonding in terms of reliable integration as a laminate comprising a combination of a laser-marked sheet and a sheet printed by UV offset printing or UV silk printing. This is because it is important not to cause defects such as peeling as a countermeasure against tampering and counterfeiting.

  Further, the technique of Patent Document 2 has room for improvement in terms of versatility and molding processability. When used as an ID card or an ID card or a passport, a public organization or a highly reliable organization often processes the data finally. In such a case, a material that is easy to handle is preferred.

  The present invention has been made to solve the above-described problems, and provides an excellent transparent laser marking sheet, laminate, and laser marking method that have both heat fusion, adhesion, and transparency. It is.

  The transparent laser marking sheet of the present invention has good adhesion between the base sheet and the transparent thermoactive adhesive, has high versatility, and is easy to mold.

  Further, in the laminate of the present invention in which at least a printing sheet is adhered to the adhesive layer of the transparent laser marking sheet of the present invention, printing by laser marking, printing by UV offset printing, etc., or by UV silk printing It can realize clear display such as printing, and is excellent in preventing falsification and forgery.

  According to the present invention, the following transparent laser marking sheet, laminate, and laser marking method are provided.

[1] A transparent laser marking sheet in which an adhesive layer is provided on at least one surface of a base sheet, wherein the base sheet is composed of a polycarbonate resin and a transparent polycarbonate resin composition containing a laser light energy absorber. It is configured as a single-layer sheet, or the base sheet has a skin layer and a core layer, and the skin layer that is both outermost layers consists of a thermoplastic resin composition made of an amorphous polyester resin, and The core layer is configured as a multilayer sheet comprising a polycarbonate resin and a transparent polycarbonate resin composition containing a laser light energy absorber, and the adhesive layer is a copolymer of a polyester resin and a monomer having a hydrophilic functional group. As a layer having a thickness of 1 to 20 μm, formed from a transparent thermoactive adhesive consisting of Made is, transparent laser marking sheet.

[2] The transparent laser marking sheet according to [1], wherein the polyester resin of the transparent thermoactive adhesive has a number average molecular weight of 10,000 to 200,000 and a glass transition temperature of 20 to 100 ° C.

[3] The transparent laser marking sheet according to [1] or [2], wherein the transparent thermoactive adhesive is a water-dispersed polyester resin made of a copolymer of a polyester resin and a monomer having a hydrophilic functional group.

[4] The transparent laser marking sheet according to any one of [1] to [3], wherein the transparent thermoactive adhesive is an aqueous dispersion, an aqueous solution, or an organic solvent solution.

[5] For the single layer sheet or the core layer of the multilayer sheet, the laser light energy absorber is selected from carbon black, titanium black, metal oxide, metal oxide, and metal carbonate. The transparent laser marking sheet according to any one of [1] to [4], wherein at least one kind is included.

[6] The single-layer sheet contains a lubricant, at least one selected from an antioxidant and an anti-coloring agent, and at least one selected from an ultraviolet absorber and a light stabilizer. The transparent laser marking sheet according to any one of [1] to [5].

[7] The skin layer of the multilayer sheet includes a lubricant, at least one selected from an antioxidant and an anti-coloring agent, and is selected from an ultraviolet absorber and a light stabilizer. The transparent laser marking sheet according to any one of [1] to [5], wherein at least one kind is included.

[8] The transparent laser marking sheet according to any one of [1] to [7], which is for electronic passports.

[9] The transparent laser marking sheet according to any one of [1] to [7], which is for a plastic card.

[10] A laminate using the transparent laser marking sheet according to any one of [1] to [7], wherein at least a printing sheet is adhered to the adhesive layer of the transparent laser marking sheet. The printed sheet is a laminate obtained by performing UV offset printing or UV silk printing.

[11] A laser marking method for laser-marking the transparent laser marking sheet according to any one of [1] to [9], wherein the transparent laser marking sheet and UV offset printing or UV silk printing are applied. After the sheet is integrated, laser light energy is irradiated toward the surface of the transparent laser marking sheet on which the adhesive layer is not formed to laser mark characters, figures, symbols, or information. Laser marking method.

  The transparent laser marking sheet of the present invention has good adhesion between the base sheet and the transparent thermoactive adhesive, has high versatility, and is easy to mold.

  Furthermore, the transparent laser marking sheet of the present invention is excellent in transparency, and characters, images, etc. formed on a printed sheet bonded to the adhesive layer surface of this transparent laser marking sheet can be clearly seen.

  In addition, the transparent laser marking sheet of the present invention is extremely excellent in heat-fusibility with another sheet other than the sheet that is printed to constitute, for example, an electronic passport or a plastic card.

  Furthermore, the transparent laser marking sheet of the present invention has high contrast and can perform clear laser marking by laser light energy irradiation. Further, the laser light energy irradiation part does not foam. In addition, the laser marking portion is not etched and has wear resistance.

  Further, in the laminate of the present invention in which at least a printing sheet is adhered to the adhesive layer of the transparent laser marking sheet of the present invention, printing by laser marking, printing by UV offset printing, etc., or by UV silk printing It can realize clear display such as printing, and is excellent in preventing falsification and forgery. In addition, a laminate of a transparent laser marking sheet and a sheet subjected to UV offset printing or UV silk printing is a heat-bonding property (adhesiveness) between the transparent laser marking sheet and the sheet subjected to the printing. Is extremely excellent.

  Furthermore, according to the laser marking method of the present invention, the transparent laser marking sheet and the printing sheet can be reliably heat-fused and integrated, and the transparent laser marking sheet has a high contrast and sharpness. New characters, figures, symbols, or information can be laser marked.

It is a schematic diagram showing one embodiment of the transparent laser marking sheet of the present invention, and shows a cross section of the transparent laser marking sheet provided with a transparent thermally active adhesive layer on one side of a base sheet composed of a single layer. It is a figure. It is a schematic diagram which shows another embodiment of the transparent laser marking sheet of this invention, Comprising: The transparent thermally active adhesive bond layer was provided in the single side | surface of the base material sheet comprised from the multilayer sheet which has a skin layer and a core layer It is the figure which showed the cross section of the transparent laser marking sheet. It is the schematic diagram which shows one Embodiment of the laminated body using the transparent laser marking sheet of this invention, Comprising: It is the figure which showed the cross section. It is the schematic diagram which shows another embodiment of the laminated body using the transparent laser marking sheet of this invention, Comprising: It is the figure which showed the cross section. It is the schematic diagram which shows another embodiment of the laminated body using the transparent laser marking sheet of this invention, Comprising: It is the figure which showed the cross section.

  Hereinafter, the form for implementing the transparent laser marking sheet of this invention, a laminated body, and the laser marking method is demonstrated concretely. However, the present invention broadly includes a transparent laser marking sheet, a laminate, and a laser marking method including the invention-specific matters, and is not limited to the following embodiments.

[I] Configuration of the transparent laser marking sheet of the present invention:
The transparent laser marking sheet 1 (1A, 1B) of the present invention is a transparent laser marking sheet in which an adhesive layer 3 is provided on at least one side of the base sheet 2, 20, as shown in FIGS. is there. The said base material sheet 2 is comprised as a single layer sheet which consists of a polycarbonate resin and the transparent polycarbonate resin composition containing a laser beam energy absorber. Or the said base material sheet 20 has the skin layer 4 and the core layer 5, the said skin layer 4 which is both outermost layers consists of a thermoplastic resin composition which consists of an amorphous polyester resin, and the said core The layer 5 is comprised as a multilayer sheet which consists of a polycarbonate resin and the transparent polycarbonate resin composition containing a laser beam energy absorber. Furthermore, the adhesive layer 3 is formed as a layer having a thickness of 1 to 20 μm while being formed from a transparent heat-active adhesive made of a polyester resin.

  Hereinafter, after describing the adhesive layer, a single layer sheet and a multilayer sheet will be described in this order.

[I-1] Adhesive layer:
The adhesive layer of the present invention is formed in a layered manner on at least one side of the base sheet. Furthermore, it is formed as a layer having a thickness of 1 to 20 μm while being formed from a transparent thermally active adhesive made of polyester resin. By comprising in this way, versatility and moldability can be improved. In particular, it is easy to integrate with another sheet on which printing by UV offset printing or printing by UV silk printing or the like has been performed, and the effects of preventing falsification and forgery can be improved.

  Here, “the adhesive layer” is “formed in a layered manner on at least one side of the base sheet” means that the adhesive layer is formed in a layered form on the entire surface of at least one side of the base sheet. Means that. By comprising in this way, a base material sheet and another sheet | seat can be integrated reliably. That is, the transparent laser marking sheet of the present invention and another sheet can be integrated, and troubles such as peeling can be made difficult to occur. In other words, it can be brought into close contact with another sheet, and combined with another sheet, effects such as falsification prevention and forgery prevention can be obtained.

  In particular, even if the surface of another sheet is subjected to printing by UV offset printing or UV silk printing, it can be reliably integrated, and defects such as peeling can be made difficult to occur. Therefore, effects such as falsification prevention and forgery prevention can be obtained.

  On the other hand, when the adhesive layer is partially formed on at least one surface of the base sheet, there is a possibility that a defect may occur in the integration with the sheet on which printing by UV offset printing or UV silk printing is performed. Is not preferable.

  The adhesive layer is formed from a transparent thermally active adhesive made of a polyester resin. By forming the adhesive layer from the material as described above, it is possible to improve the adhesion with another sheet or the like. Moreover, since the adhesive layer excellent in transparency can be formed, characters, images, etc. printed on another sheet bonded to the transparent laser marking sheet can be clearly seen.

  Further, the above-mentioned “transparent thermoactive adhesive comprising a polyester resin” is an adhesive having a property of developing or increasing adhesiveness by heating, and an adhesive layer is formed on a base sheet using this adhesive. In some cases, the adhesive layer is transparent. Examples of such “transparent thermoactive adhesive” include those made of polyester resin.

  Here, the adhesive forming the adhesive layer in the transparent laser marking sheet of the present invention has thermal activity as described above. In the present invention, when a non-thermally active adhesive is used as the adhesive for forming the adhesive layer, the non-thermally active adhesive exhibits adhesiveness at room temperature, and therefore is inferior in workability such as punching. It is not preferable. In addition, it is difficult to align at the time of molding, and dust easily adheres to the surface on which the adhesive layer is formed at the time of molding, resulting in poor molding processability. Furthermore, since non-thermoactive adhesives generally have a relatively low glass transition temperature, there are problems such as difficulty in improving heat resistance.

  The reason why the “adhesive layer” is formed as described above is to improve versatility and moldability. When the base sheet in the present invention and another sheet are integrated, the work efficiency is reduced when an adhesive is applied. In addition, the amount and thickness of the adhesive to be applied may not be uniform, and there may be variations in the final product. Furthermore, like the transparent laser marking sheet or the laminate of the present invention, when printing of data or the like is performed by a public organization or a highly reliable organization, the adhesive is applied in a desired amount and a desired thickness. Practically difficult.

  Moreover, the adhesive bond layer in the transparent laser marking sheet of this invention is comprised as a layer which has a thickness of 1-20 micrometers. By providing such a desired thickness, the adhesive layer does not need to be excessively thick, and corresponds to the general standard of electronic passports or plastic cards. That is, it becomes easy to mold an electronic passport or a plastic card using a transparent laser marking sheet having such a desired adhesive layer. Furthermore, when the adhesive layer has a desired thickness, it is possible to ensure the clarity of characters, figures, symbols, information, etc. when laser marking or printing is performed.

  On the other hand, when the thickness of the adhesive layer is less than 1 μm, sufficient adhesion with another sheet cannot be performed. That is, even if it is bonded to another sheet, it can be easily peeled off or easily peeled off. Therefore, effects such as tampering prevention and counterfeiting cannot be obtained. On the other hand, if the thickness of the adhesive layer is more than 20 μm, the adhesive layer becomes excessively thick. As described above, even if the adhesive layer becomes excessively thick, it is difficult to obtain an adhesive strength commensurate with it. Furthermore, if the adhesive layer is too thick, it becomes difficult to apply an electronic passport or a plastic card. That is, it is difficult to comply with a general thickness standard required for an electronic passport or a plastic card. Accordingly, when an adhesive layer having an excessive thickness is formed, the transparent laser marking sheet is inferior in versatility.

  Furthermore, if the adhesive layer becomes too thick, problems are likely to occur when the transparent laser marking sheet is integrated with another sheet. For example, when the transparent laser marking sheet and another sheet are heated, or heated and pressurized, and laminated and integrated, the adhesive forming the adhesive layer is solidified from the end face of the laminate Sometimes it will stick out. The protruding adhesive not only deteriorates the appearance, but also requires a removal operation, resulting in poor productivity. Moreover, since the thickness of the adhesive layer becomes excessively thick, it becomes difficult to identify data such as prints printed on another sheet from the transparent laser marking sheet side.

  Further, a “transparent thermoactive adhesive comprising a polyester resin” having a temperature of 60 to 160 ° C. at which the thermal activity is exhibited can be suitably used. It is easy to store and handle, and there is no risk of damaging another sheet that is adhered to the adhesive layer. On the other hand, when the temperature at which the thermal activity is exerted is less than 60 ° C., storage and handling become difficult and there is a risk of trouble. When the temperature exceeds 160 ° C., the energy loss increases and the production cost increases as the thermal energy required for bonding increases. Furthermore, it becomes easy to damage a base sheet or another sheet to be bonded to the adhesive layer.

  Furthermore, it is preferable that the total light transmittance of the adhesive layer is 70% or more. This is because, when the transparent laser marking sheet and another sheet are used in an integrated manner, characters, figures, symbols, information, or the like printed on the other sheet or the like can be identified from the transparent laser marking sheet side. Details of the above-mentioned “total light transmittance”, details of the measuring method, and the like will be described later.

  Furthermore, the polyester resin of the transparent thermally active adhesive preferably has a number average molecular weight of 10,000 to 200,000 and a glass transition temperature of 20 to 100 ° C. By forming such an adhesive layer made of a desired polyester resin, the transparent laser marking sheet of the present invention and another sheet can be reliably bonded. That is, defects such as peeling hardly occur, and tampering and counterfeiting can be prevented. Furthermore, in a state at room temperature, that is, in a state before molding that is heated at a desired temperature at the time of molding, it is possible to suppress the occurrence of stickiness and adhesion on the surface of the adhesive layer, and thus handling becomes easy and molding. Easy to process. Therefore, it becomes easy to use for electronic passports, plastic cards, and the like.

  On the other hand, when the number average molecular weight of the “polyester resin of the transparent thermoactive adhesive” is less than 10,000, the adhesive strength is poor. Therefore, there is a possibility that problems such as peeling occur. Further, when the number average molecular weight of the “polyester resin of the transparent heat-active adhesive” exceeds 200,000, a large amount of solvent is required for use in order to dissolve in the solvent and adjust to a desired viscosity. Therefore, it is not preferable from the viewpoint of work, environment, cost, and the like.

  Further, when the glass transition temperature of the “polyester resin of the transparent thermoactive adhesive” is less than 20 ° C., the adhesive layer may be sticky or sticky at room temperature. For this reason, working efficiency is reduced. In addition, when the glass transition temperature of the “polyester resin of the transparent thermoactive adhesive” is higher than 100 ° C., there is a risk that problems may occur when the transparent laser marking sheet and another sheet are molded and integrated. is there.

Such a transparent thermally active adhesive polyester resin can be synthesized from, for example, terephthalic acid and ethylene glycol. Among such polyester resins, it is essential to use a polyester resin obtained by copolymerizing a monomer having a hydrophilic functional group. Furthermore, it is also preferable that the polyester resin of the transparent thermoactive adhesive is a water-dispersed polyester resin made of a copolymer with a monomer having a hydrophilic functional group. By forming an adhesive layer using such a desired polyester resin, a transparent laser marking sheet having strong adhesion to another sheet can be formed.

