JP2011079284A - Multilayer hinge sheet, laser-marking laminate for electronic passport, and the electronic passport - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayer hinge sheet which is excellent in tear/tensile strength and the bound part of which has light resistance and heat resistance and further exhibits excellent resistibility to repeated bending. <P>SOLUTION: The multilayer hinge sheet C is obtained by layering a thermoplastic resin sheet P (a mark 3) having flexibility and heat weldability on another thermoplastic resin sheet R (a mark 5) having heat resistance and rigidity. The thermoplastic resin sheet P is formed of a thermoplastic resin X including the thermoplastic elastomer having ≥85 Shore A hardness and <70 Shore D hardness. The thermoplastic resin sheet R is formed of another thermoplastic resin Y having ≥1 GPa tensile modulus of elasticity measured according to ASTM D882, and ≥70°C glass transition temperature measured by a DSC method. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminated hinge sheet used for an electronic passport, a laser marking laminate for an electronic passport using the laminated hinge sheet, and an electronic passport. In particular, a laminated hinge sheet with excellent heat-fusability, durability, bendability, and workability, and multi-layer sheets are marked without damage by laser beam irradiation, and the contrast between the fabric color and the printed part is high and clear characters The present invention relates to a laser marking laminate for electronic passports that can provide symbols and images and is excellent in heat resistance and productivity, and an electronic passport using the laser marking laminate for electronic passports.

  With the progress of international exchanges, the movement of human resources has become active, and the importance of passports that record personal information is increasing as a means to identify individuals and prove their identity. In particular, the passport plays a role as a so-called identification card (identity lighting card, etc.) issued by a country that is a public organization and has reliability.

  In particular, since the September 2001 global terrorist attacks, the United Nations specialized organization ICAO (International Civil Aviation Organization) established standards and started efforts to introduce electronic passports in order to tighten the immigration control of each country. . Anti-counterfeiting is important in this effort, and technology for laser marking personal names, symbols, letters, photographs, etc. has been attracting attention.

  By the way, since this electronic passport can identify and prove an individual, if a third party other than the country (or a national agency) can easily tamper or forge personal information, The credibility of the ID card will be reduced, which 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. In addition, since electronic passports are made of light, thin and short standards, it is important how high-contrast and clear display of personal names, symbols, characters, photos, etc. is possible. The realization of an accurate display leads to the prevention of tampering and counterfeiting, so the market is highly expected.

  In addition to tampering and counterfeiting, electronic passports are carried around the world and require durability. In particular, since personally identifiable data is often attached to an electronic passport via a hinge sheet, the hinge sheet has durability that is difficult to damage, that is, damage such as the hinge sheet being torn from the electronic passport body. It is demanded to have durability that prevents the above. By providing such durability, a third party, excluding the public organization that is the issuer, can tamper or counterfeit such as deliberately (intentionally) replacing the hinge sheet, etc. Immediate response is required because it can be surely prevented.

  In order to solve such a problem, a technique for laser marking personal names, symbols, characters, photographs, and the like, specifically, a laser marking laminate has been attracting attention.

  In Patent Document 1, a multilayer sheet comprising at least a surface layer and an inner layer is provided for the purpose of obtaining a multilayer sheet that can be laser-marked with no appearance damage, good contrast, and excellent surface smoothness. (B-2) 0.01 to 5 parts by weight of an energy absorber that absorbs a laser beam and (b-3) with respect to 100 parts by weight of the thermoplastic resin (B) and (b-1) thermoplastic resin ) A multilayer sheet for laser marking is disclosed in which an inner layer made of a thermoplastic resin composition containing 0.5 to 7 parts by weight of a colorant is formed by melt coextrusion.

  In Patent Document 2, the first surface layer / inner layer / second layer is used for the purpose of obtaining a multilayer sheet having no damage to the appearance, good contrast, excellent surface smoothness and excellent heat resistance. A multi-layer sheet comprising a surface layer, wherein (A) a transparent first resin composition comprising a thermoplastic resin composition containing 0.001 to 5 parts by weight of mica and / or carbon black with respect to 100 parts by weight of a transparent thermoplastic resin. The first and second surface layers and (B) an inner layer made of a thermoplastic resin composition containing 0.001 to 3 parts by weight of an energy absorber that absorbs a laser beam with respect to 100 parts by weight of the thermoplastic resin, The thickness composition ratio of the sheet of the first surface layer / inner layer / second surface layer is 1: 4: 1 to 1: 10: 1, and the first surface layer / inner layer / second surface layer is melt coextruded. Formed laser mark Multilayer sheet is disclosed for grayed.

  Further, for example, the following Patent Documents 3 to 8 are disclosed in which the hinge sheet is disclosed as a sheet for binding information pages to other pages and the like.

  Further, Patent Document 3 discloses a technique for binding with a binding margin when binding a printed sheet or the like. Further, in Patent Document 4, when binding an information page composed of a transparent layer / colored layer / transparent layer, the transparent layer that is both outer layers of the transparent layer / colored layer / transparent layer is projected and narrowed, and this portion is bound. A technology to be used is disclosed. Patent Document 5 discloses a technique in which the face film and the back film are narrowed down and the narrowed portion is used as a binding margin.

  Patent Document 6 discloses a technique for binding an information page made of a cover foil that wraps a plastic inlay made of a plastic sheet together with other pages. Further, Patent Document 7 discloses a technique for binding several sheets of paper to a cover.

  Patent Document 8 discloses a technique for providing a sheet for binding at the center of the laminate, that is, a hinge sheet.

JP 2002-273732 A Japanese Patent No. 3889431 JP 09-123636 A International Publication No. 98/19870 Pamphlet JP 2001-213072 A US Pat. No. 5,035,503 A JP 2000-203174 A EP 1592565B1 specification

  Certainly, the multilayer sheets for laser marking in Patent Documents 1 and 2 are excellent in heat-fusibility with these multilayer sheets and thermoplastic resin sheets such as PETG sheets and ABS resin sheets. A sufficient printability for printing letters and numbers by marking is obtained and deserves evaluation. However, in Patent Document 1, the inner layer contains 0.5 to 7 parts by weight of a colorant, and printing is performed on an inlay layer that is an intermediate layer in a so-called identification such as a passport in which personal information is recorded as described above. It is common to do this. In that case, when the multilayer sheet is used for the outermost layer (overlay), transparency is not sufficient due to the influence of the coloring agent. Therefore, there has been a problem that the image clarity of the printed portion is hindered. Since the multi-layer sheet of Patent Document 2 contains mica and / or carbon black, which are laser light absorbers, on the surface layer, the outermost layer of so-called identification (such as a passport in which personal information is recorded as described above) When the multilayer sheet is used for overlay, the laser light absorber contained in the surface layer absorbs the laser light energy and causes foaming or the like due to laser light irradiation, resulting in reduced surface smoothness. There was a problem.

  Furthermore, Patent Document 3 does not disclose a technique for binding the laminate together with other sheets. Moreover, in patent document 4, since the thickness of a transparent layer / colored layer / transparent layer and the thickness of a binding margin part differ, it is difficult to produce such a laminated body stably in large quantities. Moreover, in patent document 5, also about this technique, there exists a problem similar to the above in the manufacturing method, and it is difficult to produce such a laminated body stably in large quantities. Further, in Patent Document 6, there are the same problems as described above in order to project a plurality of cover foils from the information page portion to form a narrowed binding portion. Further, in Patent Document 7, several paper sheets are attached to a cover with a synthetic resin band, and the binding portion becomes thick and there is a problem of opening when bookbinding. Not suitable for.

  Further, in Patent Document 8, the sheet for connecting to the other is the central part of the laminated body, but only part insertion is performed, and this is the part where the sheet for connecting the laminated body at the time of heat lamination is inserted. There is a difference in thickness between the part that is not so, in other words, the part where the sheet for connecting is inserted becomes more prominent than the part that is not so, and this causes the booked passport to open or bookbinding When a plurality of passports are set up, a fan shape is formed, so that a problem arises in that they cannot be sent one by one to the next printing process. Furthermore, the description of the sheet material of the joint is generally a layer structure, the surface layer is described as PE, and the core layer is described as PET. However, since the sheet material of the information page is described as PC, the PC sheet Since the adhesive layer is not heated and bonded to the surface layer PE of the joint portion, some kind of adhesive is required. However, there is no particular description about it, and only a description that it is bonded to the cover sheet or the like using a high-temperature active adhesive. Therefore, the disclosed technique requires a method such as pre-applying some adhesive to both surfaces of the sheet material of the joint, which is complicated in the production process and the adhesive strength of this part. There is no description, and it is unclear as a disclosed technique.

  As described above, none of the patent documents has solved the problem sufficiently, and an early improvement is required.

  The present invention has been made to solve the above-mentioned problems, and is excellent in heat-fusibility and dimensional accuracy of a laser marking laminate for an electronic passport, and is flexible after being bound with a cover, etc., and resistant to repeated bending. In addition, it is possible to provide a laminated hinge sheet having excellent properties, in addition, excellent binding portion tearing and tensile strength, and excellent temporal stability such as light resistance during actual use. In particular, it can be suitably used for a laser marking laminate for an electronic passport having a multilayer structure.

  In addition, it has excellent laser marking properties, a high contrast between the fabric color and the printed part, and clear characters, symbols, and images can be obtained, and heat fusion in the lamination process of the multilayer sheet is excellent. Laser marking laminate for electronic passports with improved transparency from the point of light transmittance, sheet transportability, release from mold after hot pressing, heat resistance, bendability and wear resistance It is to provide. Furthermore, the electronic passport which uses such a laser marking laminated body for electronic passports is provided. In particular, it is excellent in preventing tampering and preventing counterfeiting.

  Furthermore, when manufacturing an electronic passport using the above-described laser marking laminate for electronic passport, the laser marking laminate for electronic passport is used to bind the electronic passport cover or back cover with a simple manufacturing process such as sewing. A laser marking laminate for an electronic passport having a laminated structure using a laminated film having strength, flexibility, and transparency at the center of the same, and a method for producing an electronic passport using the laser marking laminate for an electronic passport There is.

  According to the present invention, the following laminated hinge sheet, laser marking laminate for electronic passport, and electronic passport are provided.