  Here, examples of the hydrophilic functional group described above include a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, and a quaternary ammonium base. Furthermore, examples of the monomer having a hydrophilic functional group include glycols and acrylic acids.

  The blending amount of the monomer having a hydrophilic functional group described above is such that the hydrophilic functional group content is 60% by mass or less, preferably 50% by mass or less with respect to 100 parts by mass of the polyester resin. preferable. A polyester resin having such a hydrophilic functional group has both water dispersibility and water resistance. Therefore, the aqueous system is easy. That is, the solvent can be eliminated. Therefore, VOC regulations and the like can be cleared. Further, water resistance can be imparted to the adhesive layer. If the content of the hydrophilic functional group is too large, the water resistance becomes poor.

  In addition, when forming an adhesive bond layer using the above polyester resins, even if it does not use a dispersing agent, an emulsifier, etc., it can be easily disperse | distributed to water and it can be set as an aqueous dispersion. Therefore, it becomes easy to form an adhesive layer. Furthermore, it becomes easy to coat to a desired thickness. Moreover, the adhesive layer formed using the polyester resin as described above is insoluble or hardly soluble in water. It is also excellent in water resistance. Therefore, handling is easy even in a working environment with high moisture.

  Specific examples of the polyester resin that is a transparent thermoactive adhesive that forms such an adhesive layer include Vylonal MD-1200 (trade name, manufactured by Toyobo Co., Ltd.), XJ-36 (trade name, Toagosei Co., Ltd.) Manufactured) and the like. These are merely examples, and the present invention is not limited to these.

  Further, the transparent thermoactive adhesive can be used as an aqueous dispersion, an aqueous solution, or an organic solvent solution. When forming the adhesive layer, the above-described polyester resin can be made homogeneous, and the adhesive layer can be easily formed into a uniform layer. Among these, an environmentally preferable usage mode is to use it as an aqueous dispersion.

  In addition, even if it does not use or uses surfactant, the said polyester resin can be made into a small quantity, and adhesiveness, heat-fusion property, transparency, etc. are not impaired. Furthermore, the stability of the dispersion liquid can be ensured, and when forming an adhesive layer on a base sheet described later, layer formation can be easily performed and the thickness of the adhesive layer can be easily controlled.

  Furthermore, when the polyester resin of the transparent thermoactive adhesive is used as an aqueous dispersion, aqueous solution, or organic solvent solution, the solid content concentration of the copolymer should be in the range of 10 to 40% by mass. Is preferred. By doing in this way, formation of the uniform adhesive bond layer to a base material sheet can be performed easily. When the solid content concentration is less than 10% by mass, overcoating is required to form a layer having the above-described thickness, which requires man-hours. Conversely, when the solid content concentration exceeds 40% by weight, it is difficult to form a layer having a uniform thickness.

  Examples of the organic solvent used by dissolving such a transparent thermoactive adhesive include cellosolv solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, and ketone solvents such as cyclohexanone. However, it is not limited to these, and organic solvents including known hydrocarbon solvents can be used.

  In preparing the aqueous dispersion, aqueous solution, or organic solvent solution of the polyester resin as the transparent heat-active adhesive described above, various preparation methods and means that have been conventionally employed can be employed. It is not limited to the preparation method and means.

  Furthermore, the transparent thermoactive adhesive made of a polyester resin forming the adhesive layer may contain a leveling agent, a colorant, and other additives as necessary within a range not impairing the object and effect of the present invention. Also good.

(Adhesive layer formation method)
As a method for forming the adhesive layer on at least one surface of the base sheet in the transparent laser marking sheet of the present invention, a known forming method can be employed. For example, a coating liquid composed of an aqueous dispersion, an aqueous solution, or a solvent solution is prepared. Next, the adjusted coating liquid is formed in a layer on the base sheet by a known layer forming means such as a roll coating method, a bar coating method, a spray coating method, an air knife coating method or the like. The method of drying after layer formation and forming an adhesive bond layer can be mentioned.

  In addition, as for the temperature at the time of drying mentioned above, 60-120 degreeC is preferable in general. By setting it as such temperature conditions, the layer which consists of a transparent thermoactive adhesive agent can be firmly formed in a base material sheet. On the other hand, when the drying temperature is less than 60 ° C., it is difficult to firmly form a transparent heat-active adhesive layer on the base sheet, and it takes a long time to dry, resulting in a decrease in production efficiency. On the other hand, when the drying temperature exceeds 120 ° C., there is a possibility that voids and cracks may be generated in the base sheet, which is not preferable.

  The time required for the drying is usually several tens of seconds to several minutes. The drying time depends on the drying temperature, but by setting the desired drying time as described above, the base sheet is not sticky and has strong adhesion with excellent adhesion to the base sheet. An agent layer can be formed. On the other hand, if the drying time is too short, it is necessary to raise the drying temperature more than necessary. Raising the drying temperature more than necessary is not preferable because voids and cracks may be generated in the base sheet. Moreover, if the drying time is too long, the production cost becomes excessive. Furthermore, a base material sheet and a transparent thermoactive adhesive will be exposed for a long time under a heating, and a void and a crack may generate | occur | produce in a base material sheet like the above. Also, it is difficult to expect the effect of increasing the drying time. Therefore, it is not preferable.

  For example, a transparent laser marking sheet 1 (1A) as shown in FIG. 1 can be mentioned. In the transparent laser marking sheet 1 (1A) shown in FIG. 1, the base sheet is configured as a single-layer sheet 2 described later, and an adhesive layer 3 is formed on one side thereof.

  Further, for example, a transparent laser marking sheet 1 (1B) as shown in FIG. 2 can be mentioned. In the transparent laser marking sheet 1 (1B) shown in FIG. 2, the base sheet is configured as a multilayer sheet 20 described later. The multilayer sheet 20 has a skin layer 4 and a core layer 5. Furthermore, the adhesive layer 3 is formed on one skin layer 4 surface of the multilayer sheet 20.

[I-2] Configuration of substrate sheet:
As for the transparent laser marking sheet of this invention, the base material sheet is comprised from the single layer sheet or the multilayer sheet. Furthermore, the multilayer sheet is configured as a three-layer sheet including at least a skin layer and a core layer.

(Single layer sheet)
The single layer sheet is configured as a sheet having a single layer structure. This single-layer sheet can be produced by a conventionally known method for forming a sheet-like material. However, it is preferable that a single layer sheet is formed by melt extrusion.

(Material of single layer sheet)
The single-layer sheet as the base sheet is preferably formed from the following materials.

The single layer sheet is preferably formed from a transparent resin mainly composed of a transparent polycarbonate resin. Here, the polycarbonate resin is not particularly limited, the melt volume rate can be suitably used those 4~20cm ³ / 10min. The melt volume rate of less than 4 cm 3 ^/ 10min, flexibility of the sheet, toughness, although in terms of toughness, such as fastness are improved means is, since the molding processability by melt extrusion is poor, the actual Since it is difficult to use, it is not preferable. Further, the melt volume rate is more than 20 cm ³ / 10min, since the poor toughness of the sheet, which is not preferable. By forming a single-layer sheet from a transparent resin layer containing polycarbonate resin in this way, the so-called “blowing” of the laser marking portion caused by laser light energy irradiation can be suppressed, and the laser marking portion caused by laser light energy irradiation can be suppressed. As a result, the wear resistance can be improved.

  In addition, when a base material sheet is comprised as a single layer sheet, it is important to have high transparency. Specifically, when configured as a single-layer sheet, there is no particular limitation on adding and blending a resin that does not hinder the transparency of the polycarbonate resin, such as a filler. For the purpose of improving scratch resistance or heat resistance, a blend of a general-purpose polycarbonate resin and a special polycarbonate resin, a blend of a polycarbonate resin and a polyarylate resin, or the like can be employed.

  As the above-mentioned special polycarbonate resin, for example, a graft polymer having a main chain made of a polycarbonate resin and a side chain having a polystyrene resin or a modified acrylonitrile-styrene copolymer resin, specifically, a product name manufactured by NOF Corporation “Modiper C Series” and the like. The blend ratio in this case is preferably 95/5 to 60/40 (mass ratio). Further, the blend ratio in the case of blending with a polyarylate resin is preferably set in the same range as described above.

(Multilayer sheet)
The multilayer sheet is formed by laminating a plurality of layers having a skin layer and a core layer. That is, in the present embodiment, the base sheet is configured as a multilayer sheet having a “at least three layers” structure including a skin layer and a core layer. However, the “three-layer sheet” means “at least three layers” and is not limited to a three-layer structure. In other words, in the base sheet (multilayer sheet), the “three-layer sheet” is for convenience of explanation. The “three-layer sheet” means “a sheet composed of at least three layers”. It is not intended to limit the sheet to “three layers”. That is, if it is a structure of 3 layers or more, even if it is formed of 5 layers, 7 layers, or even an odd number of layers or more, it is included in the multilayer sheet.

  However, even if the multilayer sheet is composed of the above-mentioned “odd number of more layers”, if the layer structure is too large, the layer thickness per layer of the skin layer and the core layer constituting the multilayer sheet Becomes too thin. Therefore, there is a possibility that a mold stick may be generated in the heating press process at the time of lamination. Therefore, the multilayer sheet is preferably composed of 5 layers, more preferably 3 layers.

  That is, the multilayer sheet in this embodiment is composed of odd layers as described above, even if the layer structure is a multilayer sheet composed of even layers, the skin layer or the core layer is the same or different two or more layers. In the case of a plurality of layers, each of these layers is a single layer. As a result, it always has the same configuration as a multilayer sheet composed of odd layers. Specifically, for example, a transparent laser marking sheet composed of four layers has a layer structure of skin layer / core layer / core layer / skin layer. It becomes the structure similar to the multilayer sheet comprised from an odd number layer. That is, in this case, a core layer (core layer / core layer) composed of two layers of the same type or different types is defined as one layer.

  For example, taking a multilayer sheet composed of three layers (so-called “three-layer sheet”) as an example, the outermost layer of one and the other is arranged so that a layer arrangement of skin layer / core layer / skin layer is formed. Two skin layers are arranged. Then, a single core layer is arranged so as to be sandwiched between the two skin layers to form a multilayer sheet. In the case of a multi-layer sheet composed of five layers, one and the other are arranged so that the core layer and the skin layer are arranged in the order of skin layer / core layer / skin layer / core layer / skin layer. Two skin layers are arranged on the outermost sides of the two. Thus, a multilayer sheet may be formed by alternately arranging skin layers and core layers.

  Here, as described above, even if it is configured as a single layer sheet, it has sufficient laser colorability. However, it is more preferable to form a multilayer sheet having the multilayer structure as described above. By configuring the base sheet as a multi-layer sheet having a multi-layer structure in this manner, it is possible to irradiate laser light energy at a higher output than the single-layer sheet and increase the concentration of the laser marking portion. In addition, so-called “blowing” due to foaming of the laser marking portion can be suppressed, and surface smoothness can be maintained. In addition, since the skin layer is laminated on the upper layer of the laser marking portion, the abrasion resistance of the laser marking portion is further improved as compared with the case where no skin layer is disposed.

(Skin layer of multilayer sheet)
When a skin layer is formed in a multilayer sheet, that is, when a multilayer sheet having a “three-layer structure” is used, the skin layer is configured as both outermost layers arranged outside the three-layer sheet. The skin layer is arranged so as to be sandwiched from both end surfaces (outside) of the core layer in the multilayer sheet, and plays a role as a surface layer that is both outermost layers of the three-layer sheet.

  Here, the thicknesses of the skin layers are preferably the same. In electronic passports and plastic cards, it is common to perform laser marking from the front and back. Therefore, the base sheet as a laminate is arranged in the outermost layer and the outermost layer, and the thickness of the laminated skin layers is different, so that the core layer by laser light energy irradiation is the so-called “blowing” due to the foaming of the marking The suppression effect and the abrasion resistance effect of the laser marking part are different. Therefore, it is not preferable.

  Further, for example, when the base sheet is configured as a multilayer sheet composed of three layers such as skin layer / core layer / skin layer, and the thickness of the core layer is 20% or more and less than 80% The skin layer is 20% or more and less than 80% on both sides. When the thickness on one side of the skin layer is less than 10%, the laser marking part of the core layer is foamed by the laser light energy irradiation, so-called “blowing” suppression, and the wear resistance of the laser marking part by the laser light energy irradiation The effect of improving is not sufficient. On the other hand, if the skin layer is too thick, the thickness of the core layer is inevitably reduced, and the laser marking property is inferior.

(Material for skin layer of multilayer sheet)
Here, the material for forming the skin layer is formed from a thermoplastic resin composition mainly composed of an amorphous polyester resin obtained by preparing an amorphous polyester resin, particularly a copolyester resin.

  Next, as a polyester resin as a transparent resin mainly composed of an amorphous aromatic polyester resin constituting the skin layer, a dicarboxylic acid unit mainly containing a terephthalic acid unit, an ethylene glycol unit, and 1, The polyester is composed of glycol units mainly composed of 4-cyclohexanedimethanol units, and the ethylene glycol units (I) and 1,4-cyclohexanedimethanol units (II) are (I) / (II) = A copolyester resin that is 90-20 / 10-80 mol% is used. The reason for preparing the component amounts of ethylene glycol units and 1,4-cyclohexanedimethanol units contained in this copolymerized polyester resin is that, in the copolymerized polyester resin, the component amount of ethylene glycol units is less than 20 mol%. The resulting resin is not sufficiently non-crystalline, and recrystallization proceeds in the cooling step after heat fusion, resulting in poor heat fusion. Further, a resin obtained in excess of 90 mol% does not become sufficiently non-crystalline, and recrystallization proceeds in the cooling step after heat fusion, resulting in poor heat fusion. Therefore, as in this embodiment, the resin obtained by preparing the component amounts of the ethylene glycol unit and the 1,4-cyclohexanedimethanol unit becomes sufficiently non-crystalline, and in terms of heat fusibility. Since it is excellent, it can be said to be a desirable resin.

  Further, as this copolyester resin, for example, a substantially non-crystalline aromatic polyester resin (Eastman Chemical Co., Ltd.) in which about 30 mol% of the ethylene glycol component in polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol. Product name "PETG") is commercially available.

(Core layer of multilayer sheet)
The core layer of the multilayer sheet is configured as a so-called core layer disposed in the center of the base sheet. That is, when the base sheet is configured as a multilayer sheet as a three-layer sheet, the core layer is formed as the core layer of the three-layer sheet so as to be sandwiched between the two skin layers disposed on the outermost sides. Has been.

(Material for core layer of multilayer sheet)
That is, the core layer of the multilayer sheet is formed from a transparent polycarbonate resin composition mainly composed of a transparent polycarbonate resin. However, polycarbonate resins used are particularly limited but may not, melt volume rate can be suitably used those 4~20cm ³ / 10min. The melt volume rate of less than 4 cm 3 ^/ 10min, flexibility of the sheet, toughness, although in terms of toughness, such as fastness are improved means is, since the molding processability by melt extrusion is poor, the actual Since it is difficult to use, it is not preferable. Further, the melt volume rate is more than 20 cm ³ / 10min, since the poor toughness of the sheet, which is not preferable. In this way, by forming the core layer of the multilayer sheet from a transparent polycarbonate resin composition containing a polycarbonate resin, it is possible to suppress the so-called “swelling” in which the laser marking portion is foamed by the laser light energy irradiation, and the laser light energy irradiation. The marking portion is etched and the wear resistance can be improved.