[1] A laminated hinge sheet in which a thermoplastic resin sheet P having flexibility and heat-fusibility and a thermoplastic resin sheet R having heat resistance and rigidity are laminated, and the thermoplastic resin sheet P is It is a sheet made of a thermoplastic resin X containing a thermoplastic elastomer having a hardness Shore A of 85 or more and a Shore D of less than 70, and the thermoplastic resin sheet R is a tensile elastic modulus measured in accordance with ASTM D882. A laminated hinge sheet C, which is a sheet made from a thermoplastic resin Y having a glass transition temperature of 70 ° C. or higher as measured by DSC method.

[2] The laminated hinge sheet C according to [1], wherein the laminated hinge sheet is formed by laminating three layers of thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P and integrating them by thermal lamination. .

[3] The thermoplastic resin sheet P is an outer layer, the thermoplastic resin sheet R is an inner layer, and the thermoplastic resin X that is a raw material of the thermoplastic resin sheet P is melt-extruded on both surfaces of the thermoplastic resin sheet R. The laminated hinge sheet C according to [1], wherein the thermoplastic resin sheet P is formed by being laminated by molding.

[4] The laminated hinge sheet according to any one of [1] to [3], wherein the thermoplastic resin sheet P is used as an outer layer, and the thermoplastic resin sheet R is used as an inner layer, which are laminated by two-type three-layer coextrusion molding. C.

[5] Electronic passport formed by laminating 5 layers of transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A according to any one of [1] to [4] The transparent laser marking sheet A is a transparent laser marking sheet formed by melt extrusion molding, and is used for 100 parts by mass of a transparent thermoplastic resin mainly composed of a polycarbonate resin. A single layer sheet made of a transparent polycarbonate resin composition containing 0.0005 to 1 part by mass of a light energy absorbing material, or the transparent laser marking sheet A is a transparent laser marking sheet formed by melt extrusion molding, Layer and core layer, and at least three layers by melt extrusion The skin layer, which is both outermost layers, is made of a resin mainly composed of an amorphous aromatic polyester resin, and the core layer is composed mainly of a polycarbonate resin. It consists of a transparent polycarbonate resin composition containing 0.0005 to 1 part by mass of a laser light energy absorbing material with respect to 100 parts by mass of the transparent thermoplastic resin, and the total thickness of the transparent laser marking sheet A is 50 to 200 μm. The multilayer sheet 1 having a core layer thickness ratio of less than 30 to 85%, or the transparent laser marking sheet A is a transparent laser marking sheet formed by melt extrusion, and has a skin layer and a core layer, At least three sheets are laminated by melt extrusion molding, and the skin layer as both outermost layers is polycarbonate. The transparent polycarbonate which consists of transparent resin which has resin as a main component, and the said core layer contains 0.0005-1 mass part of laser beam energy absorption materials with respect to 100 mass parts of transparent resin which has polycarbonate resin as a main component. It is composed of a resin composition, and is further configured as a multilayer sheet 2 having a total thickness of the transparent laser marking sheet A of 50 to 200 μm and a core layer thickness ratio of less than 30 to 85%. The multilayer sheet B is a skin layer And a core layer, and is a multilayer sheet formed by laminating at least three layers by melt extrusion molding, and the skin layer as both outermost layers of the multilayer sheet B is an amorphous aromatic It is made of a resin mainly composed of a polyester resin, and the core layer of the multilayer sheet B is a transparent heatable resin mainly composed of a polycarbonate resin. It is made of a plastic resin, and the skin layer and / or the core layer of the multilayer sheet B contains at least one coloring agent for 100 parts by mass of the copolyester resin and / or 100 parts by mass of the polycarbonate resin. The total thickness of the multilayer sheet B is 100 to 300 μm, and the thickness ratio of the thickness of the core layer to the total thickness of the multilayer sheet B is 30. %, A laser marking laminate for electronic passports, wherein the laminate hinge sheet C has a thickness of 80 to 250 μm.

[6] Further, the single layer sheet of the transparent laser marking sheet A contains 0.01 to 3 parts by mass of a lubricant with respect to 100 parts by mass of the transparent thermoplastic resin, and also an antioxidant and / or a coloring agent. The transparent laser marking sheet containing 0.1 to 5 parts by mass of the inhibitor and 0.1 to 5 parts by mass of the ultraviolet absorber and / or the light stabilizer, or the skin in the multilayer sheet 2 of the transparent laser marking sheet A The layer contains 0.01 to 3 parts by weight of a lubricant with respect to 100 parts by weight of the transparent thermoplastic resin, and 0.0005 to 1 parts by weight of a laser light energy absorber, an antioxidant and / or an anti-coloring agent. [5] configured as a transparent laser marking sheet containing 0.1 to 5 parts by weight of the agent and 0.1 to 5 parts by weight of the ultraviolet absorber and / or the light stabilizer. Electronic passport for laser marking laminate of the mounting.

[7] The laser light energy absorbing material of the transparent laser marking sheet A contains at least one or more selected from the group consisting of carbon black, titanium black, and metal oxide [5] or The laser marking laminate for electronic passports according to [6].

[8] The core layer and / or skin layer of the multilayer sheet B is 0.1 to 5 parts by mass of an antioxidant and / or anti-coloring agent, and an ultraviolet absorber and / or 100 parts by mass of the thermoplastic resin. The laser marking laminated body for electronic passports in any one of [5]-[7] containing 0.1-5 mass parts of light stabilizers.

[9] The laser marking for electronic passports according to any one of [5] to [8], wherein one end of the laminated hinge sheet C has an overhang portion that is 5 to 100 mm longer than the transparent laser marking sheet A and the multilayer sheet B. Laminated body.

[10] The surface of the transparent laser marking sheet A and / or the multilayer sheet B is matted with an average roughness (Ra) of 0.1 to 5 μm, according to any one of [5] to [9] The laser marking laminate for electronic passports as described.

[11] The laser marking laminate for electronic passports according to any one of [5] to [10], further comprising a forgery prevention forming portion.

[12] An electronic passport formed using the laser marking laminate for electronic passports according to any one of [9] to [11], wherein a protruding portion of the laminated hinge sheet C is a cover of the electronic passport Alternatively, an electronic passport formed by sewing and / or adhering to the back cover.

[13] A laser marking laminate for an electronic passport according to any one of [5] to [11] or a method of laser marking the electronic passport according to [12], wherein the laser marking laminate for an electronic passport A laser marking method in which printing is performed by irradiating a laser beam from the transparent laser marking sheet A side laminated on the substrate.

  According to the present invention, heat fusion and dimensional accuracy of the laminate are excellent, and after binding with a cover, etc., it is flexible and excellent in resistance to repeated bending, in addition, the binding portion is excellent in tearing and tensile strength, There is an excellent effect that it is possible to provide a laminated hinge sheet having excellent temporal stability such as light resistance during actual use. In particular, it can be suitably used for a laser marking laminate for an electronic passport having a multilayer structure and an electronic passport.

  In addition, it has excellent laser marking properties, a high contrast between the fabric color and the printed part, and clear characters, symbols, and images can be obtained, and heat fusion in the lamination process of the multilayer sheet is excellent. Laser marking laminate for electronic passports with improved transparency from the point of light transmittance, sheet transportability, release from mold after hot pressing, heat resistance, bendability and wear resistance Can be provided. Furthermore, the electronic passport which uses such a laser marking laminated body for electronic passports can be provided. In particular, it is excellent in preventing tampering and preventing counterfeiting.

  Furthermore, when manufacturing an electronic passport using the above-described laser marking laminate for electronic passport, the laser marking laminate for electronic passport is used to bind the electronic passport cover or back cover with a simple manufacturing process such as sewing. Can provide a laser marking laminate for an electronic passport having a laminated structure using a laminated film having strength, flexibility, and transparency at the center portion thereof, and a method for producing an electronic passport using the laser marking laminate for an electronic passport There is an excellent effect.

It is sectional drawing which shows one Embodiment of the lamination | stacking hinge sheet | seat of this invention, Comprising: The state which laminated | stacked the thermoplastic resin sheet P and the thermoplastic resin sheet R on 2 types and 3 layers of sheet P / sheet R / sheet P is shown. It is the figure shown typically. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows one Embodiment of the laser marking laminated body for electronic passports of this invention, Comprising: The transparent laser marking sheet A is a transparent laser marking sheet which consists of single layers, Comprising: The cross section of the laser marking laminated body for electronic passports is shown. It is the figure shown typically. It is a schematic diagram which shows another embodiment of the laser marking laminated body for electronic passports of this invention, Comprising: The transparent laser marking sheet A is a transparent laser marking sheet which consists of three layers, Comprising: Section of the laser marking laminated body for electronic passports FIG. It is a schematic diagram which shows another embodiment of the laser marking laminated body for electronic passports of this invention, Comprising: The transparent laser marking sheet A is a transparent laser marking sheet which consists of three layers, Comprising: Section of the laser marking laminated body for electronic passports FIG. It is the figure which showed typically the state which provided the overhang | projection part in the laser marking laminated body for electronic passports of this invention in a cross section. It is a schematic diagram which shows an example in the case of using the laser marking laminated body for electronic passports of this invention for an electronic passport. It is the side view which showed a mode that the softness | flexibility of a sheet | seat was measured typically. It is the side view which showed a mode that the softness | flexibility of a sheet | seat was measured typically. It is a side view which shows typically the tension test for measuring sewing machine part intensity | strength.

  Hereinafter, the laminated hinge sheet of the present invention, the laser marking laminate for an electronic passport, and the form for carrying out the electronic passport will be specifically described. However, the present invention broadly encompasses a laminated hinge sheet, a laser marking laminate for electronic passports, and an electronic passport having the invention specific matters, and is not limited to the following embodiments.

[1] Configuration of laminated hinge sheet of the present invention:
As shown in FIG. 1, the laminated hinge sheet of the present invention includes a thermoplastic resin sheet P (reference numeral 3) having flexibility and heat-fusibility, and a thermoplastic resin sheet R (reference numeral 5) having heat resistance and rigidity. The thermoplastic resin sheet P is a sheet made from a thermoplastic resin X containing a thermoplastic elastomer having a hardness Shore A of 85 or more and a Shore D of less than 70. The thermoplastic resin sheet R is a laminated hinge sheet C which is a sheet made of a thermoplastic resin Y having a tensile modulus measured in accordance with ASTM D882 of 1 GPa or more and a glass transition temperature by DSC method of 70 ° C. or more. It is configured as.

  In other words, the laminated hinge sheet of the present invention is used to make it easy to bind an electronic passport laser marking laminate (to be described later) having personal data or the like via the hinge sheet to the electronic passport. Hereinafter, after describing the thermoplastic resin sheet P and the thermoplastic resin sheet R, each relationship will be described.

[1-1] Thermoplastic resin sheet P:
The thermoplastic resin sheet P is configured as a thermoplastic resin sheet having flexibility and heat fusibility. The thermoplastic resin sheet P is formed as a single layer or an outer layer (skin layer) of a multilayer sheet by thermoplastic extrusion X (described later) by melt extrusion molding with a T-die. And has a low softening temperature and excellent fusion properties with various plastic substrates, and is therefore excellent in heat fusion properties with a thermoplastic resin sheet R made of a thermoplastic resin Y described later, and a thermoplastic resin sheet. A laminate sheet with R can be obtained.

[1-1-1] Thermoplastic resin X:
The thermoplastic resin X includes a thermoplastic elastomer having a hardness Shore A (hereinafter also referred to as “Shore-A” as appropriate) of 85 or more and Shore D (hereinafter also referred to as “Shore-D” as appropriate) of less than 70. It is a plastic resin. By forming the thermoplastic resin sheet P from the thermoplastic resin X which is such a material, the thermoplastic resin sheet P itself has not only flexibility and heat-fusibility, but also this thermoplastic resin sheet. The laminated hinge sheet of the present invention formed from P and a thermoplastic resin sheet R described later can also be provided with flexibility and heat-fusibility. That is, when the thermoplastic resin sheet is formed from the thermoplastic resin X, the thermoplastic resin sheet is easily melted when the laminated hinge sheet is formed, and is easily integrated with the thermoplastic resin sheet R described later. As a result, the laminated hinge sheet can be easily formed. In other words, by forming the thermoplastic resin sheet from a desired material (thermoplastic resin X), the thermoplastic resin sheet can be sufficiently fused and reliably integrated with the thermoplastic resin sheet R.

  When used in an electronic passport laser marking laminate comprising a laminate having a laminate structure as described below, or an electronic passport, heat fusion with the skin layer of the inlay sheet adjacent to the laminate hinge sheet in the laminate is sufficient. It can be a thing.

  For example, examples of the thermoplastic resin X include thermoplastic polyurethane elastomer (TPU) and hydrogenated styrene elastomer (SEPS).

  More specifically, for example, in the case of a thermoplastic polyurethane elastomer, one that is melt-extruded at 170 to 240 ° C. can be exemplified.

  Moreover, when forming a thermoplastic resin sheet, you may mix an inorganic filler, an organic filler, another thermoplastic resin, etc. within the range which does not inhibit the function. Furthermore, colorants such as lubricants, stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, pigments and dyes may be added and mixed. Specifically, mica, mica, micromica, silica, calcium carbonate and the like are mentioned as the inorganic filler, and organic fibers such as polyester fiber, PPS fiber and nylon fiber are mentioned as the organic filler. Examples of other thermoplastic resins include acrylonitrile-styrene copolymer resin (AS resin), polypropylene resin, ABS resin, acrylic resin, and polycarbonate resin.

  More specifically, a small amount of AS resin, polypropylene resin, ABS resin, acrylic resin, polycarbonate resin, or the like may be blended for the purpose of improving cutting processability and heat resistance. Alternatively, mica, mica, micro mica, and silica may be blended for the same purpose as the inorganic filler. Furthermore, colorants such as pigments and dyes are blended for the purpose of coloring, and lubricants, stabilizers, light stabilizers, antioxidants, UV absorbers, etc. are blended for the purpose of improving the stability during molding and use. There is.

[1-2] Thermoplastic resin sheet R:
The thermoplastic resin sheet R constituting the laminated hinge sheet of the present invention is configured as a thermoplastic resin sheet having heat resistance and rigidity, and is configured as a sheet using a thermoplastic resin Y described later as a raw material. By constituting the thermoplastic resin sheet in this way, the thermoplastic resin sheet can have a role as an intermediate layer having heat resistance and rigidity, and further integrated with a thermoplastic resin sheet R described later. It is easy to form a laminated sheet.

[1-2-1] Thermoplastic resin Y:
The thermoplastic resin Y is a thermoplastic resin having a tensile modulus measured according to ASTM D882 of 1 GPa or more and a glass transition temperature by DSC method of 70 ° C. or more. By forming the thermoplastic resin sheet R from the thermoplastic resin Y which is such a material, the thermoplastic resin sheet R itself not only has heat resistance and rigidity, but also the thermoplastic resin sheet R and the above-described one. The laminated hinge sheet of the present invention formed from the thermoplastic resin sheet P can also be provided with heat resistance and rigidity. That is, by forming the thermoplastic resin sheet R using the thermoplastic resin Y as a raw material, the thermoplastic resin melted into the thermoplastic resin sheet R having heat resistance and rigidity as a so-called core of the laminated hinge sheet. It becomes easy to fuse and integrate the resin sheet P. As a result, the laminated hinge sheet can be easily formed. In other words, since the thermoplastic resin sheet is formed using a desired material (thermoplastic resin Y) as a raw material, the thermoplastic resin sheet R and the thermoplastic resin sheet can be sufficiently fused and reliably laminated.

  Note that ASTM D882 is a thin plastic sheet tensile test method defined in “Standard Test Method for Tensile Properties of Thin Plastic Sheeting”.

[1-3] Relationship between the thermoplastic resin sheet P and the thermoplastic resin sheet R:
The laminated hinge sheet C of the present embodiment is formed by laminating a thermoplastic resin sheet P and a thermoplastic resin sheet R. This laminated hinge sheet C includes information such as images and characters written on a sheet A (described later) by laser marking, and information such as images and characters printed on a sheet B (described later) by printing, etc. A sheet that plays a very important role in order to firmly bind various information stored in a storage medium such as an IC chip arranged in an inlet sheet to the cover of the passport and other visa sheets. It is. Therefore, firm heat-fusibility with sheet B or other sheets (described later), appropriate flexibility, heat resistance in the heat-fusion process, and the like are required. In addition, for example, when the laminated hinge sheet C is bound to a cover (passport) or the like, the sewing part has excellent tearing and tensile strength, and the binding part 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 material is suitably used as the laminated hinge sheet C that meets such a purpose.

  Here, as a method of laminating the thermoplastic resin sheet P and the thermoplastic resin sheet R, the thermoplastic resin X as a raw material of the thermoplastic resin sheet P is obtained by using an extruder with a T die at a predetermined melting temperature of each resin. After forming a layer of the thermoplastic resin sheet P on one side of the thermoplastic resin sheet R by contact and pressure immediately after being melted and melt-extruded from the T die into a sheet, Similarly, a layer of the thermoplastic resin sheet P is formed on the thermoplastic resin sheet R side of the thermoplastic resin sheet R / thermoplastic resin sheet P, and the thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P is formed. A method of forming a laminate sheet of

  Alternatively, using two melt extrusion molding machines with a T die, the thermoplastic resin X as a raw material of the thermoplastic resin sheet P is melted at a predetermined melting temperature of each resin with an extruder with a T die, and T A method of forming a laminate sheet of thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P by contact / pressing with thermoplastic resin sheet R immediately after being melt-extruded into a sheet form from a die,

  Further, the thermoplastic resin X and the thermoplastic resin Y, which are the raw materials of the thermoplastic resin sheet P and the thermoplastic resin sheet R, are separately melted at a predetermined melting temperature of each resin by an extruder with a T die, and T A method of forming a laminate sheet of a thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P by melt-extruding from a die into a sheet and then thermally laminating with a hot roll or the like;

  Furthermore, as another method, a thermoplastic resin sheet P and a thermoplastic resin X which are the raw materials of the thermoplastic resin sheet R and a thermoplastic resin Y are used as a multilayer melt extrusion molding machine with two types and three layers T-die (using two melt extrusion molding machines). ), And a method of molding as a two-kind / three-layer sheet of thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P.

  As described above, a laminated hinge sheet in which three layers of the thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P are laminated and integrated by thermal lamination is also preferable. There is an advantage that it is easy to mold.

  Further, the thermoplastic resin sheet P is used as an outer layer, the thermoplastic resin sheet R is used as an inner layer, and a thermoplastic resin X, which is a raw material of the thermoplastic resin sheet P, is laminated on both surfaces of the thermoplastic resin sheet R by melt extrusion molding. It is also preferable to mold a hinge sheet on which the plastic resin sheet P is formed. By laminating three layers in this way, the contact interface between the thermoplastic resin sheet P / thermoplastic resin sheet R can be firmly fused, and the three-layer structure is flat without deformation such as warping of the laminated sheet. This is preferable because a laminated sheet having excellent properties can be obtained.

  Also, a laminated hinge sheet having the thermoplastic resin sheet P as an outer layer and the thermoplastic resin sheet R as an inner layer, and immediately after the thermoplastic resin sheet R is melt-extrusion molded, the thermoplastic resin sheet P is pressed on both sides thereof. Alternatively, the thermoplastic resin sheet P and the thermoplastic resin sheet R are laminated as three layers of thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P by pressurizing and heating contact. Is also a preferred form. In general, since the melt extrusion temperature of the thermoplastic resin sheet R is higher than the melt extrusion temperature of the thermoplastic resin sheet P, the temperature of the contact interface between the thermoplastic resin sheet P and the thermoplastic resin sheet R is kept high. Therefore, the contact interface between the thermoplastic resin sheet P / thermoplastic resin sheet R can be more firmly fused, and a flat structure free from deformation such as warping of the laminated sheet by adopting a three-layer structure. This is preferable because a laminated sheet having excellent properties can be obtained.

  Furthermore, a laminated hinge sheet laminated by two-type three-layer coextrusion molding with the thermoplastic resin sheet P as an outer layer and the thermoplastic resin sheet R as an inner layer is also one of the preferred forms. That is, a laminated hinge sheet having the thermoplastic resin sheet P as an outer layer and the thermoplastic resin sheet R as an inner layer, the thermoplastic resin X being a raw material resin of the thermoplastic resin sheet P and the raw material resin of the thermoplastic resin sheet R The thermoplastic resin Y is a two-layer / three-layer coextrusion molding by melt coextrusion molding to obtain a three-layer laminated hinge sheet of thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P. it can. By laminating in this way, the contact interface between the thermoplastic resin sheet P / thermoplastic resin sheet R is partly fused, and by forming a three-layer structure, flatness without deformation such as warping of the laminated sheet is achieved. It is preferable because an excellent laminated sheet can be formed.