(Thickness of core layer of multilayer sheet)
Here, the thickness of the core layer of the multilayer sheet is preferably formed so that the ratio of the thickness in the entire sheet is 20% or more and less than 80%. When the thickness ratio of the core layer is 20% or more, the thickness effect of the laser marking portion of the core layer by laser light energy irradiation increases the contrast with the uncolored portion due to the underlying white layer, and the visibility and clarity of the laser marking portion are improved. improves. On the other hand, if the thickness ratio of the core layer is 80% or more, the skin layer becomes too thin. When a transparent laser marking sheet having a base sheet composed of such multilayer sheets is irradiated with laser light energy at a high output, the laser light energy absorbent blended in the core layer absorbs the laser light energy. It is converted into heat and high heat is generated. For this reason, the effect of suppressing the so-called “blowing” in the laser light energy irradiating portion is poor, which is not preferable. Even if the laser light energy output is adjusted to obtain a preferable laser color, the laser marking portion is etched compared to the case where the thickness of the skin layer is within the above-mentioned desired range. Wearability is not sufficient and not preferable.

  Further, if the thickness ratio of the core layer is 80% or more, the total thickness with another sheet or the like on which the transparent laser marking sheet is laminated is defined, so that the skin layer becomes relatively thin. . In this case, even if a lubricant is mixed in the skin layer, there is a problem of a mold stick that sticks to the mold in the heating press process in the laminating process, which is not preferable. Also, when the thickness ratio of the core layer is less than 20%, the problem of the mold stick does not occur in the laminating process because the skin layer is thick, but since the laser marking property is poor and the heat resistance is poor, the sheet is warped. It is not desirable to occur. Moreover, since laser marking property is inferior, it is not preferable. More preferably, the thickness of the core layer of the multilayer sheet is 40% or more and less than 75%.

(Base sheet thickness)
The thickness of the base sheet is preferably 50 to 200 μm in the case of a single layer sheet. When the thickness of the single layer sheet is less than 50 μm, the blending amount of the laser light energy absorber is decreased, and the laser marking property is insufficient, which is not preferable. On the other hand, when the thickness of the single-layer sheet exceeds 200 μm, it becomes too thick, making it difficult to put it to practical use, such as inconvenience in handling. For example, when a multilayer sheet for an electronic passport is laminated using a laser marking multilayer sheet (laminate) composed of a single-layer sheet exceeding 200 μm and a core multilayer sheet laminated thereon, The maximum thickness exceeds 800 μm.

  When the base sheet is configured as a multilayer sheet (so-called three-layer sheet) composed of a skin layer and a core layer, the total thickness of the multilayer sheet is preferably 50 to 200 μm.

  Thus, when a single-layer sheet is used as a base sheet, or when a multilayer sheet is used as a base sheet, transparent laser marking is performed by setting the total thickness of the base sheet to a desired thickness. It makes it easier to draw out the characteristics of the sheet. Furthermore, not only the total thickness of the entire multilayer sheet, but also the ratio of the thickness of the skin layer and the core layer constituting the multilayer sheet to the multilayer sheet is set to the desired ratio as described above, thereby increasing the thickness of the entire multilayer sheet. Combined with setting the thickness within a desired range, the laser marking property is easily improved.

(Laser light energy absorber)
Moreover, the laser beam energy absorber is contained in the base material sheet which comprises a transparent laser marking sheet. By comprising in this way, it is excellent in the laser coloring property at the time of laser marking, the contrast of a ground part and a laser marking part becomes high, and a clear character, a figure, a symbol, or information is obtained. The “background portion” means a portion that is not laser-marked, and the same applies to the following.

  Furthermore, when a base material sheet is comprised as a single layer sheet, 0.0005-1 mass part of laser beam energy absorbers may be contained with respect to 100 mass parts of transparent resin which has polycarbonate resin as a main component. More preferred. When the base sheet is configured as a multilayer sheet, 0.0005 to 1 mass of the laser light energy absorber is used with respect to 100 mass parts of the transparent polycarbonate resin mainly composed of the polycarbonate resin in the core layer. It is more preferable to contain part. Thus, by including a laser light energy absorber, it is excellent in laser colorability when laser-marking, the contrast between the background portion and the laser marking portion is reliably increased, and more vivid characters, figures, symbols, Or information is obtained.

  On the other hand, when the content of the laser light energy absorber exceeds 1 part by mass, the transparency of the transparent laser marking sheet is lowered. Furthermore, when the laser beam energy is irradiated, the amount of absorbed energy is excessively increased and the resin is deteriorated. As a result, sufficient contrast cannot be obtained. Furthermore, if the content of the laser light energy absorber exceeds 1 part by mass, abnormal heat generation may occur. When abnormal heat generation occurs, the resin constituting the sheet is decomposed and foamed, and desired laser marking cannot be performed. On the other hand, when the content of the laser light energy absorber is less than 0.0005 parts by mass, sufficient contrast between the background portion and the laser marking portion cannot be obtained.

  Further, the laser light energy absorber described above is not particularly limited as long as it can absorb laser light energy and can be changed to a color, tone, and brightness different from those of the background portion. Specific examples include at least one selected from the group consisting of carbon black, titanium black, metal oxide, metal sulfide, metal nitride, metal soot oxide, and metal carbonate. A preferable laser light energy absorber is at least one selected from carbon black, titanium black, metal oxide, metal oxide, and metal carbonate. More preferable laser light energy absorber is at least one selected from carbon black, titanium black, and metal oxide, or two or more.

  Here, the average particle size of carbon black, titanium black, metal oxide, metal sulfide, metal nitride, metal soot oxide, and metal carbonate as the laser light energy absorber is preferably less than 150 nm. More preferably, it is less than 100 nm. Further, carbon black having an average particle diameter of 10 to 90 nm and dibutyl phthalate (DBT) oil absorption of 60 to 170 ml / 100 gr, or a combination of carbon black and titanium black having an average particle diameter of less than 150 nm, or a metal oxide is preferable. . If the average particle size of the laser energy absorber exceeds 150 nm, the transparency of the transparent laser marking sheet is undesirably lowered. Also, large irregularities may occur on the surface of the transparent laser marking sheet, which is not preferable. Further, when the average particle diameter of carbon black is less than 10 nm, the laser colorability is lowered and the fine particle is too fine to be handled, which is not preferable. Further, when the DBT oil absorption is less than 60 ml / 100 gr, the dispersibility is poor, and when it exceeds 170 ml / 100 gr, the concealability is poor, which is not preferable.

  In addition, among the metal oxides that are laser light energy absorbers, the metals that form oxides are zinc, magnesium, aluminum, iron, titanium, silicon, antimony, tin, lead, copper, manganese, cobalt, vanadium, bismuth. , Niobium, molybdenum, ruthenium, tungsten, palladium, silver, platinum and the like. Further, examples of the composite metal oxide include ITO, ATO, and AZO.

  Furthermore, examples of the metal sulfide that is a laser light energy absorber include zinc sulfide and cadmium sulfide. Further, examples of the metal nitride include titanium nitride. Examples of metal oxalates include magnesium oxalate and copper oxalate. Further, examples of the metal carbonate include basic copper carbonate.

  In addition, the addition amount (blending amount) of the laser light energy absorber is 0.0005 to 1 part by weight (mixing) in the case of carbon black with respect to 100 parts by weight of the transparent resin mainly composed of polycarbonate resin. Is more preferable. Most preferably, it is 0.0008-0.1 mass part. In addition, when carbon black and at least one selected from metal oxides, metal sulfides, and metal nitrides having an average particle diameter of less than 150 nm are used in combination, the amount of the mixture added is 0.0005 to 1 part by mass. More preferably. Most preferably, it is 0.0008-0.5 mass part.

  Thus, the addition amount of the laser light energy absorber is adjusted to a desired amount because the transparent laser marking sheet is preferably transparent. That is, when a transparent laser marking sheet is used for an electronic passport, a printed white sheet (printed inlay sheet) (hereinafter, printing of a white sheet printed with characters, graphics, etc. is referred to as “printing section” as appropriate) It is used by forming a layer called overlay or laminating a transparent laser marking sheet. In this case, laser light energy is applied to the unprinted part of the overlay to develop a black color to mark characters, figures, symbols, or information, and to prevent forgery by design and laser marking in the printed part. Often used in combination with effects.

  By using in combination as described above, since the base layer is white, it is possible to obtain clear characters, figures, symbols, or information due to the sharpness of the printed portion and the black / white contrast of the laser marking portion. In other words, if the overlay laminated on the above-mentioned printed inlay sheet is inferior in transparency, the printed image, characters, etc. will be unclear, and the black / white contrast of the laser marking part will be inferior. It becomes an upper problem. Therefore, carbon black having a small average particle diameter is preferably used, and at least one selected from carbon black and titanium black, other metal oxides, metal sulfides, metal nitrides, metal soot oxides, and metal carbonates. In the case of using a mixture of these as a laser light energy absorber, the average particle size of these metal oxides, metal sulfides, metal nitrides, metal soot oxides, and metal carbonates is at least less than 150 nm, preferably less than 100 nm. It is.

(Lubricants, antioxidants, anti-coloring agents, UV absorbers, and light stabilizers)
Moreover, in this embodiment, it is preferable to make a base material sheet which comprises a transparent laser marking sheet contain a lubricant. When the transparent laser marking sheet is composed of a multilayer sheet, it is preferable to contain a lubricant in the skin layer. By containing a lubricant, it is possible to prevent fusion to the press plate during molding and heating.

  Examples of the lubricant include fatty acid ester-based lubricants, fatty acid amide-based lubricants, and fatty acid metal salt-based lubricants, and it is preferable to add at least one lubricant selected from them.

  Examples of the fatty acid ester lubricants include butyl stearate, cetyl palmitate, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, montan wax acid ester, wax ester, dicarboxylic acid ester, and complex ester. Examples of fatty acid amide-based lubricants include stearic acid amide and ethylene bisstearyl amide. Furthermore, examples of the fatty acid metal salt lubricant include calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, and barium stearate.

  Furthermore, in this embodiment, when the base sheet of the transparent laser marking sheet is configured as a single layer sheet, if necessary, at least one of an antioxidant and an anti-coloring agent, and UV absorption It is also preferable to contain at least one of an agent and a light stabilizer. Further, when the base sheet of the transparent laser marking sheet is configured as a multilayer sheet, at least one of an antioxidant and an anti-coloring agent may be added to at least one of the skin layer and the core layer as necessary. It is also preferable to contain at least one of an ultraviolet absorber and a light stabilizer. Adding (compounding) at least one of an antioxidant and an anti-coloring agent effectively acts on physical property reduction and hue stabilization due to molecular weight reduction during molding processing. Here, a phenolic antioxidant or a phosphite ester colorant is used as at least one of the antioxidant and the colorant. In addition, the addition (formulation) of at least one of an ultraviolet absorber and a light stabilizer is a light deterioration resistance during storage of the transparent laser marking sheet and during actual use of electronic passports and plastic cards as final products. It works effectively on the suppression. As such an ultraviolet absorber, a benzotriazole ultraviolet absorber, a hydroxyphenyltriazine ultraviolet absorber, a cyclic imino ester ultraviolet absorber, or the like can be used.

  As said antioxidant, a phenolic antioxidant, an amine antioxidant, etc. can be used, for example.

  Examples of the phenol-based antioxidant include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3 -5-di-t-butyl-4-hydroxytoluene, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- ( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2- t-butyl-6- (3′-t-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylpheny Acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis ( 4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 2,2 '-Methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis (4,6-di-) -T-butylphenol), 2,2'-butylidene-bis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t) Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis { 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] Undecane, 4,4'-thiobis (6-t-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-thiobis 4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4′-di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-t-butylphenol), 2,2-thiodiethylenebis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-t-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3 , 5-di-t-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1, 3-Tris (2-methyl- 4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3 5-di-t-butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-) t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [3- (3,5-di-tert-butyl-4-hydroxypheny) ) Propionyloxymethyl] can be exemplified methane.

  Among these examples, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (among others) 3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane is preferred, especially n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. is there. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  Examples of coloring inhibitors include phosphite compounds, such as triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, dioctyl Decyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-t- Butylphenyl) octyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-) -Butylphenyl) phosphite, tris (2,6-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  Furthermore, as another phosphite compound in the coloring inhibitor, those having a cyclic structure by reacting with dihydric phenols can be used. For example, 2,2′-methylenebis (4,6-di-t-butylphenyl) (2,4-di-t-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-t- Butylphenyl) (2-t-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-t-butylphenyl) (2-t-butyl-4-methylphenyl) phosphite And 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Among the above-described coloring inhibitors, tris (2,4-di-t-butylphenyl) phosphite is particularly preferable because of its extremely high purity and excellent hydrolysis resistance and volatilization resistance. The phosphite ester coloration inhibitor may be used alone or in combination of two or more. Moreover, you may use together with a phenolic antioxidant.

  Specific examples of the above-described ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers, and cyclic iminoester-based ultraviolet absorbers.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzo. Triazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) ) -5-chlorobenzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [ Compounds represented by condensates of 3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol You can list things.

  Examples of the hydroxyphenyl triazine-based compound ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4,6). -Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol and the like.

  Further, examples of the cyclic imino ester ultraviolet absorber include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m (2) -phenylenebis (3 , 1-benzoxazin-4-one) and 2,2′-4,4′-diphenylenebis (3,1-benzoxazin-4-one).

  Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2 , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2 , 3,4-Butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2, 6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-oxy- [4- (2,2,6,6- Tetramethyl) pipette Jiniru] hindered amine compound represented by the siloxane and the like may also be used. Such a light stabilizer exhibits better performance in terms of weather resistance and the like when used in combination with the ultraviolet absorber and optionally various antioxidants.

  More preferably, if the base sheet constituting the transparent laser marking sheet is a single-layer sheet, the base sheet is a lubricant 0.01 to 3 parts relative to 100 parts by mass of the transparent polycarbonate resin containing a polycarbonate resin as a main component. It consists of a transparent polycarbonate resin composition containing a mass part. Furthermore, the base sheet constituting the transparent laser marking sheet contains 0.1 to 5 parts by mass of at least one of an antioxidant and an anti-coloring agent with respect to 100 parts by mass of the transparent polycarbonate resin mainly composed of the polycarbonate resin. And 0.1-5 parts by mass of at least one of an ultraviolet absorber and a light stabilizer.

  Further, if the base sheet constituting the transparent laser marking sheet is a multilayer sheet (so-called three-layer sheet), the skin layer of the multilayer sheet in the base sheet constituting the transparent laser marking sheet is mainly composed of an amorphous polyester resin. A transparent polycarbonate resin composition containing 0.01 to 3 parts by mass of a lubricant with respect to 100 parts by mass of the transparent resin, and at least one of the skin layer of the multilayer sheet and the core layer is made of a polycarbonate resin. To 100 parts by mass of the transparent polycarbonate resin as a main component, 0.1 to 5 parts by mass of at least one of an antioxidant and an anti-coloring agent, and at least one of an ultraviolet absorber and a light stabilizer. It is containing 0.1-5 mass parts.