For example, as shown in FIG. 1, the thermoplastic resin P is laminated by two-type three-layer coextrusion molding with the thermoplastic resin P as an outer layer and the thermoplastic resin R as an inner layer as described above. And the thermoplastic resin R are firmly integrated at the interfaces K ₁ and K ₂ .

  The shape, size, etc. of the hinge sheet are not particularly limited as long as the shape, size, etc. are easy to bind the laser marking laminate for electronic passports. It is preferable to select as appropriate.

  However, as described later, when used in a laser marking laminate for an electronic passport, an electronic passport, or the like, the thickness of the hinge sheet C is 80 to 250 μm, more preferably 100 to 200 μm. If the thickness of the hinge sheet C is less than 80 μm, the strength of the sewing binding portion is insufficient, and there is a concern that the multilayer sheet on which personal information such as personal images, characters, numbers, and the like is laser-marked is peeled off from the electronic passport. In addition, if it exceeds 250 μm, the total thickness of the laser marking laminate for electronic passports becomes too thick, and when bound to the cover with other sheets such as a visa sheet, the electronic passport becomes a fan shape, which makes it possible to produce electronic passports in the bookbinding process. In addition to causing problems, there is a problem that the rigidity of the hinge sheet C becomes so large that the electronic passport opens naturally, which is not preferable.

  The same applies to an electronic passport and a conventional ordinary passport, but in an electronic passport, a plastic multilayer sheet in which personal data / images called data pages are described is bound to a cover together with other sheets such as a visa sheet, Alternatively, a blank passport is bound by binding a laminated body containing an IC chip for recording personal biometric information called an e-card together with other sheets such as a visa sheet on a cover. After that, the personal information for which the passport application has been applied is written on the bound blank passport by a method such as laser marking. In this case, if the data page or the e-card is thick, a blank passport is likely to open, and there is a problem that continuous production cannot be performed. These are preferably thin. Accordingly, the thickness of the data page is generally 400 to 600 μm, but a thinner one is preferable. In other words, if the hinge sheet C inevitably exceeds 250 μm, the other four sheets become very thin. In the transparent laser marking sheet A, the problem of poor laser marking occurs, and the multilayer sheet In B, since the problem of inferior printing concealment arises, it tends to be difficult to use.

  Here, the laminated hinge sheet of the present embodiment described above and, for example, a sheet made of a thermoplastic elastomer is used as a thermoplastic resin sheet P, and a sheet made of polyester resin and nylon resin is used as a thermoplastic resin sheet R, respectively. When the so-called laminated hinge sheet (i) used in 1) or the two-type two-layer laminated sheet of the thermoplastic resin sheet P / thermoplastic resin sheet R having the above-described structure is compared, the following difference occurs. That is, when the thermoplastic resin sheet P is used as a single single-layer sheet for a hinge sheet, it is excellent in fusion property and flexibility by heat lamination with a multilayer sheet (PETG / PC / PETG) adjacent to the hinge sheet, The strength of the cover and the sewing binding portion is also good, but the flexibility of the thermoplastic resin sheet P is too good, and a problem arises in the transportability when the hinge sheet is transported to the heating and laminating process. In addition, since these resins have a relatively low softening temperature (less than about 130 ° C.), they are excellent in short-term heating laminating and fusing properties in a rotary vacuum press at 140 to 160 ° C. for 90 to 120 seconds. In the heat-sealing process, “wrinkles” etc. occur in the part where the hinge sheet protrudes from other sheets, which not only makes it look bad, but also causes problems in the process of sewing with the cover and other sheets. is there.

  Further, when the thermoplastic resin sheet R is used as a single single-layer sheet for a hinge sheet, as an example, when a PET film is used alone as the thermoplastic resin sheet R, there is a problem that the PET film has low tear strength. Therefore, there arises a problem that the strength of the binding portion of the cover and other sheets and the sewing machine is insufficient. On the other hand, when a nylon resin film is used alone, there is a problem that it is inferior in fusibility at the time of heat lamination with an adjacent multilayer sheet (PETG / PC / PETG) in the heat lamination process, both of which are forgery prevention Such a hinge sheet cannot be used.

  Further, when a two-type two-layer laminated sheet of thermoplastic resin sheet P / thermoplastic resin sheet R is used as the hinge sheet, if nylon is used as the thermoplastic resin sheet R, the heat fusion on the thermoplastic resin sheet R side is performed. Since this is inferior in nature, this part can be easily removed by hand. Therefore, as with the case where the thermoplastic resin sheet R is used as a single single-layer sheet for a hinge sheet, it is a big problem in terms of prevention of forgery, and such a hinge sheet cannot be used. Furthermore, since the thermal expansion coefficient of each layer is different in the two-kind two-layer laminated sheet of different types of resins, such a two-kind two-layer laminated sheet is warped in either direction during the heating lamination process, and sometimes the sheet is “ There is also a problem that the curling may occur and the sewing machine cannot be bound. Therefore, it is not preferable.

  In addition, it is preferable that one end of the laminated hinge sheet C has an overhanging portion that is 5 to 100 mm longer than the transparent laser marking sheet A and the multilayer sheet B (see the overhanging portion 29 in FIG. 3). This is because forming the projecting portion on the laminated hinge sheet C facilitates the assembly to the electronic passport. That is, the overhanging portion is for assembling one end of the laminated hinge sheet C in the longitudinal direction to the electronic passport by sewing and / or bonding using an overhanging portion longer than the transparent laser marking sheet A and the multilayer sheet B.

  When the overhanging portion is formed on the laminated hinge sheet C, the length of the overhanging portion is preferably determined by the sewing and / or bonding workability and the strength and bonding strength of the sewing binding. However, as described later, when used for a laser marking laminate for an electronic passport, an electronic passport or the like, the dimension of the overhanging portion is preferably 5 to 100 mm, more preferably 5 to 50 mm, and still more preferably. Is 5-20 mm.

  Thus, by forming the overhanging portion, it becomes easier to assemble the electronic passport by sewing and / or bonding (using this overhanging portion).

  In addition, when an overhang | projection part is provided in the lamination | stacking hinge sheet | seat C, the 5 layer laminated body (5 layers) of transparent laser marking sheet A / multilayer sheet B / lamination hinge sheet C / multilayer sheet B / transparent laser marking sheet A which mentions later, for example. A laser marking laminate for electronic passports) or a transparent laser marking sheet A / multilayer sheet B / inlet sheet E / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A (consisting of 6 layers) The laser marking laminate for electronic passport) is preferable because it can be easily formed as an electronic passport formed by sewing and / or adhering to the electronic passport cover or back cover.

[2] Configuration of laser marking laminate for electronic passport of the present invention:
Further, it is a laser marking laminate for electronic passports using the laminated hinge sheet described so far, and includes five layers of transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A. The transparent laser marking sheet A is a transparent laser marking sheet formed by melt extrusion molding, and is a transparent thermoplastic resin 100 mainly composed of a polycarbonate resin. A single layer sheet made of a transparent polycarbonate resin composition containing 0.0005 to 1 part by mass of a laser light energy absorbing material with respect to part by mass, or the transparent laser marking sheet A is a transparent laser formed by melt extrusion molding A marking sheet, Resin which has a quin layer and a core layer, is formed by laminating at least three sheets by melt extrusion molding, and the skin layer as both outermost layers is mainly composed of an amorphous aromatic polyester resin And the core layer is made of a transparent polycarbonate resin composition containing 0.0005 to 1 part by mass of a laser light energy absorbing material with respect to 100 parts by mass of a transparent thermoplastic resin mainly composed of a polycarbonate resin. Further, the transparent laser marking sheet A has a total thickness of 50 to 200 μm and a core layer thickness ratio of less than 30 to 85%, or the transparent laser marking sheet A is transparent formed by melt extrusion molding. A laser marking sheet, which has a skin layer and a core layer, and is laminated by at least three layers by melt extrusion. The skin layer, which is both outermost layers, is made of a transparent resin mainly composed of a polycarbonate resin, and the core layer is 100 parts by mass of the transparent resin mainly composed of a polycarbonate resin. It consists of a transparent polycarbonate resin composition containing 0.0005 to 1 part by mass of a laser light energy absorber, and further, the total thickness of the transparent laser marking sheet A is 50 to 200 μm, and the core layer thickness ratio is less than 30 to 85%. The multilayer sheet B is a multilayer sheet having a skin layer and a core layer and formed by laminating at least three layers by melt extrusion molding. The skin layers, which are both outermost layers, are made of a resin mainly composed of an amorphous aromatic polyester resin, and The core layer of B is made of a transparent thermoplastic resin mainly composed of a polycarbonate resin, and the skin layer and / or the core layer of the multilayer sheet B includes 100 parts by mass of the copolyester resin and / or the polycarbonate resin. 1 part by mass or more of at least one kind of resin colorant such as dyes and pigments is contained with respect to 100 parts by mass, and the total thickness of the multilayer sheet B is 100 to 300 μm. The thickness ratio of the core layer to the total thickness of the multilayer sheet B is 30% or more and less than 85%, and the laminated hinge sheet C has a thickness of 80 to 250 μm. It is preferably configured as a laser marking laminate for an electronic passport.

[2-1] Configuration of laser marking laminate for electronic passport of the present invention:
That is, as the laser marking laminate for electronic passports of the first invention, as shown in FIG. 2A, the laser marking laminate for electronic passports using the laminated hinge sheet C described so far, which is a transparent laser marking It is a laser marking laminate for electronic passports in which five layers of sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A are laminated, and the transparent laser marking sheet A is melt extruded A transparent laser marking sheet formed by molding, comprising 0.0005 to 1 part by weight of a laser light energy absorbing material with respect to 100 parts by weight of a transparent thermoplastic resin mainly composed of a polycarbonate resin Constructed as a single-layer sheet 13 consisting of The multilayer sheet B (reference numeral 15) has a skin layer 15a and a core layer 15b, and is a multilayer sheet formed by laminating at least three layers by melt extrusion molding. The skin layer 15a, which is the outermost layer, is made of a resin mainly composed of an amorphous aromatic polyester resin, and specific examples thereof include a dicarboxylic acid unit mainly composed of a terephthalic acid unit and an ethylene glycol unit (I). And a polyester comprising a glycol unit mainly comprising 1,4-cyclohexanedimethanol unit (II), and ethylene glycol unit (I) and 1,4-cyclohexanedimethanol unit (II), (I) / (II) = 90 to 30/10 to 70 mol% of a transparent copolyester tree mainly comprising a copolyester resin Or the transparent copolyester resin composition mainly composed of the copolyester resin, and the core layer 15b of the multilayer sheet B is composed of a transparent thermoplastic resin mainly composed of a polycarbonate resin, In the skin layer and / or the core layer of B, 1 mass of at least one colorant of a resin such as a dye or a pigment is used with respect to 100 mass parts of the copolyester resin and / or 100 mass parts of the polycarbonate resin. Further, the total thickness of the multilayer sheet B is 100 to 300 μm, and the thickness ratio of the thickness of the core layer to the total thickness of the multilayer sheet B is 30%. The electronic passport is configured as a colored multilayer sheet having a thickness of less than 85%, and the laminated hinge sheet C has a thickness of 80 to 250 μm. Configured as a use laser marking laminate 11A.