  Here, the addition amount of the lubricant is 0.01 to 3 parts by mass, preferably 0.05 to 1.5 parts by mass. If the addition amount of the lubricant is less than 0.01 parts by mass, it will be fused to the press plate at the time of hot pressing, and if it exceeds 3 parts by mass, there will be a problem with the interlayer heat-fusibility at the time of multi-layer heating press of electronic passport or plastic card. Since it occurs, it is not preferable. Furthermore, when the addition amount of at least one of the antioxidant and the coloring inhibitor is less than 0.1 parts by mass, problems such as the thermal oxidation reaction of the polycarbonate resin in the melt extrusion molding process and thermal discoloration resulting therefrom occur. Cheap. On the other hand, if it exceeds 5 parts by mass, problems such as bleeding of these additives are likely to occur. Furthermore, when the added amount of at least one of the ultraviolet absorber and the light stabilizer is less than 0.1 parts by mass, the effect is poor and problems such as light resistance deterioration and discoloration associated therewith are likely to occur. Furthermore, if it exceeds 5 parts by mass, problems such as bleeding of these additives are likely to occur, which is not preferable.

  In addition, the fusion and concealment properties of multilayer sheets such as electronic passports and plastic cards, and the contrast with the laser marking part are extremely important, such as whether they can meet the practical use and productivity of multilayer sheets, market needs, etc. It becomes an element.

(Base sheet forming method)
In the present invention, in order to obtain a base sheet constituting the transparent laser marking sheet, for example, in the case of a single layer sheet, a method of melt extrusion molding a transparent polycarbonate resin composition can be employed. Also, in the case of a multilayer sheet, a method of melt extrusion molding the resin composition constituting each layer, a method of forming a film of what constitutes each layer, a method of laminating this, and a melt extrusion of the two layers, Although there is a method of laminating a separately formed film, etc., it is preferable to laminate and integrate by melt extrusion from the viewpoint of production and cost.

  Specifically, in the case of a multi-layer sheet, each resin composition constituting each layer is blended, or pelletized as necessary, and charged into each hopper of a three-layer T-die extruder with T-die jointly connected. To do. And it melts at the temperature of 200-300 degreeC, and performs 3 layer T-die melt extrusion molding. After molding, it can be cooled and solidified with a cooling roll or the like to form a three-layer sheet. In addition, it is not limited to the said method, It can form by a well-known method. For example, it can be obtained according to the description in JP-A-10-71763, pages (6) to (7).

(Total light transmittance)
Furthermore, the total light transmittance of the base sheet is preferably 70% or more, and more preferably 85% or more. For example, when the transparent laser marking sheet of the present invention is used for an electronic passport, printing is generally performed for those applications. Therefore, the laser light energy is applied to the non-printing portion that does not correspond to the printing portion of the printing inlay sheet of the transparent laser marking sheet that is the outermost layer by, for example, laminating the printing inlay sheet under the transparent laser marking sheet of the present embodiment. In many cases, a black color is developed to mark characters, figures, symbols, or information, and a combination of design in the printing section and prevention of counterfeiting by laser marking is often used. By combining in this way, since the base layer is white, a clear character, figure, symbol, or information can be obtained by vividness of the printed portion and black / background color contrast of the laser marking portion. That is, when laminating white sheets or the like, these effects can be maximized by setting the transparency of the outermost layer to the above-mentioned desired range of total light transmittance. That is, the sharpness of the black / white contrast can be emphasized. In other words, the transparency of the outermost layer is important for ensuring the sharpness of the printed part and the black / white contrast of the laser marking part. When the total light transmittance is less than 70%, the black / white is transparent. Since the contrast is insufficient and a problem that sufficient marking properties cannot be ensured occurs, and printing is performed on the base white sheet, this causes a problem in the visibility of the printing.

  Here, the “total light transmittance” is an index indicating the ratio of light transmitted through the light incident on the sheet, film, film, etc., and the total light transmittance when all the incident light is transmitted is 100%. In the present specification, “total light transmittance” indicates a value measured in accordance with JIS K7105 (plastic optical property test method). For example, it can be measured by using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “NDH 2000”), a spectrophotometer (manufactured by Macbeth, trade name “EYE7000”) and the like.

  For example, as shown in FIG. 1, the transparent laser marking sheet 1 (1 </ b> A) having the base material sheet 2 as a single layer sheet and the adhesive layer 3 provided on one side of the base material sheet 2 as described above. Can be illustrated.

  Further, as shown in FIG. 2, the base sheet 20 as a multilayer sheet having the skin layer 4 and the core layer 5 described above, and the adhesive layer 3 is provided on the base sheet 20. The transparent laser marking sheet 1 (1B) can be illustrated.

[II] Laser marking sheet for electronic passport:
Next, the laser marking sheet for electronic passports using the transparent laser marking sheet described so far will be described. However, this is an example and is not limited.

  First, as a first aspect of the laser marking sheet for electronic passport, there can be mentioned the laser marking sheet 100 (100A) for electronic passport shown in FIG. That is, the laser marking sheet for electronic passport 100 (100A) is composed of a transparent laser marking sheet 1 (1A) in which a base sheet is formed as a single layer sheet / core multilayer sheet 6 / binding sheet 10 / core multilayer sheet 6 / It is a laser marking sheet for electronic passports which has the structure which laminates | stacks five layers of the transparent laser marking sheet 1 (1A) by which a base material sheet is comprised as a single layer sheet. The transparent laser marking sheet 1 (1A) is a transparent laser marking sheet in which the adhesive layer 3 is provided on at least one surface of the base sheet 2 as described above. That is, the base sheet 2 is configured as a single layer sheet made of a transparent polycarbonate resin composition containing a polycarbonate resin and a laser light energy absorber. Further, the adhesive layer 3 is a transparent laser marking sheet formed as a layer having a thickness of 1 to 20 μm while being formed from a transparent thermoactive adhesive made of a polyester resin. The binding sheet 10 will be described later.

  The core multilayer sheet 6 has a skin layer 7 and a core layer 8 and is a sheet formed by laminating at least three layers by melt extrusion. The skin layer 7 which is both outermost layers of the core multilayer sheet 6 comprises a dicarboxylic acid unit mainly composed of terephthalic acid units, an ethylene glycol unit (I), and a 1,4-cyclohexanedimethanol unit (II). It is a polyester composed mainly of glycol units, and the ethylene glycol unit (I) and the 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90-30 / 10-70. It consists of a copolymerized polyester resin that is mol%. Further, the core layer 8 of the core multilayer sheet 6 is made of a transparent resin mainly composed of a polycarbonate resin. In at least one layer of the skin layer 7 and the core layer 8, at least one dye or pigment is 1 part by mass or more with respect to 100 parts by mass of the copolyester resin and / or 100 parts by mass of the polycarbonate resin. It is included. Furthermore, the total thickness of the core multilayer sheet 6 is 50 to 200 μm, and the ratio of the thickness of the core layer 8 to the total thickness of the core multilayer sheet 6 is 20% or more, It consists of less than 80%. A laser marking sheet for an electronic passport configured as described above can be given.

  Moreover, as an application example of the laser marking sheet for electronic passports, the laser marking sheet 100 (100B) for electronic passports shown in FIG. 4 can be mentioned. That is, the laser marking sheet 100 (100B) for electronic passport is composed of five layers: transparent laser marking sheet 1 (1B) / multilayer sheet 6 for core / binding sheet 10 / multilayer sheet 6 for core / transparent laser marking sheet 1 (1B). It is the laser marking sheet for electronic passports which has the structure which laminates | stacks. The transparent laser marking sheet 1 (1B) is a transparent laser marking sheet in which the adhesive layer 3 is provided on at least one surface of the base material sheet 20 composed of the skin layer 4 and the core layer 5 as described above. is there. Furthermore, the base sheet 20 has a skin layer 4 and a core layer 5, and the skin layer 4, which is both outermost layers, is made of a thermoplastic resin composition containing an amorphous polyester resin, and the core The layer 5 is comprised as a multilayer sheet which consists of a polycarbonate resin and the transparent polycarbonate resin composition containing a laser beam energy absorber. Further, the adhesive layer 3 is a transparent laser marking sheet formed as a layer having a thickness of 1 to 20 μm while being formed from a transparent thermoactive adhesive made of a polyester resin.

  Further, the core multilayer sheet 6 has a skin layer 7 and a core layer 8 as described above, and is a sheet formed by laminating at least three layers by melt extrusion molding. The skin layer 7 which is both outermost layers of the core multilayer sheet 6 comprises a dicarboxylic acid unit mainly composed of terephthalic acid units, an ethylene glycol unit (I), and a 1,4-cyclohexanedimethanol unit (II). It is a polyester composed mainly of glycol units, and the ethylene glycol unit (I) and the 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90-30 / 10-70. It consists of a copolymerized polyester resin that is mol%. Further, the core layer 8 of the core multilayer sheet 6 is made of a transparent resin mainly composed of a polycarbonate resin. At least one of the skin layer and the core layer includes 100 parts by mass of the copolymer polyester resin, and / Or 1 part by mass or more of at least one dye or pigment per 100 parts by mass of the polycarbonate resin. Furthermore, the total thickness of the multilayer sheet 6 is 50 to 200 μm, and the ratio of the thickness of the core layer 8 to the total thickness of the core multilayer sheet 6 is 20% or more and 80%. Less than. A laser marking sheet for an electronic passport configured as described above can be given. The core multilayer sheet 6 and the binding sheet 10 shown in FIG. 4 are the same sheets as in FIG.

(Multi-layer sheet for core)
Here, the core multilayer sheet 6 is configured as a sheet (three-layer sheet) having at least a three-layer structure including the skin layer 7 and the core layer 8, and is laminated by melt extrusion molding. That is, the core multi-layer sheet 6 is also composed of 7 layers even if it is composed of 5 layers as long as it is composed of 3 layers or more, like the base sheet 20 constituting the transparent laser marking sheet 1 (1B). Or may be formed of an odd number of layers or more, and it is sufficient that the core layer 8 is interposed between the skin layers 7.

  On the other hand, when the core multilayer sheet 6 has a multilayer structure too much, the layer thickness per layer of the skin layer 7 and the core layer 8 to be disposed becomes too thin. In that case, there arises a problem that the heat fusion property with the transparent laser marking sheet according to the present invention is inferior. Therefore, a multi-layer sheet for a core composed of 5 layers and more preferably 3 layers is preferable.

  For example, in the case of a core multilayer sheet composed of three layers, two skin layers are arranged on one and the other outermost side so that a layer arrangement of skin layer / core layer / skin layer is formed. Is done. Then, one core layer is arranged so as to be sandwiched between the two skin layers to form a core multilayer sheet. In the case of a multi-layer core sheet composed of five layers as an example, the outermost layer of one and the other is arranged so that the layer arrangement of skin layer / core layer / skin layer / core layer / skin layer is made. Two skin layers are arranged. In addition, the core multilayer sheet may be formed by alternately arranging the skin layers and the core layers. By forming the core multi-layer sheet having a multi-layer structure in this way, sufficient heat-fusibility can be ensured.

(Thickness of multilayer sheet for core)
Here, the total thickness (total thickness) of the core multilayer sheet 6 is 50 to 200 μm, and the core layer 8 of the core multilayer sheet 6 occupies the total thickness of the core multilayer sheet 6. It is preferable that the thickness ratio is 20% or more and less than 80%. If the total thickness of the core multilayer sheet 6 is less than 50 μm, the skin layer 7 of the core multilayer sheet 6 inevitably becomes thin. In this case, the heat-fusability between the transparent laser marking sheet 1 (1A, 1B) laminated on the outermost layer and the core multilayer sheet 6 cannot be ensured at the time of heat-sealing in the multilayer sheet laminating step. In addition, when the total thickness of the core multilayer sheet 6 exceeds 200 μm, when the laser marking sheet for electronic passport is formed using the core multilayer sheet 6 exceeding 200 μm, the total thickness becomes too thick, Usability is inferior.

  When the skin layer 7 of the core multilayer sheet 6 is too thin, the transparent laser marking sheet 1 (1A, 1B) laminated on the outermost layer at the time of heat-sealing in the multilayer sheet laminating process, and the core multilayer sheet 6 cannot be secured. On the other hand, when the skin layer 7 of the core multilayer sheet 6 is too thick, the thickness of the core layer 8 of the core multilayer sheet 6 to be described later is inevitably thin. In this case, it is not possible to ensure concealment when printing on the core multilayer sheet 6. Furthermore, when a coloring agent is not added to the skin layer 7 of the multilayer sheet 6 for core, when the black marking is performed on the transparent laser marking sheet 1 (1A, 1B) which is the outermost layer by laser light energy irradiation This is not preferable because a problem arises in that the contrast and the visibility of the laser marking portion cannot be ensured by ensuring the contrast.

  Thus, by setting the thickness of the entire core multilayer sheet 6 to a desired thickness, local characteristics such as the characteristics of the core multilayer sheet 6 can be easily extracted. Furthermore, the characteristics of the laser marking sheet for electronic passports composed of the transparent laser marking sheet 1 (1A, 1B) and the core multilayer sheet 6 can be easily extracted. Furthermore, not only the total thickness of the core multilayer sheet 6 as a whole, but also the ratio of the thickness of the skin layer 7 and the core layer 8 constituting the core multilayer sheet 6 to the core multilayer sheet 6, Each of the above-mentioned desired ratios is preferable because the thickness of the entire core multilayer sheet 6 is set within the desired range, and the effects such as easy improvement of the contrast can be exhibited.

(Skin layer in the core multilayer sheet)
Furthermore, it is preferable that the thickness of the skin layer 7 in the core multilayer sheet 6 is the same. When the core multilayer sheet 6 is composed of skin layers having different thicknesses, the heat fusion between the outermost transparent laser marking sheet 1 (1A, 1B) and the core multilayer sheet 6 at the time of heat fusion in the multilayer sheet laminating process. This is not preferable because it causes variation in wearing characteristics. Furthermore, warpage may occur in the laminate after hot pressing, which is not preferable.

  On the other hand, if the skin layer 7 in the core multilayer sheet 6 is too thin, the heat bondability is lowered. As described above, if the thickness of the skin layer 7 in the core multilayer sheet 6 is too thick, the thickness of the core layer 6 in the core multilayer sheet 6 is inevitably reduced. Here, when the colorant is blended only in the core layer 8 of the core multilayer sheet 6, it is only necessary to add the resin containing the colorant to only one extruder, and therefore the skin layer 7 of the core multilayer sheet 6. Compared with the case where the core layer 8 is mixed with a colorant, the cleaning of the colorant at the time of cleanup after the sheet production is extremely reduced, and half the labor is required. However, the concealability when a part or the entire surface of the core multilayer sheet 6 is printed is insufficient. Further, when a colorant is blended in the skin layer 7 and the core layer 8 of the core multilayer sheet 6, the above-described concealing problem does not occur. However, for example, two extruders are used for the three-layer sheet melt extrusion molding with two kinds of resins, and a resin containing a colorant is charged into these two extruders. In this case, it takes a lot of labor and time to clean the colorant at the time of cleanup after the production of a sheet formed by two-type three-layer melt extrusion molding, and productivity and cost problems are likely to occur. Accordingly, the total thickness (total thickness) of the core multilayer sheet 6 and the ratio of the thickness of the core layer 8 to the total thickness of the core multilayer sheet 6 are within the desired range as described above. It is preferable to select.

  Here, examples of the material for forming the skin layer 7 in the core multilayer sheet 6 include the polyester-based resin composition described above. That is, the skin layer 7 is preferably formed as a layer made of a substantially non-crystalline aromatic polyester resin composition prepared from a copolyester resin. For example, a substantially non-crystalline aromatic polyester-based resin (manufactured by Eastman Chemical Co., Ltd.) in which about 30 mol% of the ethylene glycol component in commercially available polyethylene terephthalate is replaced with 1,4-cyclohexanedimethanol. , Trade name “PETG”).