[2-2] Configuration of laser marking laminate for electronic passport of the present invention:
The laser marking laminate for an electronic passport according to the second invention is a laser marking laminate for an electronic passport using the laminated hinge sheet C described so far, as shown in FIG. This is a laser marking laminate for electronic passports in which five layers of sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A are laminated, and the transparent laser marking sheet A (reference numeral 23) Is a transparent laser marking sheet formed by melt extrusion, which has a skin layer 23a and a core layer 23b, is formed by laminating at least three layers by melt extrusion, and is both outermost layers The skin layer 23a has a non-crystalline aromatic polyester resin as a main component. Specific examples include polyesters composed of dicarboxylic acid units mainly composed of terephthalic acid units, ethylene glycol units (I), and glycol units mainly composed of 1,4-cyclohexanedimethanol units (II). A copolymer polyester resin in which the ethylene glycol unit (I) and the 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90 to 30/10 to 70 mol%. A transparent thermoplastic resin comprising a transparent copolyester resin having a main component, or a transparent copolyester resin composition having the copolyester resin as a main component, and the core layer 23b having a polycarbonate resin as a main component. Transparent polycarbonate containing 0.0005 to 1 part by mass of a laser beam energy absorbing material with respect to 100 parts by mass The multilayer sheet B is composed of an nate resin composition, and is further configured as a multilayer sheet 1 having a total thickness of the transparent laser marking sheet A of 50 to 200 μm and a core layer thickness ratio of less than 30 to 85%. Is a multilayer sheet having a skin layer 15a and a core layer 15b, and is formed by laminating at least three layers by melt extrusion, wherein the skin layer 15a, which is both outermost layers of the multilayer sheet B, is And a resin mainly composed of an amorphous aromatic polyester-based resin. Specific examples include a dicarboxylic acid unit mainly composed of a terephthalic acid unit, an ethylene glycol unit (I), and 1,4-cyclohexanedi A polyester composed of glycol units mainly composed of methanol units (II), and 1,4,4 with ethylene glycol units (I) The transparent copolymer polyester resin whose main component is a copolymer polyester resin in which the cyclohexanedimethanol unit (II) is (I) / (II) = 90-30 / 10-70 mol%, or the copolymer polyester resin And the core layer 15b of the multilayer sheet B is made of a transparent thermoplastic resin whose main component is a polycarbonate resin, and the skin layer of the multilayer sheet B and / or The core layer contains 100 parts by mass of the copolyester resin and / or 100 parts by mass of the polycarbonate resin, and contains 1 part by mass or more of at least one colorant of a resin such as a dye or pigment, Further, the total thickness of the multilayer sheet B is 100 to 300 μm, and the thickness of the core layer is the multilayer sheet. A laser marking laminate for an electronic passport, which is configured as a colored multilayer sheet having a thickness ratio of 30% or more and less than 85% with respect to the total thickness of B, and the thickness of the laminated hinge sheet C is 80 to 250 μm 11B.

[2-3] Structure of laser marking laminate for electronic passport of the present invention:
The laser marking laminate for electronic passport of the third invention is a laser marking laminate for electronic passport using the laminated hinge sheet C described so far, as shown in FIG. This is a laser marking laminate for electronic passports in which five layers of sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A are laminated, and the transparent laser marking sheet A (reference numeral 33) Is a transparent laser marking sheet formed by melt extrusion molding, and has a skin layer 33a and a core layer 33b, and is formed by laminating at least three layers by melt extrusion molding, both of which are the outermost layers. The skin layer 33a is made of a transparent resin mainly composed of a polycarbonate resin. The core layer 33b is made of a transparent polycarbonate resin composition containing 0.0005 to 1 part by mass of a laser light energy absorbing material with respect to 100 parts by mass of a transparent resin mainly composed of a polycarbonate resin, The transparent laser marking sheet A is configured as a multilayer sheet 2 having a total thickness of 50 to 200 μm and a core layer thickness ratio of less than 30 to 85%. The multilayer sheet B (reference numeral 15) includes a skin layer 15a and a core layer 15b. A multilayer sheet formed by laminating at least three layers by melt extrusion, wherein the outermost layer of the multilayer sheet B is a non-crystalline aromatic polyester-based skin layer 15a. The resin is composed mainly of a resin. Specific examples include dicarboxylic acid units mainly composed of terephthalic acid units and ethylene glycol. And a 1,4-cyclohexanedimethanol unit (II), which is a polyester comprising a glycol unit, and an ethylene glycol unit (I) and a 1,4-cyclohexanedimethanol unit ( II) and (I) / (II) = 90-30 / 10-70 mol% of a transparent copolyester resin having a copolyester resin as a main component, or the copolyester resin as a main component. The core layer 15b of the multilayer sheet B is made of a transparent thermoplastic resin mainly composed of a polycarbonate resin, and the skin layer and / or the core layer of the multilayer sheet B includes a transparent copolymer polyester resin composition. Dye and pigment with respect to 100 parts by mass of the copolyester resin and / or 100 parts by mass of the polycarbonate resin The multilayer sheet B contains at least one type of resin colorant in an amount of 1 part by mass or more, and further has a total thickness of the multilayer sheet B of 100 to 300 μm and a thickness of the core layer. As a laser marking laminate 11C for electronic passports, which is configured as a colored multilayer sheet having a thickness ratio of 30% or more and less than 85% with respect to the total thickness of the laminated hinge sheet C is 80 to 250 μm in thickness. Composed.

  Hereinafter, each structure of the laser marking laminated body 11A, 11B, and 11C for electronic passports is demonstrated.

[A] Transparent laser marking sheet A:
The transparent laser marking sheet A of the present invention is either a single-layer transparent laser marking sheet having only a core layer or a transparent laser marking multilayer sheet composed of at least three layers of a skin layer and a core layer. It is a transparent multilayer sheet laminated | stacked by shaping | molding.

[A-1] Configuration of transparent laser marking sheet A:
When the transparent laser marking sheet A is configured as a single-layer sheet having a single-layer structure, it is preferably formed by melt extrusion molding.

  When the transparent laser marking sheet A is configured as a single layer sheet, the transparent laser marking sheet A is formed of a polycarbonate resin (PC), particularly a transparent resin layer mainly composed of a transparent polycarbonate resin. However, the polycarbonate resin to be used is not particularly limited, but those having a melt volume rate of 4 to 20 can be suitably used. If the melt volume rate is less than 4, it is meaningful in that the toughness of the sheet is improved, but the molding processability is inferior. On the other hand, a melt volume rate exceeding 20 is not preferable because the sheet has poor toughness. In this way, by forming the transparent laser marking sheet A from a transparent resin layer mainly composed of polycarbonate resin (PC), so-called “fluff” due to foaming of the marking portion by laser light irradiation is suppressed and laser light irradiation is performed. The wear resistance of the marking portion can be improved.

  In addition, when the transparent laser marking sheet A is configured as a single layer sheet, it is important to have high transparency. The raw material of the transparent laser marking sheet A configured as a single layer sheet is not particularly limited as long as it is a resin or filler that does not hinder the transparency of the polycarbonate resin, but for the purpose of improving scratch resistance or improving heat resistance. And a blend of a general-purpose polycarbonate resin and a special polycarbonate resin or a blend of a polycarbonate resin and a polyarylate resin.

  More preferably, the transparent laser marking sheet A is configured as a “multiple sheet” having a “at least three layers” structure including a skin layer and a core layer (hereinafter referred to as “multilayer sheet” or “multilayer sheet A” as appropriate). That is. However, the “three-layer sheet” means “at least three layers” and is not limited to a sheet having a three-layer structure. In other words, in the transparent laser marking sheet A, “three-layer sheet” is for convenience of explanation, and “three-layer sheet” means “a sheet composed of at least three layers”. This means that it is not intended to limit the sheet to “three layers”. That is, if it is composed of 3 layers or more, this transparent laser marking sheet A can be used as a multilayer sheet, whether it is composed of 5 layers, 7 layers, or an odd number of layers. include.

  Further, when the transparent laser marking sheet A is configured as a multilayer sheet having a “at least three layers” structure including a skin layer and a core layer, it is preferably laminated by melt extrusion.

  When the transparent laser marking sheet A is configured as a multilayer sheet having a multilayer structure such as “at least three layers” described above, the skin layer of the transparent laser marking sheet A described later is a multilayer sheet configured with a multilayer structure. It is necessary to arrange | position so that a core layer may be pinched | interposed into both skin layers (between). In addition, the thickness of the skin layer of the transparent laser marking sheet A is not particularly limited, but it is more preferable that the thickness is formed in a predetermined range described later.

  However, even when the transparent laser marking sheet A is composed of the above-mentioned “odd-numbered odd number layers” or more, if it has a multi-layer structure, the layers per layer of the skin layer and the core layer to be arranged If the thickness is too thin, a so-called mold stick may be generated in the heating press process during lamination. Accordingly, a multilayer sheet composed of 5 layers is more preferable, and a 3-layer structure is more preferable.

  That is, the transparent laser marking sheet A in the present embodiment is composed of odd layers as described above because a multilayer sheet composed of even layers always has the same structure as a multilayer sheet composed of odd layers. For example, in the case of a transparent laser marking sheet comprising four layers, the layers may be arranged as skin layer (PETG) / core layer (PC) / core layer (PC) / skin layer (PETG), or skin layer (PC) / This is because the arrangement of the core layer (PC) / core layer (PC) / skin layer (PC) layer is obtained, and, after all, the configuration is the same as that of the transparent laser marking sheet composed of odd layers.

  For example, when the transparent laser marking sheet A composed of three layers (so-called “three-layer sheet”) is taken as an example, an arrangement of layers such as skin layer (PETG) / core layer (PC) / skin layer (PETG) is made. Two skin layers are arranged on the outermost side of one and the other so that the arrangement of layers such as skin layer (PC) / core layer (PC) / skin layer (PC) is made, One core layer is arranged to be sandwiched between the two skin layers to form a multilayer sheet. Taking a multilayer sheet composed of five layers as an example, the arrangement of layers such as skin layer (PETG) / core layer (PC) / skin layer (PETG) / core layer (PC) / skin layer (PETG) One or the other so that the arrangement of layers such as skin layer (PC) / core layer (PC) / skin layer (PC) / core layer (PC) / skin layer (PC) is made Two skin layers may be disposed on the outermost sides of the two, and the skin layer and the core layer may be alternately arranged to form the transparent laser marking sheet A. Here, as described above, even if configured as a single-layer transparent laser marking sheet having only a core layer, it has sufficient laser colorability and can exhibit the effects of the present invention. The transparent laser marking sheet A is formed as the multilayer sheet 1 or the multilayer sheet 2 having the multilayer structure as described above. By constructing the transparent laser marking sheet A as the multilayer sheet 2 having such a multilayer structure, the laser beam is irradiated at a higher power than the transparent laser marking sheet formed as a single layer sheet having only the core layer, and the laser This is because the concentration of the marking portion can be increased, and in addition, so-called “swelling” due to foaming of the core layer 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 core layer marking portion, a synergistic effect that the wear resistance of the marking portion is further improved as compared with the case without the skin layer can be achieved. Moreover, by constituting the transparent laser marking sheet A as the multilayer sheet 1, sufficient heat-fusibility can be ensured, sheet transportability in the laminating process, releasability from the mold after hot pressing, bendability, Fine adjustment is possible in terms of transparency and the like.

  Moreover, it is preferable that the total thickness (total thickness) of the transparent laser marking sheet A is 50-200 micrometers in any of a single layer sheet or a three layer sheet (multilayer sheet 1, multilayer sheet 2). If the total thickness of the transparent laser marking sheet A is less than 50 μm, the laser marking property becomes insufficient, which is not preferable. In the case of the multilayer sheet 1, a so-called mold stick problem that the multilayer sheet sticks to the mold at the time of heat-sealing in the multilayer sheet laminating process is likely to occur. In order to remove such trouble, it is necessary to control the heat fusion temperature, the press pressure at the time of heat fusion, the heat fusion time, and the like. However, this control is not preferable because it is complicated and tends to hinder the molding process. When the total thickness of the transparent laser marking sheet A exceeds 200 μm, for example, when the transparent laser marking sheet A and the multilayer sheet B exceeding 200 μm are used, the laser marking laminate for electronic passport is laminated and formed In this case, the total maximum thickness exceeds 800 μm and becomes too thick to be practically used.

  Further, the transparent laser marking sheet A is a multilayer sheet (so-called three-layer sheet) composed of a skin layer and a core layer, and in the case of the multilayer sheet 2, the total thickness (total thickness) of the transparent laser marking sheet A ) Is preferably 50 to 200 μm, and the ratio of the thickness of the core layer to the total sheet thickness of the multilayer sheet is preferably 35% or more and less than 85%. If the thickness of the core layer is less than 35%, the laser marking property is inferior, which is not preferable. Further, if it exceeds 85%, the skin layer becomes too thin, and when the laser beam is irradiated with high power, the laser beam energy absorbent blended in the core layer absorbs the laser beam energy and converts it into heat. This is not preferable because high heat is generated and the effect of suppressing the so-called “fluff generation” in the laser light irradiation part is poor. In addition, even if the laser light energy is adjusted and a preferable laser color is obtained, the laser marking portion (region where laser marking has been applied) is compared with the case where the thickness of the skin layer is within the aforementioned desired range. This is not preferable because the wear resistance is not sufficient.

  The transparent laser marking sheet A is a multilayer sheet (so-called three-layer sheet) composed of a skin layer and a core layer. In the case of the multilayer sheet 1, the total thickness (total thickness) of the transparent laser marking sheet A is used. ) Is 50 to 200 μm, and the ratio of the thickness of the core layer to the total sheet thickness of the multilayer sheet is preferably 30% or more and less than 85%. If the thickness of the skin layer is too thin, the generation of a mold stick and a decrease in heat-fusibility will occur. On the other hand, if the thickness of the skin layer is too large, the thickness of the core layer described later will be too small. This is because it is undesirably caused by the problem that the film is inevitably thinned and the laser marking property is inferior or warpage occurs after the multilayer sheets are laminated.

  Thus, local characteristics such as the characteristics of the transparent laser marking sheet A can be obtained by setting the total thickness of the transparent laser marking sheet A composed of a single-layer sheet or multilayer sheets 1 and 2 (three-layer sheet) to a desired thickness. It becomes easy to pull out. Furthermore, not only the total thickness of the entire three-layer sheet, but also the ratio of the thickness of the skin layer and the core layer constituting the three-layer sheet in the three-layer sheet is set to the above-described desired ratio, thereby providing three layers. This is preferable because the effect of the present invention can be further exhibited, for example, by making it easy to improve the laser marking property in combination with the thickness of the entire sheet being in the desired range.

  Moreover, it is preferable that the total light transmittance of the said transparent laser marking sheet A is 70% or more, More preferably, it is 85% or more. For example, when the laser marking laminate for an electronic passport of this embodiment is used for an electronic passport, printing is generally performed in this application. Therefore, under the transparent laser marking sheet A, for example, a white sheet on which characters, figures, etc. are printed (hereinafter, printing of a white sheet on which letters, figures, etc. are printed is referred to as “printing part” as appropriate). For example, the non-printing part of the transparent laser marking sheet A that is the outermost layer is irradiated with laser light to develop a black color to mark images and characters, and to prevent forgery by design and laser marking in the printing part. Often used in combination. By manufacturing and using in this way, a clear image can be obtained by virtue of the sharpness of the printed portion and the black / white contrast of the laser marking portion because the underlayer is white. 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 (clearness of black / white contrast). Sex can stand out). 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 contrast is important. This is not preferable because a problem occurs in that the ink is insufficient and sufficient marking properties cannot be secured, and printing is performed on the base white sheet, which causes a problem in the visibility of the printing.

  Here, the “total light transmittance” is an index indicating the ratio of transmitted light among the light incident on the film or the like, 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 (light transmittance and total light reflectance). Measurement of this total light transmittance Can be measured using, for example, a Nippon Denshoku Industries haze meter (trade name: “NDH 2000”), a spectrophotometer (trade name “EYE7000” manufactured by Macbeth).

[A-1-1] Skin layer in transparent laser marking sheet A:
When a skin layer is formed on the transparent laser marking sheet A, that is, when a multilayer sheet is formed from a multilayer structure as a “three-layer structure”, the skin layer is arranged outside the multilayer sheet (three-layer sheet). It is configured as both outermost layers. That is, this skin layer plays a role as a surface layer (both outermost layers) of the multilayer sheet (three-layer sheet), which is arranged so as to be sandwiched from both end surfaces (outside) of the core layer in the multilayer sheet described later. Yes.

  Here, the thicknesses of the skin layers are preferably the same. For example, in the case of the skin layer constituting the multilayer sheet 2, when the transparent laser marking sheet A is constructed as a multilayer sheet from skin layers having different thicknesses, the front and back sides of the laser marking laminate or card for electronic passports Laser marking is common. In this case, because the thickness of the outermost skin layer and the outermost skin layer of the laminate is different, the so-called “swelling” suppression effect by the foaming of the core layer marking by laser light irradiation and the abrasion resistance of the marking part This is because the effects are different. Further, for example, in the case where the transparent laser marking sheet A is configured as a multilayer sheet from three layers of skin layer (PC) / core layer (PC) / skin layer (PC), the thickness of the core layer is 30%. When the content is less than 85%, the skin layer is 15% or more and less than 70% on both sides. When the thickness of the skin layer is less than 15%, the effect of suppressing the so-called “fluff” caused by foaming of the core layer marking portion by laser light irradiation and improving the wear resistance of the marking portion by laser light irradiation is not sufficient. . On the other hand, when the thickness of the skin layer is too large, the thickness of the core layer, which is a laser marking layer, is inevitably thinned, and the laser marking property is inferior.

  Further, for example, in the case of the skin layer constituting the multilayer sheet 1, when the multilayer sheet A is composed of skin layers having different thicknesses, as described above, the sheet warpage occurs in the pressing process of the multilayer sheet. This is because it is not preferable. In addition, for example, when the multilayer sheet A is composed of three layers of skin layer (PETG) / core layer (PC) / skin layer (PETG), the thickness of the core layer is 30% or more and less than 85%. In this case, the skin layer is 15% or more and less than 70% on both sides. If the thickness of the skin layer is too thin, the generation of a mold stick and a decrease in heat-fusibility will occur.On the other hand, if the thickness of the skin layer is too large, the thickness of the core layer, which will be described later, The film is inevitably thinned, and it is not preferable because the laser marking property is inferior or warpage occurs after the multilayer sheets are laminated.

  In the case of the multilayer sheet 2, the skin layer is preferably formed of a polycarbonate resin (PC), particularly a transparent resin layer mainly composed of a transparent polycarbonate resin. However, the polycarbonate resin to be used is not particularly limited, but those having a melt volume rate of 4 to 20 can be suitably used. If the melt volume rate is less than 4, it is meaningful in that the toughness of the sheet is improved, but the molding processability is inferior. On the other hand, a melt volume rate exceeding 20 is not preferable because the sheet has poor toughness. By forming the skin layer from a transparent resin layer mainly composed of polycarbonate resin (PC) in this way, so-called “blowing” due to foaming of the core layer marking portion by laser light irradiation is suppressed and marking by laser light irradiation is performed. The wear resistance of the portion can be improved.

  In the case of the multilayer sheet 2, it is important that the skin layer has high transparency, and there is no particular limitation as long as it is a resin, filler or the like that does not hinder the transparency of the polycarbonate resin. For the purpose of improving the scratch resistance or improving the heat resistance, a blend of a general-purpose polycarbonate resin and a special polycarbonate resin or a blend of a polycarbonate resin and a polyarylate resin can be used.

  In the case of the multilayer sheet 1, as a material for forming the skin layer, a polyester-based resin composition, that is, a copolyester resin described later, and a lubricant described below are prepared. It forms as a layer which consists of a characteristic aromatic polyester-type resin composition.