(Core layer in core multilayer sheet)
Further, the core layer 8 in the core multilayer sheet 6 is configured as a so-called core layer disposed at the center of the three-layer sheet. That is, the core layer 8 is formed as a core layer of a three-layer sheet so as to be sandwiched between two skin layers 7 disposed on the outermost sides. The thickness of the core layer 8 is preferably formed so that the ratio of the thickness in all sheets is 20% or more and less than 80%. A more preferable range is 40% or more and less than 75%. When the thickness ratio of the core layer 8 is 80% or more, since the total thickness of the core multilayer sheet 6 is as thin as 50 to 200 μm, the skin layer is also relatively thinned. This is not preferable because it causes variations in heat-fusability between the transparent laser marking sheet 1 (1A, 1B) and the transparent laser marking sheet 1 (1A, 1B), which are outer layers, and the core multilayer sheet 6. Moreover, when the thickness ratio of the core layer 8 is less than 20%, the concealability when printing on the core multilayer sheet 6 cannot be ensured. Furthermore, the contrast when the black marking is performed on the transparent laser marking sheet 1 (1A, 1B), which is the outermost layer, by laser light energy irradiation, and the visibility and clarity of the laser marking portion cannot be ensured. This is not preferable.

As a material (raw material) constituting the core layer 8 in the core multilayer sheet 6, a polycarbonate resin, particularly a transparent polycarbonate resin, is used as described above. However, polycarbonate resin used in particular, without limitation, melt volume rate can be suitably used those 4~20cm ³ / 10min. The melt volume rate of less than 4 cm 3 ^/ 10min, although in terms of toughness of the sheet is improved mean is, since the moldability is inferior, unfavorably a difficulty in practical use. Also the melt volume rate is more than 20 cm ³ / 10min, from becoming inferior in toughness of the sheet, which is not preferable.

(Colorant in the core multilayer sheet)
At least one layer of the skin layer 7 and the core layer 8 of the core multilayer sheet 6 is made of 100 parts by mass of the copolyester resin and / or 100 parts by mass of the polycarbonate resin with a resin such as a dye or a pigment. It is preferable to contain 1 part by mass or more of at least one colorant. In this respect, it differs from the base material sheet 20 constituting the transparent laser marking sheet 1 (1B) provided with an adhesive layer. In this way, 1 part by mass or more of a resin colorant such as a coloring dye or pigment is blended, as will be described later, a transparent laser marking sheet 1 (1A, 1B) and a multilayer for a core that functions as a colored multilayer sheet. This is because when the sheets 6 are laminated and then marked by irradiating with laser light energy, the contrast becomes good. Furthermore, it is for ensuring the concealment property when printing on the core multilayer sheet 6.

  As a coloring agent for resin such as coloring dyes and pigments, titanium oxide, barium oxide, zinc oxide as white pigment, iron oxide, titanium yellow as yellow pigment, iron oxide as red pigment, cobalt blue ultramarine blue as blue pigment, etc. Is mentioned. However, in order to improve the contrast, a light colored and lightly colored system is preferable.

  Among the above-mentioned colorants, it is more preferable to add resin colorants such as white dyes and pigments, which are conspicuous in contrast.

  Furthermore, at least one of the core layer 8 and the skin layer 7 in the core multilayer sheet 6 is at least one of an antioxidant and a coloring inhibitor with respect to 100 parts by mass of the copolyester resin or the polycarbonate resin. It is also one of the preferable forms to contain 0.1-5 mass parts and 0.1-5 mass parts of at least 1 sort (s) of a ultraviolet absorber and a photostabilizer. In the case where at least one of an antioxidant and an anti-coloring agent is added (blended), it effectively acts on physical property reduction and hue stabilization due to molecular weight reduction during molding. In addition, when at least one of an ultraviolet absorber and a light stabilizer is added (mixed), the light deterioration resistance during storage of the electronic marking and the actual use of the electronic passport as the final product This is preferable because it effectively acts on suppression. That is, by adopting such a configuration, a desired amount of at least one of an antioxidant and an anti-coloring agent and at least one of an ultraviolet absorber and a light stabilizer can be appropriately and selectively contained. it can. In addition, since the region to be contained can be selected as appropriate, the effect of the present invention can be further exhibited synergistically as the entire sheet.

  Note that the lubricant, the antioxidant, the anti-coloring agent, and the like of the core multilayer sheet 6 are the same as the lubricant, the antioxidant, and the anti-coloring agent contained in the transparent laser marking sheet described above. Therefore, please refer to the description relating to the transparent laser marking sheet.

(Binding sheet)
The binding sheet 10 in the laser marking sheet for electronic passport is printed by (1) characters, figures, symbols, or information written on the transparent laser marking sheet by laser marking, and (2) printed on the core multilayer sheet 6 described above. Information such as images, characters, etc., and (3) for example, various kinds of information are stored in a storage medium such as an IC chip, or a storage medium such as an IC chip provided in a so-called inlet sheet It is a sheet that plays a very important role in order to firmly bind various stored information together with the passport cover and other visa sheets. Therefore, firm heat-fusibility, moderate flexibility, heat resistance in the heat-fusion process, and the like are required. For example, when the binding sheet 10 is bound on a cover (passport) or the like, it is required that the sewing portion is excellent in tearing and tensile strength, and that the binding portion has light resistance and heat resistance. Furthermore, it is required to have excellent resistance to repeated bending, in other words, excellent hinge characteristics. Therefore, the following materials are preferably used as the binding sheet 10 meeting such a purpose.

  The binding sheet 10 having such a role is formed of at least one selected from a thermoplastic polyester resin, a thermoplastic polyester elastomer, a thermoplastic polyamide resin, a thermoplastic polyamide elastomer, a thermoplastic polyurethane resin, and a thermoplastic polyurethane elastomer. Preferably configured as a sheet. Further, the binding sheet 10 is a polyester resin and / or polyamide resin woven fabric, the woven fabric and a thermoplastic polyester resin, a thermoplastic polyester elastomer, a thermoplastic polyamide resin, a thermoplastic polyamide elastomer, a thermoplastic polyurethane resin, or a thermoplastic polyurethane elastomer. It is also preferable that the laminated sheet is composed of a sheet formed of at least one selected from

(Binding sheet dimensions)
The binding sheet 10 is used for easy binding to the electronic passport as described above. Accordingly, the shape, the length, and the like are not particularly limited as long as the shape and size are easy to bind, and can be appropriately selected as necessary.

  More preferably, the binding sheet 10 has a thickness of 50 to 500 μm, preferably 50 to 250 μm. If the thickness of the binding sheet 10 is less than 50 μm, the strength of the sewing binding portion is insufficient, so that the multilayer sheet on which personal information such as personal characters, figures, symbols, or information is laser-marked may be peeled off from the electronic passport. There is. Further, when the thickness exceeds 500 μm, the rigidity of the sheet becomes too large, and there is a problem that the electronic passport is naturally opened even when not in use.

(Spread sheet overhang)
Further, as shown in FIG. 5, one end of the binding sheet 10 is projected from the transparent laser marking sheet 1 (1A, 1B) and the core multilayer sheet 6 to form the projecting portion 11. preferable. By being configured in this way, it becomes easier to assemble the electronic passport by sewing binding or bonding using the overhanging portion, or by sewing binding and bonding.

  Here, it is preferable that the length of the overhang portion is determined by the sewing binding or bonding workability, or the sewing binding and bonding workability, the strength of the sewing binding part, and the bonding strength. Specifically, the length of the overhang portion is preferably 5 to 100 mm, more preferably 5 to 50 mm, and still more preferably 5 to 20 mm.

  By forming the protruding portion on the binding sheet 10, it becomes easy to assemble the electronic passport. The overhanging portion is formed by using a protruding portion having one end in the longitudinal direction of the binding sheet 10 longer than the transparent laser marking sheet 1 (1A, 1B) and the core multilayer sheet 6, by sewing binding, bonding, or sewing binding. And for assembling to the electronic passport by bonding. In the figure, reference numeral 12 denotes a sewing machine binding portion.

  In the case where the binding sheet 10 is made of a thermoplastic polyester resin, a thermoplastic polyamide resin, or a thermoplastic polyurethane resin, if necessary, on one side or both sides of the portion other than the overhanging portion, a thermoplastic adhesive, or A thermosetting adhesive may be applied. When a thermoplastic adhesive or a thermosetting adhesive is applied, the thickness of the thermoplastic adhesive or the thermosetting adhesive is preferably 0.1 to 20 μm. By doing in this way, it can have adhesive strength and the malfunction at the time of shaping | molding can be suppressed. On the other hand, if the coating thickness of the adhesive is less than 0.1 μm, sufficient adhesive strength cannot be expressed. On the other hand, if the coating thickness of the adhesive exceeds 20 μm, the whole becomes too thick, or problems such as the adhesive sticking out at the time of hot pressing are not preferable.

  Furthermore, when the binding sheet 10 is a woven fabric, it is preferable that the fiber diameter of the fibers constituting the woven fabric is 40 to 250 μm. When there is a mesh opening, the fiber diameter is more preferably 60 to 300 μm. By molding into the desired dimensions as described above, not only the laser marking sheet for electronic passports can be easily molded but also manufactured easily. As the woven fabric, any of a woven fabric having a close eye and a woven fabric having an opening (mesh opening) can be used.

  The binding sheet 10 is made of flat yarn and has a woven sheet (mesh cloth or non-woven fabric) having an opening, and the opening of the woven sheet is closed with a thermoplastic elastomer or a mixture of thermoplastic elastomers. The composite hinge sheet can be preferably used. Here, the fabric-like sheet is a biaxial structure composed of a plurality of warp and weft yarns, or a triaxial structure composed of a plurality of warp, weft and diagonal yarns. Among the plurality of warp yarns, weft yarns, or diagonal yarns, at least one type of yarn is preferably made of a flat yarn having a flat cross section. The binding sheet having such a structure is excellent in the tear strength and tensile strength of the binding portion. In particular, the composite hinge sheet can be surely prevented from being torn off from the passport body. In addition, without losing flexibility, it has sufficient strength against repeated bending and is excellent in temporal stability such as light resistance during actual use.

  Further, as the binding sheet 10, a combination sheet in which a sheet made of a thermoplastic resin and a hinge sheet are joined and connected by point bonding or line bonding can be used. As the thermoplastic resin constituting the sheet, polycarbonate resin, amorphous polyester resin, polymer alloy of polycarbonate resin and amorphous polyester resin, thermoplastic polyurethane elastomer, thermoplastic polyamide elastomer, thermoplastic polyester elastomer, Examples thereof include thermoplastic olefin elastomers, thermoplastic styrene elastomers, thermoplastic acrylic elastomers, thermoplastic ethylene vinyl acetate copolymer elastomers, and the like. Further, as the hinge sheet, a woven fabric, a knitted fabric, or a nonwoven fabric made of at least one selected from a polyester resin, a polyamide resin, a polypropylene resin, and a polyethylene naphthalate resin, and the above-described thermoplastic elastomer or the thermoplastic elastomer. Mention may be made of a composite hinge sheet formed from a mixture comprising. Furthermore, as the woven fabric, knitted fabric or non-woven fabric, the cross section of the yarn is a circular, oval or quadrilateral biaxial structure composed of a plurality of warp and weft yarns, or warp, weft and diagonal yarns. A triaxial structure composed of a plurality of yarns can be mentioned. According to this combination sheet, it has both moldability, workability, and versatility, and has the characteristics of a sheet made of a thermoplastic resin such as heat-fusibility, flexibility, toughness, heat resistance, moldability, and workability. The hinge sheet can have the characteristics such as tear resistance, rupture resistance, flexibility, bending resistance, durability, heat-fusibility, workability, and dimensional accuracy.

  Here, FIG. 5 is a schematic view showing an embodiment of an application example of the transparent laser marking sheet of the present invention to an electronic passport. Specifically, a cross section of a laser marking sheet for electronic passports, in which a core multilayer sheet and a transparent laser marking sheet are laminated and integrated on both sides of a binding sheet for binding to the front cover or back cover of an electronic passport, is schematically illustrated. It is the figure shown in.

(Manufacturing method of multilayer sheet for core and laser marking sheet for electronic passport)
In the present invention, in order to obtain the core multilayer sheet 6, for example, as with the multilayer sheet 20 constituting the transparent laser marking sheet, for example, a method of laminating a resin composition constituting each layer by melt extrusion molding, forming each layer There is a method of forming a resin composition to be formed into a film, laminating it, melt extruding two layers, laminating a separately formed film, etc., but melt extrusion molding from the production and cost aspects. It is preferable to laminate and integrate.

  Specifically, the resin composition of each layer is blended, or pelletized as necessary, and each is put into each hopper of a three-layer T-die extruder having a T-die shared, and the temperature is 200 to 300 ° C. 3 layer T-die melt extrusion molding, and solidification by cooling with a cooling roll or the like can form a three-layer laminate.

  The transparent laser marking sheet 1 (1A, 1B) and the core multilayer sheet 6 obtained as described above are cut into predetermined dimensions and then laminated. In this lamination, the adhesive layer 3 provided on the transparent laser marking sheet 1 (1A, 1B) is arranged so as to be in contact with the core multilayer sheet 6. By arranging in this way, the transparent laser marking sheet (1A, 1B) and the core multilayer sheet 6 can be firmly integrated. Here, it is possible to obtain an integrated sheet as shown in FIGS. 3 to 5 by bonding by heat fusion or the like at a desired temperature at a desired pressure for a desired time.

  Further, the transparent laser marking sheet 1 (1A, 1B) and the core multilayer sheet 6 are each formed by extrusion molding of a two-kind three-layer sheet by melt coextrusion molding. After extrusion molding in this manner, the roll-shaped sheet wound up in a roll shape is passed between heating rollers heated to a predetermined temperature. For example, transparent laser marking sheet 1 (1A, 1B) / multilayer sheet 6 for core / transparent laser marking sheet 1 (1A, 1B), core multilayer sheet 6 / polyester elastomer sheet, or polyester mesh cloth / core It is good to manufacture by the method of cutting to a predetermined dimension, etc., after manufacturing the elongate laminated body sheet | seat by heating and a pressurizing roller through the multilayer sheet 6, and pressurizing. The adhesive layer 3 of the transparent laser marking sheet 1 (1A, 1B) is made of a polyester resin on at least one surface thereof after melt extrusion molding of the base sheet 2, 20 in the transparent laser marking sheet 1 (1A, 1B). The transparent heat-activatable adhesive is coated (applied) to form the adhesive layer 3. It is preferable that the core multilayer sheet 6 is in contact with the side on which the adhesive layer 3 is formed and heated and pressed to be molded.

  Further, after the transparent laser marking sheet 1 (1A, 1B) and the core multilayer sheet 6 are cut into predetermined dimensions, the transparent laser marking sheet 1 (1A, 1B) is, for example, the same as described above by a hot press machine. / Multilayer sheet for core 6 / Transparent laser marking sheet 1 (1A, 1B), Transparent laser marking sheet 1 (1A, 1B) / Multilayer sheet for core 6 / Polyester elastomer sheet, or polyester mesh cloth / multilayer sheet for core 6 / transparent laser marking sheet 1 (1A, 1B), or a multi-layer sheet 6 for core / another sheet / multi-layer sheet 6 for core can also be produced. Also in this laminated manufacturing, it is preferable to manufacture a single-wafer laminated sheet such that the adhesive layer 3 provided on the transparent laser marking sheet 1 (1A, 1B) is in contact with the core multilayer sheet 6.