(Copolymerized polyester resin)
The copolyester resin used for the multilayer sheet 1 is preferably blended as a main component of the amorphous aromatic polyester resin composition. The polyester resin here means a dehydration condensation product of an aromatic dicarboxylic acid and a diol, and the substantially non-crystalline aromatic polyester resin used in the present invention is a crystalline resin among aromatic polyester resins. Low thing. These do not cause white turbidity due to crystallization or decrease in fusing property even if heat molding is frequently performed with a hot press or the like. As a specific example of the copolymer polyester resin, the skin layer mainly includes a dicarboxylic acid unit mainly composed of a terephthalic acid unit, an ethylene glycol unit (I), and a 1,4-cyclohexanedimethanol unit (II). And an ethylene glycol unit (I) and a 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90 to 30/10 to 70 mol%. A copolyester resin is used. The reason for preparing the component amounts of ethylene glycol and 1,4-cyclohexanedimethanol contained in this copolymerized polyester resin is that the amount of substitution of the ethylene glycol component in the copolymerized polyester resin is less than 10 mol%. This is because the obtained resin does not become sufficiently amorphous, and recrystallization proceeds in the cooling step after heat fusion, resulting in poor heat fusion. Moreover, it is because the resin obtained exceeding 70 mol% is not sufficiently amorphous, and recrystallization proceeds in the cooling step after heat fusion, resulting in poor heat fusion. Therefore, as in this embodiment, the resin obtained by adjusting the component amounts of ethylene glycol and 1,4-cyclohexanedimethanol becomes sufficiently amorphous, and is excellent in terms of heat fusibility. Therefore, it can be said to be a preferable resin.

  As this copolyester resin, for example, a substantially non-crystalline aromatic polyester resin (abbreviated as “PETG”) in which about 30 mol% of the ethylene glycol component in polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol. (Trade name “Easter Copolyester”, manufactured by Eastman Chemical Co., Ltd.)) is commercially available.

[A-1-2] Core layer in transparent laser marking sheet A:
As described above, the core layer is composed of the three-layer sheet (multilayer sheets 1 and 2) and the skin layer is formed on the outermost layer, and the core layer is arranged at the center of the three-layer sheet. Configured as a so-called nuclear layer. That is, in the case of a three-layer sheet, the core layer is formed as a core layer of the three-layer sheet so as to be sandwiched between two skin layers disposed on the outermost side.

  Here, the thickness of the core layer of the multilayer sheet 2 is preferably formed such that the ratio of the thickness in all the sheets is 30% or more and less than 85%. When the thickness ratio of the core layer is 30% or more, the thickness effect of the core layer marking portion by laser light irradiation increases the contrast with the uncolored portion due to the base white layer, and the visibility and sharpness of the marking portion are improved. On the other hand, when the thickness ratio of the core layer exceeds 85%, the effect of suppressing the so-called “swelling” by the foaming of the core layer marking by laser light irradiation and the effect of improving the wear resistance of the marking portion by laser light irradiation are not sufficient. . Moreover, if the thickness ratio of the core layer is less than 30%, the laser marking property is inferior, which is not preferable.

  Moreover, as thickness of the core layer of the multilayer sheet 1, it is preferable to form so that the ratio of the thickness which occupies in all the sheets may be 30% or more and less than 85%. When the thickness ratio of the core layer is 85% or more, since the total thickness of the transparent laser marking sheet A is as thin as 50 to 150 μm, the skin layer is relatively thin, and the lubricant is mixed in the skin layer. However, it is not preferable because the problem of the mold stick that the transparent laser marking sheet A sticks to the mold in the heating press process in the lamination process occurs. Also, if the thickness ratio of the core layer is less than 30%, the problem of the mold stick does not occur because the skin layer is thick in the laminating process, but the laser marking property is inferior and the heat resistance is poor, so the sheet warps. It is not preferable.

  More preferably, the ratio of the thickness of the core layers of the multilayer sheets 1 and 2 to the total sheet is 40% or more and less than 85%. The core layer thickness ratio in the case of a so-called three-layer transparent laser oversheet is a major factor in laser color development (contrast property). In other words, the core layer thickness is the main factor for laser marking properties in both PC / PC (laser mark compatible) / PC 3 layer structure and PETG / PC (laser mark compatible) / PETG 3 layer structure. The thicker the core layer, the better. Moreover, since the thickness of a skin layer contributes to heat-fusibility with an inlay layer, the thinner one is preferable. Therefore, the regulation of the core layer thickness ratio of the three-layer transparent laser marking oversheet is more preferably 40% or more and less than 85%. In this regard, in the three-layer transparent laser marking oversheet of 85% or more, the skin layer becomes too thin, so that in the two-type three-layer coextrusion molding, it becomes difficult to control the thickness of the skin layer, and the molding is stably performed. It will be difficult.

  As a material (raw material) constituting the core layer, a polycarbonate resin, particularly a transparent polycarbonate resin is used. However, the polycarbonate resin to be used is not particularly limited, but those having a melt volume rate of 4 to 20 can be suitably used. If the melt volume rate is less than 4, it is meaningful in that the toughness of the sheet is improved, but the molding processability is inferior. On the other hand, a melt volume rate exceeding 20 is not preferable because the sheet has poor toughness.

[A-1-3] Laser light energy absorbing material:
When the transparent laser marking sheet A is configured as a single layer sheet having a single layer structure, the transparent laser marking sheet A or the multilayer sheets 1 and 2 in which the transparent laser marking sheet A is at least a three layer sheet. When it is configured as, it is preferable that the core layer contains 0.0005 to 1 part by mass of the laser light energy absorbing material with respect to 100 parts by mass of the transparent resin mainly composed of the polycarbonate resin. Such a configuration is preferable because it is excellent in laser colorability when laser-marked, the contrast between the fabric color and the printed portion is increased, and clear characters, symbols, and images can be obtained.

  Examples of the laser light energy absorbing material include at least one selected from the group consisting of carbon black, titanium black, metal oxide, metal sulfide, and metal nitride. More preferably, the laser light energy absorbing material is at least one or more selected from the group consisting of carbon black, titanium black, and metal oxide in the core layer of the single layer sheet or multilayer sheets 1 and 2. Is contained.

  Here, the average particle size of carbon black, titanium black, metal oxide, metal sulfide, and metal nitride added to the multilayer sheet 2 is preferably less than 150 nm, more preferably less than 100 nm, 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 titanium black or metal oxide having an average particle diameter of less than 150 nm is preferable. If the average particle size of carbon black, titanium black, metal oxide, metal sulfide, or metal nitride exceeds 150 nm, the transparency of the sheet may decrease or large irregularities may occur on the sheet surface, which is not preferable. . Furthermore, if the average particle size of the carbon black is less than 10 nm, the laser colorability is lowered, and it is too fine to be difficult to handle. Further, if the DBT oil absorption is less than 60 ml / 100 gr, the dispersibility is poor, and if it exceeds 170 ml / 100 gr, the concealability is poor, which is not preferable.

  The average particle diameter of titanium black, metal oxide, metal sulfide, and metal nitride added to the multilayer sheet 1 is the same as that of the multilayer sheet 1 described above. Carbon black having an average particle diameter of 10 to 90 nm and a dibutyl phthalate (DBT) oil absorption of 60 to 170 ml / 100 gr is preferable. If the average particle size of the carbon black is less than 10 nm, the laser colorability is lowered and handling is too fine, and if it exceeds 90 nm, the transparency of the sheet is lowered or large irregularities are generated on the surface of the sheet. Is not preferable. Further, if the DBT oil absorption is less than 60 ml / 100 gr, the dispersibility is poor, and if it exceeds 170 ml / 100 gr, the impermeability is inferior.

  In addition, as the metal oxide added to the multilayer sheets 1 and 2, as the metal forming the oxide, zinc, magnesium, aluminum, iron, titanium, silicon, antimony, tin, copper, manganese, cobalt, vanadium, bismuth, Examples thereof include niobium, molybdenum, ruthenium, tungsten, palladium, silver, and platinum. Furthermore, ITO, ATO, AZO, etc. are mentioned as a composite metal oxide.

  Examples of the metal sulfide added to the multilayer sheets 1 and 2 include zinc sulfide and cadmium sulfide. Furthermore, examples of the metal nitride include titanium nitride.

  Thus, as the energy absorber to be added to the multilayer sheets 1 and 2, carbon black, metal oxide, and composite metal oxide are preferably used, and each is used alone or in combination.

  Furthermore, the energy absorber to the multilayer sheet 2 is preferably added (blended) with 0.0005 to 1 part by mass of carbon black, more preferably 0.0008 to 0.1 part by mass. Further, 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 blending amount of the mixture is 0.0005 to 1 part by mass More preferably, it is 0.0008 to 0.5 parts by mass.

  Here, the reason why the energy absorber is added to the multilayer sheet 2 in the desired amount (blending amount) is that the transparent laser marking sheet A is preferably transparent. In other words, a laser marking laminate for electronic passports, or when used for electronic passports, a transparent laser marking sheet (layer called overlay) is laminated on a printed white sheet (layer called inlay). The laser beam is irradiated to the overlay of the part that has not been printed, and the black color is developed to mark images and characters, combining the design in the printed part and the anti-counterfeit effect by laser marking. Often used. By manufacturing and using in this way, a clear image can be obtained by virtue of the sharpness of the printed portion and the black / white contrast of the laser marking portion because the underlayer is white. In other words, if the overlay layer laminated on the above inlay layer is inferior in transparency, the printed image, characters, etc. will be unclear, and the black / white contrast in the laser marking part will be inferior. It becomes an upper problem. For this purpose, carbon black having a small average particle diameter is preferably used, and a mixture of carbon black and at least one selected from other metal oxides, metal sulfides, metal carbonates and metal silicates is used as laser energy. Also when used as an absorbent, the average particle size of these metal oxides and metal sulfides is at least less than 150 nm, preferably less than 100 nm.

  Therefore, when the average particle diameter of the laser energy absorber added to the multilayer sheet 2 exceeds 150 nm, the transparency of the transparent laser marking sheet A is not preferable. Moreover, when the compounding amount of these laser energy absorbers exceeds 1 part by mass, the transparency of the transparent laser marking sheet A (multilayer sheet) is lowered, and the amount of absorbed energy is too much, thereby deteriorating the resin. As a result, sufficient contrast cannot be obtained. On the other hand, if the addition amount of the laser energy absorber is less than 0.0005 parts by mass, a sufficient contrast cannot be obtained, which is not preferable. Furthermore, if the amount of the laser energy absorber added exceeds 1 part by mass, the transparency of the transparent laser marking sheet A is lowered, which is not preferable, and abnormal heat generation occurs, which causes decomposition and foaming of the resin. However, the desired laser marking cannot be performed.