  Here, the desired time, the desired pressure, and the desired temperature are not particularly limited, such as transparent laser marking sheet 1 (1A, 1B), core multilayer sheet 6, polyester elastomer sheet, or polyester mesh cloth. It is preferable to select appropriately considering the composition, type and the like. In general, examples include 10 to 6 minutes, 1 to 20 Mpa, and 120 to 170 ° C. as an example. If the time is less than 10 seconds, a reliable integrated laminate may not be obtained, and even if the time exceeds 6 minutes, an effect commensurate with it cannot be obtained and the production efficiency becomes inferior. Absent. Further, if the pressure is less than 1 Mpa, stacking failure may occur, and if it exceeds 20 Mpa, the dimensional accuracy of the laminate may be affected, which is not preferable. Further, when the temperature is less than 120 ° C., stacking failure may occur as in the case where the pressure is too low. When the temperature exceeds 170 ° C., the laminate is warped or shrunk, and printed on the core layer. Images, characters, etc. may be unclear, which is not preferable.

(5-layer laminate)
As described above, the laser marking sheet for electronic passport is transparent laser marking sheet 1 (1A, 1B) / multilayer sheet 6 for core / binding sheet 10 / multilayer sheet 6 for core / transparent laser marking sheet 1 (1A, 1B). It is preferable that it is comprised as a 5 layer laminated body which consists of. That is, by forming a laminated structure of transparent laser marking sheet 1 (1A, 1B) / core multilayer sheet 6, a two-layer laminated structure consisting of at least a transparent laser marking and a colored sheet (including a white type) is formed. Compared to a laminate composed of a laser marking layer and a white layer, the contrast ratio in laser marking is further improved, and the clarity of characters, figures, symbols, information, etc. is improved.

  In addition, by forming a 5-layer laminate structure of transparent laser marking sheet 1 (1A, 1B) / multilayer sheet 6 for core / binding sheet 10 / multilayer sheet 6 for core / transparent laser marking sheet 1 (1A, 1B), Laser marking can be performed from either the front surface and / or the back surface. Further, when these five-layer laminates are heat-bonded and integrated by hot press molding, the resulting five-layer laminate sheet is hardly warped. As described in detail above, the thickness of each layer is 50 to 200 μm for the transparent laser marking sheet 1 (1A, 1B), 50 to 200 μm for the core multilayer sheet 6, and 50 to 50 for the binding sheet 10. It is preferable that it is 500 micrometers.

  More preferably, the transparent laser marking sheet / multi-layer sheet for core / binding sheet / multi-layer sheet for core / transparent laser marking sheet has a five-layer laminate structure, and the base material sheet constituting the transparent laser marking sheet is described above. It has a three-layer structure.

  The five-layer laminate can be produced by various methods. For example, after laminating transparent laser marking sheet 1 (1A, 1B) / multi-layer sheet 6 for core / binding sheet 10 / multi-layer sheet 6 for core / transparent laser marking sheet 1 (1A, 1B), heat fusion is performed by a heating press. A five-layer laminate can be produced by wearing (thermal lamination).

(Printing method of 5-layer laminate)
When it is desired to print the laminate as described above, after applying UV offset printing or UV silk printing on one side of the core multilayer sheet 6, the transparent laser marking sheet 1 (1A, 1B) / After stacking the printed core multilayer sheet / binding sheet 10 / printed core multilayer sheet / transparent laser marking sheet 1 (1A, 1B), heat fusion (thermal lamination) is performed with a heating press. Alternatively, after the core multilayer sheet 6 / binding sheet 10 / core multilayer sheet 6 are laminated by heat fusion using a hot press, UV offset printing or UV silk printing is further applied to the surface of the hot press laminate. . The laminated body and the transparent laser marking sheet 1 (1A, 1B) subjected to the printing are laminated with the transparent laser marking sheet 1 (1A, 1B) / (core multilayer sheet 6 / binding sheet 10 / core multilayer sheet 6). It can also be manufactured by laminating and heat-pressing the body / transparent laser marking sheet 1 (1A, 1B). In addition, when laminating and heat pressing, the transparent laser marking sheet 1 (1A, 1B) is disposed such that the adhesive layer forming surface is in contact with the printed surface of the printed core multilayer sheet. .

  Here, a preferable UV ink that can be used in the present invention is an ink (ultraviolet curable ink) that is cured (dried) by causing a photochemical reaction by applying ultraviolet energy. In the present invention, as long as it is a UV ink, there is no limitation on the photopolymerizable resin, photopolymerization initiator, pigment, and other components and compositions constituting the UV ink. Any known one can be used and is not particularly limited. Such UV ink requires a short time for curing (drying), and printing with UV ink is excellent in chemical resistance and abrasion resistance. In the present invention, ink by other curing methods such as osmotic curing (drying), heat evaporation curing (drying), or oxidative polymerization is not preferable.

  The offset printing in the present invention is a conventionally known printing method. Specifically, it is a printing system in which ink is printed from a plate to a printing medium (multilayer sheet for core) through a blanket. There are no particular limitations on the type of blanket, the presence or absence of dampening water, and the like for this offset printing.

  Furthermore, UV silk printing is a conventionally known printing method similar to the offset printing described above. Specifically, a silk cloth is used for the plate material, an appropriate amount of ink is pushed out by rubbing the ink between the silks with a spatula, and the printing medium (multi-layer sheet for core) is loaded from the gap in the original plate It is. Various methods employed in the silk printing field can also be adopted for this silk printing. There is no particular limitation.

  According to the UV silk printing, it is possible to print in a subtle color tone with a three-dimensional effect, and with offset printing, multicolor printing is easy and can be performed at an advantageous cost. Therefore, UV silk printing and offset printing are preferable to letterpress printing and intaglio printing.

  Furthermore, as described above, after UV offset printing or UV silk printing is performed on one side of the core multilayer sheet 6, a varnish, which is a kind of adhesive, is thinly applied to the printed surface. After drying, the transparent laser marking sheet 1 (1A, 1B) / core multi-layer sheet coated with varnish / binding sheet 10 / core multi-layer sheet coated with varnish / transparent laser It can also be manufactured by laminating the marking sheets 1 (1A, 1B) and heat-pressing them. Thus, by apply | coating varnish to a printing surface, it can anticipate further performing strong adhesion | attachment with the adhesive bond layer of transparent laser marking sheet 1 (1A, 1B).

  In addition, after applying a thermoplastic or thermosetting adhesive to a thickness of 0.1 to 20 μm in advance on one side or both sides of the core multilayer sheet 6 and the binding sheet 10, transparent laser marking is performed in the same manner as described above. After laminating sheet 1 (1A, 1B) / core multilayer sheet 6 / binding sheet 10 / core multilayer sheet 6 / transparent laser marking sheet 1 (1A, 1B), heat lamination (heat fusion) or transparent After laminating the laser marking sheet 1 (1A, 1B) / core multilayer sheet 6 / binding sheet 10 / core multilayer sheet 6 / transparent laser marking sheet 1 (1A, 1B), dry lamination (pressure bonding) is performed. Also good. A known apparatus and method can be employed for the thermal lamination or dry lamination.

  Further, when printing is performed on such a laminate sheet, it is more preferable that a transparent laser marking sheet (1A, 1B) is applied after UV offset printing or UV silk printing is performed on one side of the core multilayer sheet 6. ) / Printed core multilayer sheet / binding sheet 10 / printed core multilayer sheet / transparent laser marking sheet (1A, 1B), and then heat lamination by a hot press. Or, after applying UV offset printing or UV silk printing on one side of the core multilayer sheet 6, a thin varnish, which is one type of adhesive, is applied to the printed surface, and after drying, a transparent laser Marking sheet (1A, 1B) / Multilayer sheet for core coated with varnish / Binding sheet 10 / Multilayer sheet for core coated with varnish / Transparent laser marking sheet (1A, 1B) A laser marking sheet for electronic passports is formed by laminating and thermal lamination. According to this, convenience such as easy molding is improved.

  In the case of thermal lamination, the heating press temperature is 100 to 170 ° C., preferably 130 to 160 ° C., although it varies depending on the type of sheet constituting the laser marking sheet for electronic passports. Adhesion failure may occur if the heating press temperature is less than 100 ° C, and if it exceeds 170 ° C, abnormalities such as warpage, shrinkage, or protrusion of the sheet are undesirable.

  Furthermore, between the above-mentioned core multilayer sheet 6 and the binding sheet 10, a dicarboxylic acid unit mainly composed of terephthalic acid units, an ethylene glycol unit (I), and a 1,4-cyclohexanedimethanol unit (II) are mainly composed. And an ethylene glycol unit (I) and a 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90 to 30/10 to 70 mol%. A laser marking sheet for electronic passports obtained by inserting a sheet made of a copolymerized polyester resin or the like or another adhesive thermoplastic resin sheet is also preferable. Specifically, transparent laser marking sheet (1A, 1B) / multilayer sheet 6 for core / sheet made of copolymer polyester resin, other adhesive thermoplastic resin sheet / binding sheet / sheet made of copolymer polyester resin, and others 7 layers of adhesive thermoplastic resin sheet / multilayer sheet for core / transparent laser marking sheet (1A, 1B). The sheet made of the copolyester resin or other adhesive thermoplastic resin sheet is also a laser marking sheet for electronic passports that has been subjected to mat processing with a thickness of 50 to 300 μm and an average roughness (Ra) of 0.1 to 5 μm. One of the preferred forms.

  Thus, a binding sheet is obtained by laminating a sheet made of a desired copolyester resin, another adhesive thermoplastic resin sheet, between the core multilayer sheet and the binding sheet, and between the binding sheet and the core multilayer sheet. When the laser marking sheet for electronic passports is used as an electronic passport, the peel strength between the sewing binding cloth with the front cover or the back cover and the laminate can be improved. Therefore, this is one of the preferred forms.

  Specifically, for example, as will be described later, the electronic passport is formed by binding or adhering to the electronic passport cover or the back cover using the protruding portion 11 of the binding sheet, or by binding and bonding the sewing pass. In the case of molding, if the sheet is artificially peeled between the binding sheet and the multilayer sheet, this portion is peeled off, and forgery is performed by re-adhesion with another sheet. However, with the configuration as described above, the binding sheet and another sheet are more integrated to prevent artificial peeling, thereby preventing the electronic passport from being counterfeited.

  Further, the above-described laser marking sheet for electronic passports is configured as a five-layer laminate of transparent laser marking sheet / multilayer sheet for core / inlet sheet / multilayer sheet for core / the transparent laser marking sheet, At least an IC chip and an antenna are disposed on the binding sheet. Alternatively, on the binding sheet and / or below the dicarboxylic acid unit mainly composed of a terephthalic acid unit and the ethylene glycol unit (I) and the glycol unit mainly composed of 1,4-cyclohexanedimethanol unit (II). Copolymer in which ethylene glycol unit (I) and 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90-30 / 10-70 mol% A polyester resin is laminated, and an IC chip and an antenna are provided as an inlet sheet. In addition, it is preferable to be configured as a laser marking sheet for electronic passports in which the total thickness of the laminated sheets after lamination is thinner than the total thickness of each sheet thickness before lamination. An IC chip and an antenna can be easily disposed, and can be used as a so-called IC chip built-in type laser marking sheet for an electronic passport.

  For example, each sheet having a desired configuration as described above, and having a thickness before lamination of a transparent laser marking sheet of 50 to 200 μm, a core multilayer sheet of 50 to 200 μm, and a thickness of 200 to 400 μm The laser marking sheet for electronic passports, wherein the total thickness of the laser marking sheet for electronic passports is less than the total thickness of the transparent laser marking sheet, the core multilayer sheet, and the inlet sheet. Can be illustrated as an example.

  As another example, each of the sheets having a desired configuration as described above, the sheet thickness before lamination of the transparent laser marking sheet having a thickness of 50 to 200 μm, and a multilayer for a core having a thickness of 50 to 200 μm. The sheet is formed as an inlet sheet composed of 200 to 400 μm, and one end of the binding sheet is provided with an overhang portion that is 5 to 100 mm longer than the transparent laser marking sheet and the core multilayer sheet. As an example, it is possible to exemplify a structure in which the inlet sheet is formed or bonded to the electronic passport using the overhanging portion, or is assembled and bonded to the electronic passport. .

  Here, the above-described IC chip built-in type (so-called IC chip model) electronic passport laser marking sheet can be manufactured, for example, as follows. (1) First, the transparent laser marking sheet, the core multilayer sheet, and the binding sheet are manufactured by the manufacturing method described above. (2) Next, on the upper and lower sides of the binding sheet, a dicarboxylic acid unit mainly composed of a terephthalic acid unit, an ethylene glycol unit (I), and a glycol unit mainly composed of 1,4-cyclohexanedimethanol unit (II). Polyester, and a copolymerized polyester in which ethylene glycol unit (I) and 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90-30 / 10-70 mol% A layer made of resin is formed. (3) The copolyester resin layer / binding sheet / copolyester resin layer thus obtained is hot-pressed to form a laminate. (4) Further, an IC chip and an antenna are disposed on the laminated body after the heat pressing.

  Next, (5) a dicarboxylic acid unit mainly composed of a terephthalic acid unit, an ethylene glycol unit (I), and a 1,4-cyclohexanedimethanol unit (II) are mainly composed so as to cover the IC chip and the antenna. And an ethylene glycol unit (I) and a 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90 to 30/10 to 70 mol%. A layer made of a copolyester resin is formed. As described above, when the layer made of the above-described copolymer polyester resin is formed so as to cover the IC chip and the antenna, the IC chip and the antenna are prevented from being damaged due to stress or heat during the heat press. Is preferable.

  Thereafter, (6) heating press is performed to form an inlet sheet. (7) Further, using the inlet sheet, the above-mentioned transparent laser marking sheet, and the multilayer sheet for core, transparent laser marking sheet / multilayer sheet for core / inlet sheet / multilayer sheet for core / transparent laser marking sheet By forming a five-layer laminate, the above-mentioned IC chip built-in type (so-called IC chip model) electronic passport laser marking sheet can be formed. However, the above-described manufacturing method is an example and is not particularly limited thereto.

  In the production of a laser marking sheet for an electronic passport of an IC chip built-in type (so-called IC chip model), a layer was formed so as to cover the IC chip and the antenna, “dicarboxylic acid unit mainly composed of terephthalic acid unit” And a glycol unit mainly composed of an ethylene glycol unit (I) and a 1,4-cyclohexanedimethanol unit (II), and the ethylene glycol unit (I) and 1,4-cyclohexanedimethanol It is also preferable to use, for example, an adhesive sheet instead of the “copolymerized polyester resin in which the unit (II) is (I) / (II) = 90 to 30/10 to 70 mol%”. It is possible not only to omit the subsequent heat pressing step for forming the inlet sheet, but also to reduce the damage to the IC chip and the antenna from stress and heat that are easily applied during excessive heat pressing. Examples of such an adhesive sheet include a polyester adhesive sheet having a thickness of about 30 μm (for example, trade name “Aron Melt PES-111EE sheet” manufactured by Toa Gosei Co., Ltd.). It is not limited to anything.

  Further, as described above, the IC sheet and the antenna are coated on the inlet sheet so that “dicarboxylic acid unit mainly composed of terephthalic acid unit and ethylene glycol unit (I) and 1,4-cyclohexanedimethanol unit. (II) is a polyester composed of glycol units, and the ethylene glycol unit (I) and the 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90-30. Even in the case of using a copolymer polyester resin that is / 10 to 70 mol% or an adhesive sheet as described above, the thickness of the inlet sheet is preferably within the above-mentioned desired range as a whole.

  Moreover, the transparent laser marking sheet in this embodiment can be used suitably for an electronic passport.

  For example, when used in an electronic passport, two transparent laser marking sheets according to the present embodiment are prepared, and a binding sheet is disposed between the transparent laser marking sheets for easy binding, and a sewing binding portion is provided as necessary. In addition, a cover, a laminate using the present embodiment, a visa sheet, an IC chip, and the like may be arranged to create an electronic passport. However, this is an example, and the present invention is not necessarily limited to such a configuration.

  Furthermore, the transparent laser marking sheet in the present embodiment can be suitably used for plastic cards.

  Here, examples of the plastic card to which the transparent laser marking sheet of the present invention can be applied include a prepaid card, a members card, an ID card, a telephone card, a commuter pass, and a cash card. However, it is not limited to this.

  For example, a transparent laser marking sheet formed with a transparent thermally active adhesive layer made of polyester resin is bonded to one side or both sides of a plastic information medium sheet forming a plastic card. At the time of joining, the adhesive layer provided on the transparent laser marking sheet is heated and integrated so as to be in contact with the plastic information medium sheet. At this time, the transparent thermally active adhesive made of polyester resin provided on the transparent laser marking sheet can be firmly bonded without softening or deforming the plastic information medium sheet forming the plastic card. it can. The plastic card as described above is frequently used by being taken in and out of a card case or a bag, and is passed through a data reading machine.

  The transparent laser marking sheet formed with the transparent heat-active adhesive layer made of the above-described polyester resin is firmly joined and integrated with the plastic information medium sheet, so there is no possibility of peeling off. In addition, since the transparent laser marking sheet has high transparency, it is excellent in the visibility of the printed information printed on the plastic information medium sheet, and the characters, figures, symbols, information, etc. are clearly displayed by the laser mark. Can be marked.

(Matte processing)
Moreover, it is preferable that the surface of at least one of the transparent laser marking sheet, the core multilayer sheet, and another sheet is matted with an average roughness (Ra) of 0.1 to 5 μm. As described above, the reason why the mat processing is selectively formed on the surface of each sheet as described above is, for example, that the configuration of the sheet of the present embodiment is the transparent laser marking sheet of the present embodiment / another sheet. This is because when the hot press molding is performed, air between the transparent laser marking sheet of this embodiment and another sheet can be easily removed, and the same applies to other sheets. On the other hand, if these sheets are not mat processed when transported to the lamination process, they are sucked, adsorbed and transported, these sheets are aligned and stacked, and then air is injected to remove the sheets. When doing so, there is a tendency that problems such as difficulty in detachment and shifting of the stacking position even if detachable can occur.

  On the other hand, if the average roughness (Ra) of mat processing exceeds 5 μm, the heat-sealing property of the transparent laser marking sheet / other sheet of the present embodiment tends to be lowered. Furthermore, it is preferable that the sheet as a whole can be easily adjusted by making it appropriately selectable. Further, when the average roughness (Ra) of the surface is less than 0.1 μm, as described above, there is a tendency that a problem such as sticking of the sheet to the conveying machine during sheet conveyance and lamination is likely to occur.

  Also, the above-mentioned laser marking sheet for electronic passport is used, and a transparent laser marking sheet / multi-layer sheet for core / binding sheet / multi-layer sheet for core / laminated sheet of transparent laser marking sheet, or transparent laser marking sheet / core Multi-layer sheet / Inlet sheet / Multi-layer sheet for core / transparent laser marking sheet, or transparent laser marking sheet / multi-layer sheet for core / separate sheet / binding sheet / separate sheet / multi-layer sheet for core / transparent laser Formed to be an electronic passport formed by binding or bonding to the electronic passport cover or back cover using the overhanging portion of the binding sheet of the 7-layer laminated sheet of the marking sheet, or by sewing and bonding. It is preferable to do. Such a configuration is preferable because the electronic passport can be easily formed.

[III] Laser marking method:
The transparent laser marking sheet in the present embodiment is one that develops color by irradiating laser light energy. Examples of the laser light energy include gas lasers such as He—Ne laser, Ar laser, CO ₂ laser, and excimer laser, and YAG. Examples of the laser include solid lasers such as a laser, Nd · YVO ₄ laser, semiconductor lasers, and dye lasers. Of these, YAG laser and Nd · YVO ₄ laser are preferable.

  In the laser marking method of the present embodiment, the laser beam may be single mode or multimode as the laser light energy. Further, in addition to a beam diameter reduced to 20 to 40 μm, a beam diameter as wide as 80 to 100 μm can be used. However, in the single mode, the beam diameter of 20 to 40 μm is preferable from the viewpoint of obtaining the print quality with good contrast by setting the contrast of the printing by laser marking or the like and the contrast of the base to 3 or more.

  Thus, when the transparent laser marking sheet of this embodiment is irradiated with laser light energy, the laser light energy absorbent contained in the base sheet (single layer sheet or core layer of the multilayer sheet) absorbs the laser light energy. Color. However, since this transparent laser marking sheet is mainly composed of a polycarbonate resin having high heat resistance, it can be irradiated with high-power laser light energy. Therefore, characters, figures, symbols, information, etc. can be marked easily and more clearly.

  Further, the base sheet is configured as a multilayer sheet as described above, and thus, in the single-layer sheet, “foaming” is generated by irradiation with laser light energy of higher output, and this foaming causes “swelling” of the sheet surface. The “swelling” phenomenon is suppressed by the action of the skin layer of the multilayer sheet even under the condition where the phenomenon occurs. Therefore, characters, figures, symbols, information, etc. can be marked more clearly. The action of this skin layer does not stop there. In the case of a single-layer sheet, the laser marking portion is directly cut by friction with the outside. On the other hand, by providing a skin layer, even if the skin layer is shaved, the laser marking portion is not shaved. For this reason, the abrasion resistance of the laser marking part becomes more excellent.

  Furthermore, since the sheet | seat which consists of polycarbonate resin has high heat resistance, in the multilayer sheet | seat, it is necessary to make the heat-fusion temperature into the high temperature of 200-230 degreeC. There is also a problem with the productivity of the hot press process. In addition, it is common for plastic data sheets for electronic passports to perform various types of printing on an intermediate layer called an inlay sheet. In the process of performing the multilayer lamination heating press after printing on the inlay sheet, when the heat fusion temperature is set to a high temperature of 200 to 230 ° C., the printing is often “yake”. Therefore, in this case, the printed characters and images may cause discoloration, which is not preferable.

  For this problem, the base sheet is a transparent laser marking sheet composed of the above-mentioned single-layer sheet, or the core is a base layer of the transparent laser marking sheet composed of the above-mentioned multilayer sheet. A colored three-layer sheet composed of skin layer / core layer (colored) / skin layer is laminated on the multilayer sheet. Thereby, the glass transition temperature of the skin layer is about 80 ° C., which is about 60 to 70 ° C. lower than the glass transition temperature of the polycarbonate resin of the core layer. Therefore, the heat fusion temperature can be lowered to about 150 to 170 ° C. and about 50 to 60 ° C. Therefore, the characters and images printed on the core multilayer sheet have an effect of suppressing discoloration. Therefore, the transparent laser marking sheet of the present embodiment is excellent in sharpness such as printing by laser marking, and the surface layer, or the core layer of the surface layer, is colored black by laser light energy irradiation to produce characters, figures, symbols, or information. However, since the underlayer is white, it is possible to mark clear characters, figures, symbols, or information with black / white contrast.

  More preferable is a method of laser marking on the above-described transparent laser marking sheet, and printing is performed by irradiating laser light energy from the transparent laser marking sheet side (opposite side of the adhesive layer forming surface). . Thus, by irradiating desired laser light energy from the base sheet side of the transparent laser marking sheet, it is possible to easily and clearly mark characters, figures, symbols, information, or the like. Therefore, the transparent laser marking sheet of the present embodiment is excellent in laser marking properties and heat fusion properties, and is also excellent in wear resistance of the laser marking portion.

  More preferably, in the laser marking method for laser marking on the transparent laser marking sheet described so far, the transparent laser marking sheet is integrated with the printing sheet subjected to UV offset printing or UV silk printing. It is preferable to laser mark a character, a figure, a symbol, or information by irradiating laser light energy toward the surface where the adhesive layer is not formed. Characters, figures, symbols, or information can be marked by irradiating laser light energy from the side where the adhesive layer is not formed. The laser marking portion has a high contrast, a clear laser marking is obtained, and it is excellent in preventing falsification and forgery.

  By forming the transparent heat-active adhesive made of the above-described polyester resin on at least one surface of the base material sheet in advance, a predetermined amount of the transparent heat-active adhesive is formed in a predetermined thickness on the base material sheet at the site. Work becomes unnecessary. Therefore, it is highly versatile and easy to mold. The transparent thermally active adhesive made of a polyester resin formed on at least one side of the above-described base material sheet, by irradiating laser light energy, in the laser marking property when marking characters, figures, symbols, or information, Has no adverse effect at all. That is, the contrast and sharpness of laser-marked characters, figures, symbols, or information are not reduced. And even if it irradiates with a laser beam energy, the adhesiveness of an adhesive bond layer will not become inferior, and it will not discolor.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto, and various evaluations and measurements in the examples and comparative examples were performed by the following methods.

[1] Transparency of transparent laser marking sheet:
About the transparent laser marking sheet used in Examples 1-5 and Comparative Examples 1-6, the total light transmittance of the sheet was measured using a spectrophotometer (manufactured by Macbeth, trade name “EY7000”). As evaluation, it evaluated by the following criteria.
"Evaluation criteria"
A: Total light transmittance is 80% or more and total light transmittance is very good.
○: Total light transmittance is 60% or more and less than 80%, and the total light transmittance is good.
X: The total light transmittance is less than 60%, and the total light transmittance is poor.

[2] Adhesiveness between transparent thermoactive adhesive and substrate sheet:
For the transparent laser marking sheets used in Examples 1 to 5 and Comparative Examples 1 to 4, the cross-cut test (25 squares) was performed on the adhesion between the transparent thermally active adhesive and the base sheet in accordance with JIS K 5600. Observed and evaluated according to the following criteria.
"Evaluation criteria"
A: No peeling at all and adhesion is very good.
○: Adhesiveness is good only for very small peeling within 5 locations.
Δ: Small peeling and adhesion at about 10 locations are normal.
X: 10-20 or more small peeling and adhesiveness are bad.
Xx: The entire surface is peeled off and the adhesion is extremely poor.

[3] Heat fusion property:
About the transparent laser marking sheet used in Examples 1 to 5 and Comparative Examples 1 to 6, the heat fusion property between the transparent laser marking sheet A1, A2, or A3 and the printed multilayer sheet B is determined according to the following criteria. evaluated.
"Evaluation criteria"
(Double-circle): There is no peeling, it is excellent in heat-fusion property, and heat-fusion property is very good.
○: Partial peeling occurs, but the fracture mode is good for material destruction and heat fusion.
Δ: Peeling and heat fusing properties are normal with a fairly strong force.
X: The entire surface is peeled off with a small force and the heat fusion property is poor.

[4] Laser marking property:
To the transparent laser marking multilayer sheets obtained in Examples 1 to 5 and Comparative Examples 1 to 6, Nd · YVO ₄ laser (trade name “LT-100SA” manufactured by Laser Technology Co., Ltd. “RSM10E”) was used to evaluate laser marking properties. Specifically, the laser marking property was evaluated at a laser light energy irradiation speed of 400 mm / second, and the sharpness of the image and the surface state of the laser marking portion were evaluated according to the following criteria.
"Evaluation criteria"
◯: Excellent sharpness, no abnormalities such as “blowing” of the laser light energy irradiation part, and laser marking properties are extremely good.
Δ: Sharpness is good, but slight “swelling” occurs in the laser light energy irradiated area, and laser marking property is normal.
X: Visibility is good, but “swelling” occurs in the laser light energy irradiated part, and the laser marking property is poor.

(Production Example 1) Base sheet A1 (single layer sheet):
Polycarbonate resin (manufactured by Idemitsu Kosan Co., Ltd., trade name "TARFLON FN2500A", melt volume rate ⁼ 8cm 3 / 10min) with 100 parts by weight of carbon black (manufactured by Mitsubishi Chemical Corporation # 10 as an energy absorber that absorbs laser light energy, 0.0015 parts by mass of an average particle size of 75 nm and DBP oil absorption of 86 ml / 100 gr) is added, and n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) is used as a phenolic antioxidant. ) Propionate (manufactured by Ciba Specialty Chemicals, trade name “Irganox 1076”) as 0.1 part by mass, and UV absorber, 2- (2′-hydroxy-3 ′, 5′-di-t-) Butylphenyl) -5-chlorobenzotriazole (Ciba Specialty Chemi) Luz Co., trade name "TINUVIN 327"), by blending 0.2 part by weight, to obtain a substrate having a thickness of 100μm monolayer sheet A1 (monolayer sheet) by a T-die extrusion method.

(Production Example 2) Substrate sheet A2 (multilayer sheet):
As a skin layer, an amorphous polyester resin (manufactured by Eastman Chemical Co., Ltd., trade name “Easter GN071”, EG / CHDM (ethylene glycol unit / 1,4-cyclohexanedimethanol unit, the same shall apply hereinafter) = 70/30 mol%) In 100 parts by mass, 0.1 part by mass of calcium stearate was blended as a lubricant. Polycarbonate resin as the core layer (manufactured by Idemitsu Kosan Co., Ltd., trade name "TARFLON FN2500A", melt volume rate ⁼ 8cm 3 / 10min) was used 100 parts by weight of carbon black (manufactured by Mitsubishi Chemical Corporation as an energy absorber that absorbs laser light energy # 10, 0.0015 parts by mass of average particle size 75 nm, DBP oil absorption 86 ml / 100 gr) and (n-octadecyl-3- (3,5-di-t-butyl-) as a phenolic antioxidant 0.1 part by mass of 4-hydroxyphenyl) propionate (“Irganox 1076” manufactured by Ciba Specialty Chemicals) and 2- (2′-hydroxy-3 ′, 5′-di-t) as an ultraviolet absorber -Butylphenyl) -5-chlorobenzotriazole (Ciba Specialty) Chemicals, Inc., trade name “Tinuvin 327”) was blended in an amount of 0.2 parts by mass, and a three-layer transparent laser marking multilayer sheet A2 of skin layer / core layer / skin layer was obtained by a T-die coextrusion method. The total thickness of the sheet is 100 μm, and the thicknesses of the skin layers on the front and back sides are the same, and the layer structure is configured as skin layer (16 μm) / core layer (68 μm) / skin layer (16 μm). A base sheet A2 (multilayer sheet) having a core layer thickness ratio of 68% was obtained.

(Production Example 3) Multi-layer sheet for core:
100 parts by mass of an amorphous polyester resin (trade name “Easter GN071”, EG / CHDM = 70/30 mol%) manufactured by Eastman Chemical Co., Ltd. as a skin layer, 0.1 parts by mass of calcium stearate as a lubricant, and titanium oxide 15 blended parts by weight of a polycarbonate resin as the core layer (manufactured by Idemitsu Kosan Co., trade name "TARFLON FN2500A", melt volume rate ⁼ 8cm 3 / 10min) 100 parts by weight, as a phenolic antioxidant, (n- octadecyl-3- 0.1 parts by mass of (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals, trade name “Irganox 1076”), and UV absorber, 2- ( 2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5- Lobenzotriazole (Ciba Specialty Chemicals, Inc., trade name “Tinuvin 327”) 0.2 parts by mass and titanium oxide 15 parts by mass are blended, and skin layer / core layer / skin layer by T-die coextrusion method The total thickness of the sheet was set to 300 μm, and the thicknesses of the skin layers on the front and back sides were the same, and the structure of the layers was skin layer (40 μm) / core layer (220 μm). / The thickness of the core layer was set to 73% while the skin layer (40 μm) was formed, and the average surface roughness (Ra) on both sides was 0.5 to 1.8 μm. A processed multilayer core sheet was obtained, and printing was performed on one side of the core multilayer sheet by UV offset printing.

Example 1
The base sheet A1 (single layer sheet) obtained in Production Example 1 was used. Further, as a transparent thermoactive adhesive used for the adhesive layer, a water-dispersed polyester resin (trade name “Vylonal MD-1200” manufactured by Toyobo Co., Ltd. (solid content concentration: 34% by mass, butyl cellosolve: 11% by mass, number average molecular weight) 15000, glass transition temperature 67 ° C.) On one side of the base sheet A1, the above-mentioned transparent thermally active adhesive was applied and dried using an automatic film applicator (manufactured by Yasuda Seiki Seisakusyo). As a result, a transparent laser marking sheet having a transparent heat-active adhesive layer having a dry coating thickness of 6 to 8 μm was obtained for the core subjected to the UV offset printing manufactured in this transparent laser marking sheet and Production Example 3. A release agent was applied to each end of the multilayer sheet, then the surface of the transparent laser marking sheet on which the transparent thermally active adhesive layer was formed, and the core Layered sheet UV offset printing surface is in contact with transparent laser marking sheet / core multilayer sheet with UV offset printing / core multilayer sheet with UV offset printing / transparent laser marking sheet After lamination, the film was sandwiched between two chrome-plated plates, and preheated for 2 minutes at a preheating temperature of 100 ° C. using a vacuum press (manufactured by Nissei Plastic Industry Co., Ltd.) After preheating, the heating temperature was 160 ° C. and the surface pressure was 30 kg. / Cm ² for 2 minutes (hereinafter referred to as “heat fusion process”), and then cooled to room temperature to obtain a transparent laser marking multilayer sheet. Fusing property was evaluated, and a transparent laser marking multilayer sheet was obtained in the same manner as above except that no release agent was used. A transparent laser marking multilayer sheet, and evaluated the laser marking property.

  Hereinafter, also in Examples 2 to 4 and Comparative Examples 1 to 6, laser marking properties were evaluated in the same manner as in Example 1.

(Example 2)
The base sheet A1 (single layer sheet) obtained in Production Example 1 was used. In addition, as a transparent thermally active adhesive used for the adhesive layer, a polyester resin (XJ-36 manufactured by Toa Gosei Co., Ltd. (solid content concentration: 25 mass%, cyclohexanone solvent) is prepared, and an automatic film applicator is used to form a single layer. A transparent laser marking sheet having a transparent thermally active adhesive layer having a dry coating film thickness of 6 to 8 μm was obtained by coating and drying on one side of the base sheet A1.This transparent laser marking sheet and Production Example 3 The same as in Example 1 except that a release agent is applied to one end of each of the core multilayer sheets subjected to UV offset printing manufactured in Step 1 so that the UV offset printing surface of the core multilayer sheets subjected to UV offset printing is in contact with each other. After the lamination, after the same heat-sealing process, the laminate was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Example 3)
The base sheet A2 (multilayer sheet) obtained in Production Example 2 was used (the thickness of the base sheet A2 is 100 μm). Further, the same water-dispersed polyester resin as that used in Example 1 was prepared as a transparent thermally active adhesive used in the adhesive layer. With an automatic film applicator, coating and drying were performed on one side of the substrate sheet A2 (multilayer sheet) to obtain a transparent laser marking sheet on which a transparent thermally active adhesive layer having a dry coating thickness of 6 to 8 μm was formed. A release agent is applied to each end of the transparent laser marking sheet and the core multilayer sheet printed in Production Example 3 so that the UV offset printing surface of the core multilayer sheet subjected to UV offset printing is in contact with the transparent laser marking sheet. Then, the layers were laminated so as to have the same configuration as in Example 1. After laminating, after the same heat fusion process, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

Example 4
The base sheet A1 (single layer sheet) obtained in Production Example 1 was used. Moreover, as a transparent thermoactive adhesive used for an adhesive layer, water-dispersed polyester resin (solid content concentration 20% by mass, ethyl cellosolve / butyl cellosolve mixed solvent (mass ratio 1/1), number average molecular weight 5000, glass transition temperature 80 ° C.). In the same manner as in Example 1, with an automatic film applicator, a transparent laser marking sheet was formed by coating and drying on one side of the base sheet A1 to form a transparent thermally active adhesive layer having a dry coating thickness of 6 to 8 μm. Obtained. A release agent is applied to each end of the transparent laser marking sheet and the core multilayer sheet subjected to UV offset printing manufactured in Production Example 3 so that the printing surface of the core multilayer sheet subjected to UV offset printing is in contact with the transparent laser marking sheet. Then, the layers were laminated so as to have the same configuration as in Example 1. After the lamination, in the same manner, after the heating and fusing step, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Example 5)
The base sheet A1 (single layer sheet) obtained in Production Example 1 was used. Moreover, as a transparent thermoactive adhesive used for the adhesive layer, a water-dispersed polyester resin (solid content concentration 20% by mass, ethyl cellosolve / butyl cellosolve mixed solvent = 1/1 (mass ratio), number average molecular weight 25000, glass transition Temperature 80 ° C.). In the same manner as in Example 1, with an automatic film applicator, a transparent laser marking sheet was formed by coating and drying on one side of the base sheet A1 to form a transparent thermally active adhesive layer having a dry coating thickness of 6 to 8 μm. Obtained. A release agent is applied to one end of each of the transparent laser marking sheet and the core multilayer sheet subjected to UV offset printing manufactured in Production Example 3, and the UV offset printing surface of the core multilayer sheet subjected to UV offset printing is provided. The layers were laminated so as to have the same configuration as in Example 1. After the lamination, in the same manner, after the heating and fusing step, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Comparative Example 1)
The base sheet A1 (single layer sheet) obtained in Production Example 1 was used. Further, as a transparent thermoactive adhesive used for the adhesive layer, vinyl chloride-vinyl acetate copolymer (manufactured by Nissin Chemical Industry Co., Ltd., trade name “Solvine CN” (solid content concentration 20 mass%, ethyl cellosolve / butyl cellosolve / Dioxane mixed solvent = 1/1/2 (mass ratio), vinyl chloride / vinyl acetate content = 89/11 (mass ratio), polymerization degree = 750)). In the same manner as in Example 1, with an automatic film applicator, a transparent laser marking sheet was formed by coating and drying on one side of the base sheet A1 to form a transparent thermally active adhesive layer having a dry coating thickness of 6 to 8 μm. Obtained. A release agent is applied to one end of each of the transparent laser marking sheet and the core multilayer sheet subjected to UV offset printing manufactured in Production Example 3, and the UV offset printing surface of the core multilayer sheet subjected to UV offset printing is provided. The layers were laminated so as to have the same configuration as in Example 1. After the lamination, in the same manner, after the heating and fusing step, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Comparative Example 2)
The base sheet A1 (single layer sheet) obtained in Production Example 1 was used. Moreover, as a transparent thermoactive adhesive used for the adhesive layer, an acrylic resin emulsion (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “New Coat MT-1177B”, solid concentration 45% by mass, ethyl cellosolve / butyl cellosolve mixed solvent = 1/1 (mass ratio) was prepared. Transparent laser marking in which an automatic film applicator was used in the same manner as in Example 1 and applied to one side of the single-layer base sheet A1 and dried to form a transparent thermally active adhesive layer having a dry coating thickness of 6 to 8 μm. A sheet was obtained. A release agent is applied to one end of each of the transparent laser marking sheet and the core multilayer sheet subjected to UV offset printing manufactured in Production Example 3, and the UV offset printing surface of the core multilayer sheet subjected to UV offset printing is provided. The layers were laminated so as to have the same configuration as in Example 1. After the lamination, in the same manner, after the heating and fusing step, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Comparative Example 3)
The base sheet A1 (single layer sheet) obtained in Production Example 1 was used. Moreover, as a transparent thermoactive adhesive used for the adhesive layer, a vinyl chloride-acrylic copolymer emulsion (manufactured by Nissin Chemical Industry Co., Ltd., trade name “Viniblanc 690”, vinyl chloride / acrylic content ratio = 80/20 ( (Mass ratio) and solid content concentration = 54 mass% were diluted with an ethyl cellosolve / butyl cellosolve mixed solvent (mass ratio = 1/1) to a solid content concentration of 20 mass%. In the same manner as in Example 1, with an automatic film applicator, a transparent laser marking sheet was formed by coating and drying on one side of the base sheet A1 to form a transparent thermally active adhesive layer having a dry coating thickness of 6 to 8 μm. Obtained. A release agent is applied to one end of each of the transparent laser marking sheet and the core multilayer sheet subjected to UV offset printing manufactured in Production Example 3, and the UV offset printing surface of the core multilayer sheet subjected to UV offset printing is provided. The layers were laminated so as to have the same configuration as in Example 1. After the lamination, in the same manner, after the heating and fusing step, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Comparative Example 4)
The base sheet A2 (multilayer sheet) obtained in Production Example 2 was used. Moreover, the same thing as what was used in the comparative example 1 was prepared as a transparent thermoactive adhesive used for an adhesive bond layer. Using the automatic film applicator in the same manner as in Example 1, a transparent laser marking sheet was formed by coating and drying on one side of the base sheet A2 to form a transparent thermally active adhesive layer having a dry coating thickness of 6 to 8 μm. Obtained. A release agent is applied to each end of the transparent laser marking sheet and the multilayer sheet subjected to UV offset printing manufactured in Production Example 3, so that the UV offset printing surface of the core multilayer sheet subjected to UV offset printing is in contact with the transparent laser marking sheet. Then, the layers were laminated so as to have the same configuration as in Example 1. After the lamination, in the same manner, after the heating and fusing step, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Comparative Example 5)
The base sheet A1 (single layer sheet) obtained in Production Example 1 was used. A release agent was applied to one end of this base sheet (transparent laser marking sheet with no adhesive layer formed) and a multilayer sheet produced in Production Example 3 and subjected to UV offset printing. Next, it laminated | stacked so that it might become the same structure as Example 1 so that the transparent laser marking sheet in which an adhesive bond layer was not formed, and the UV offset printing surface of a multilayer sheet may contact | connect. After the lamination, in the same manner, after the heating and fusing step, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Comparative Example 6)
The base sheet A2 (multilayer sheet) obtained in Production Example 2 was used. A release agent was applied to one end of the base sheet (transparent laser marking sheet with no adhesive layer formed) and one of the core multilayer sheets subjected to UV offset printing produced in Production Example 3. Next, it laminated | stacked so that it might become the same structure as Example 1 so that the transparent laser marking sheet in which an adhesive bond layer was not formed, and the UV offset printing surface of a multilayer sheet may contact | connect. After the lamination, in the same manner, after the heating and fusing step, it was cooled to room temperature to obtain a transparent laser marking multilayer sheet.

(Discussion)
As shown in Tables 1 and 2, the transparent laser marking sheets obtained in Examples 1 to 3 and 5 are those in which a transparent thermally active adhesive is firmly formed on the base sheet and there is no peeling at all in the cross cut test Met. Further, the transparency was good and the visibility was excellent, and the heat-fusibility exceeded the material destruction. Further, even when the laser beam energy was irradiated, there was no abnormality such as “bulging” and the marking could be performed clearly. Furthermore, it was provided for practical use as an electronic passport or plastic card. Moreover, although Example 4 is excellent in transparency and adhesiveness, although heat fusion property and laser marking property are somewhat inferior to Examples 1-3 and 5, it is excellent with respect to Comparative Examples 1-6. It was a thing.

  In addition, the transparent laser marking sheet formed with the vinyl chloride copolymer system or acrylic resin-based transparent heat-activatable adhesive obtained in Comparative Examples 1 to 4 is good in transparency and adhesion, but peels off with a slight force. However, it was inferior in heat fusibility. Furthermore, when the laser beam energy is irradiated, “swelling” occurs in the irradiated portion, which cannot be put to practical use. Further, as in the transparent laser marking sheets obtained in Comparative Examples 5 to 6, without using a transparent thermoactive adhesive, the one by the resin fusion itself between the sheets is in the heat fusion property and the laser marking property. It was inferior.

  The transparent laser marking sheet according to the present invention has good adhesiveness particularly to a printing sheet subjected to UV offset printing or UV silk printing, and is suitably used for electronic passports, plastic cards and the like. be able to.

1 (1A, 1B): transparent laser marking sheet, 2, 20: base material sheet, 3: adhesive layer, 4: skin layer (base material sheet), 5: core layer (base material sheet), 6: Multi-layer sheet for core, 7: skin layer (multi-layer for core), 8: core layer (of multi-layer sheet for core), 10: binding sheet, 11: overhanging portion, 12: sewing binding portion, 100 (100A, 100B) : Laser marking sheet for electronic passports.

Claims (11)

A transparent laser marking sheet provided with an adhesive layer on at least one side of a substrate sheet,
The base sheet is configured as a single layer sheet made of a polycarbonate resin and a transparent polycarbonate resin composition containing a laser light energy absorber,
Alternatively, the base sheet has a skin layer and a core layer, and the skin layer that is both outermost layers is made of a thermoplastic resin composition made of an amorphous polyester resin, and the core layer is made of a polycarbonate resin. And a multilayer sheet comprising a transparent polycarbonate resin composition containing a laser light energy absorber,
The adhesive layer is formed of a transparent thermoactive adhesive made of a copolymer of a polyester resin and a monomer having a hydrophilic functional group, and is configured as a layer having a thickness of 1 to 20 μm. Marking sheet.   The transparent laser marking sheet according to claim 1, wherein the polyester resin of the transparent thermally active adhesive has a number average molecular weight of 10,000 to 200,000 and a glass transition temperature of 20 to 100C. The transparent laser marking sheet according to claim 1 or 2, wherein the transparent thermally active adhesive is a water-dispersed polyester resin comprising a copolymer of a polyester resin and a monomer having a hydrophilic functional group.   The transparent laser marking sheet according to any one of claims 1 to 3, wherein the transparent thermally active adhesive is an aqueous dispersion, an aqueous solution, or an organic solvent solution.   In the single layer sheet or the core layer of the multilayer sheet, as the laser light energy absorber, carbon black, titanium black, metal oxide, metal sulfide, metal nitride, metal soot oxide, and metal carbonate are used. The transparent laser marking sheet according to any one of claims 1 to 4, wherein at least one selected from chemicals is contained.   The single-layer sheet includes a lubricant, at least one selected from an antioxidant and an anti-coloring agent, and includes at least one selected from an ultraviolet absorber and a light stabilizer. The transparent laser marking sheet of any one of Claims 1-5.   The skin layer of the multilayer sheet contains a lubricant, at least one selected from an antioxidant and an anti-coloring agent, and at least one selected from an ultraviolet absorber and a light stabilizer. The transparent laser marking sheet according to any one of claims 1 to 5, wherein:   It is an object for electronic passports, The transparent laser marking sheet of any one of Claims 1-7.   It is an object for plastic cards, The transparent laser marking sheet of any one of Claims 1-7. A laminate using the transparent laser marking sheet according to any one of claims 1 to 7,
At least a printing sheet is bonded to the adhesive layer of the transparent laser marking sheet,
The printed sheet is a laminate obtained by performing UV offset printing or UV silk printing. A laser marking method for laser-marking the transparent laser marking sheet according to any one of claims 1 to 9,
After integrating the transparent laser marking sheet and a printing sheet subjected to UV offset printing or UV silk printing, a laser is directed toward the surface of the transparent laser marking sheet on which the adhesive layer is not formed. A laser marking method for irradiating light energy to laser mark characters, figures, symbols or information.

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