  Moreover, it is preferable that 0.0001-3 mass parts of carbon black is added (mixed) to the energy absorber to the multilayer sheet 1, More preferably, it is 0.0001-1 mass part. When carbon black and at least one selected from metal oxides, metal sulfides, metal carbonates and metal silicates having an average particle diameter of less than 150 nm are used in combination, the blending amount of the mixture is 0.0001. -6 mass parts is mix | blended, More preferably, it is 0.0001-3 mass parts. Thus, the addition amount (blending amount) of the energy absorber is prepared for the following reason. That is, the transparent laser marking sheet A is preferably transparent, and in many cases, the colored laser marking multilayer sheet B, which is the lower layer of the transparent laser marking sheet A, is printed. In that case, the transparency of the transparent laser marking sheet A is If it is inferior, the printed image, characters, etc. will become unclear and cause a practical problem. For this purpose, carbon black having a small average particle diameter is preferably used, and a mixture of carbon black and at least one selected from other metal oxides, metal sulfides, metal carbonates and metal silicates is used as laser energy. Also when used as an absorbent, the average particle size of these metal oxides, metal sulfides, metal carbonates and metal silicates is at least less than 150 nm, preferably less than 100 nm, and more preferably less than 50 nm.

  Therefore, when the average particle diameter of the laser energy absorbent added to the multilayer sheet 1 exceeds 150 nm, the transparency of the transparent laser marking sheet A is not preferable. In addition, if the blending amount of the laser energy absorber exceeds 6 parts by mass, the transparency of the transparent laser marking sheet A (multilayer sheet) is lowered, and the amount of absorbed energy is too much, causing the resin to deteriorate and sufficient contrast. Cannot be obtained. On the other hand, if the addition amount of the laser energy absorber is less than 0.0001 parts by mass, a sufficient contrast cannot be obtained, which is not preferable.

[A-1-4] Lubricant, antioxidant and / or anti-coloring agent:
Moreover, in this embodiment, it is preferable to make a transparent laser marking sheet A comprised as a single layer sheet or the multilayer sheets 1 and 2 contain a lubricant, and when the transparent laser marking sheet A consists of what is called a three-layer sheet. It is preferable that a lubricant is contained in the skin layer. This is because the inclusion of the lubricant can prevent fusion to the press plate at the time of hot pressing.

  Furthermore, in this embodiment, an antioxidant and / or an anti-coloring agent, and an ultraviolet absorber and / or light as necessary for the transparent laser marking sheet A configured as a single-layer sheet or multilayer sheets 1 and 2. It is also preferable to contain a stabilizer. When the transparent laser marking sheet A is a so-called three-layer sheet (multi-layer sheet), an antioxidant and / or coloring may be added to the skin layer and / or the core layer as necessary. It is also preferable to contain an inhibitor and an ultraviolet absorber and / or a light stabilizer. Addition (compounding) of an antioxidant and / or an anti-coloring agent effectively acts on physical property reduction and hue stabilization due to molecular weight reduction during molding processing. As this antioxidant and / or anti-coloring agent, a phenol-based antioxidant or a phosphite-based anti-coloring agent is used. Further, the addition (formulation) of an ultraviolet absorber and / or a light stabilizer effectively acts to suppress light deterioration resistance during storage of the transparent laser marking sheet A and during actual use of the electronic passport as the final product.

  Examples of phenolic antioxidants include, for example, α-tocopherol, butylhydroxytoluene, sinapir 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-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl)- -Methylphenyl 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-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butyl) Enol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1 , 6-Hexanediol bis [3- (3,5-di-tert-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-tert-butyl) -M-cresol), 4,4'-thiobis (3-methyl-6-tert-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-tert-butylphenol) 2,2-thiodiethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-tert-butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxy Hydrocinnamide), N, N′-bis [3- (3,5-di-tert-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-tert- Butyl-4-hydroxyphenyl) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionyloxymethyl] methane and the like.

  Among these examples, n-octadecyl-3- (3,5-di-tert-butyl-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (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-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane is preferred, and n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is particularly preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  Examples of the phosphite ester colorant include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, and dioctyl monophenyl. Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like.

  Further, as other phosphite compounds, those that react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Among these, tris (2,4-di-tert-butylphenyl) phosphite is particularly preferable. 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.

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2,2′methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], condensate with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol The benzotriazole type compound represented by can be mentioned.

  Further, examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-bis (2,4). Examples thereof include hydroxyphenyl triazine compounds such as -dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Furthermore, as an ultraviolet absorber, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazine-4) -One), and cyclic imino ester compounds such as 2,2'-p, p'-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]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetra Methyl) piperi Nil] siloxane and other hindered amines can also be included, and such light stabilizers can be used in combination with the ultraviolet absorbers and, in some cases, various antioxidants, in terms of better weather resistance and the like. Demonstrate.

  Examples of the lubricant include fatty acid esters, fatty acid amides, and fatty acid metal salts, and it is preferable to add at least one lubricant selected from them.

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

  Further, the single layer sheet of the transparent laser marking sheet A contains 0.01 to 3 parts by mass of a lubricant with respect to 100 parts by mass of the transparent thermoplastic resin, and an antioxidant and / or an anti-coloring agent. The skin layer in the multilayer sheet 2 of the transparent laser marking sheet or the transparent laser marking sheet A containing 1 to 5 parts by mass and the ultraviolet absorber and / or light stabilizer 0.1 to 5 parts by mass is transparent. While containing 0.01 to 3 parts by mass of lubricant with respect to 100 parts by mass of the thermoplastic resin, 0.0005 to 1 part by mass of a laser light energy absorbing material, 0.1 to 0.1 parts of antioxidant and / or anti-coloring agent. It is preferable to be configured as a transparent laser marking sheet containing 5 parts by mass and 0.1 to 5 parts by mass of an ultraviolet absorber and / or light stabilizer.

  Here, as addition amount of a lubricant, it is preferable that 0.01-3 mass parts is added with a single layer sheet and the multilayer sheets 1 and 2, More preferably, it is 0.02-1 mass parts. If it 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 in interlayer heat fusion at the time of multi-layer heating press of electronic passports and cards. Furthermore, if the antioxidant and / or anti-coloring agent is less than 0.1 parts by mass, problems such as thermal oxidation reaction of the polycarbonate resin in the process of melting, extruding and molding, and thermal discoloration resulting therefrom are likely to occur. Exceeding the part is not preferable because problems such as bleeding of these additives are likely to occur. Furthermore, if the ultraviolet absorber and / or light stabilizer is less than 0.1 parts by mass, the effect is poor, and light defects such as deterioration due to light resistance and discoloration are likely to occur. It is not preferable because defects are likely to occur.

[B] Configuration of multilayer sheet B:
The multilayer sheet B of the present invention is configured as a sheet having at least a three-layer structure composed of a skin layer and a core layer, and is laminated by melt extrusion molding. The three-layer sheet according to the present embodiment is “at least three layers” and is not limited to a sheet having a three-layer structure. That is, in the multilayer sheet B in the present embodiment, “three-layer sheet” is for convenience of description, and “three-layer sheet” means “a sheet composed of at least three layers”. This is not intended to limit the sheet to “three layers”. In other words, the multilayer sheet B of the present embodiment may be composed of 5 layers, 7 layers, or an odd number of layers. include.

  However, also in the case where the multilayer sheet B of the present embodiment is configured from the multilayer structure described above, the skin layer described later is disposed at the outermost position of the sheet configured by the multilayer structure, and both surfaces of the sheet Furthermore, it is necessary that the core layer is disposed between the skin layers (between). The thickness of the skin layer is not particularly limited, but it is more preferable that the skin layer is formed to have a thickness within a predetermined range described later.

  On the other hand, even when the multilayer sheet B is composed of the above-mentioned “odd-numbered odd number layers” or more, if the multilayer sheet B is too multilayered, the layer thickness per layer of the skin layer and the core layer to be arranged is The film becomes too thin, and the problem of poor heat fusion with the transparent laser marking sheet A occurs. Therefore, it is preferably composed of 5 layers, more preferably 3 layers.

  Here, the multilayer sheet B is composed of odd layers as described above because a multilayer sheet composed of even layers always has the same structure as a multilayer sheet composed of odd layers. For example, in a multilayer sheet composed of four layers, the layers are arranged such as skin layer (PETG) / core layer (PC) / core layer (PC) / skin layer (PETG). It is because it becomes the same structure as a multilayer sheet.

  Further, for example, in the case of a multilayer sheet composed of three layers, both one and the other are arranged so that the layers are arranged such as skin layer (PETG) / core layer (PC) / skin layer (PETG). Two skin layers are arranged on the outermost side, and one core layer is arranged so as to be sandwiched between the two skin layers to form a multilayer sheet. Taking a multilayer sheet composed of five layers as an example, the arrangement of layers such as skin layer (PETG) / core layer (PC) / skin layer (PETG) / core layer (PC) / skin layer (PETG) As is done, two skin layers may be disposed on the outermost sides of one and the other, and a multilayer sheet may be formed by alternately arranging skin layers and core layers. By forming a multilayer sheet having a multilayer structure in this manner, sufficient heat-fusibility can be ensured.

  Further, the total thickness (total thickness) of the three-layer sheet (multilayer sheet B) is 100 to 300 μm, and the thickness of the core layer occupies the total thickness of the multilayer sheet B. The thickness ratio (thickness ratio) is preferably 30% or more and less than 85%. If the total thickness of the three-layer sheet (multilayer sheet B) is less than 100 μm, the PETG layer, which is the skin layer of the multilayer sheet B, is inevitably thinned and is laminated on the outermost layer during heat fusion in the multilayer sheet lamination process. The heat-sealing property between the transparent laser marking sheet A (including both “single-layer sheet” and so-called “three-layer sheet”) and the multilayer sheet B cannot be ensured. When the thickness exceeds 300 μm, when a laser marking laminate for an electronic passport is formed using a three-layer sheet exceeding 300 μm, the total thickness becomes too thick to be used. It is preferable that the ratio of the thickness of the core layer to the thickness is 30% or more and less than 85%, in order to ensure the compatibility when printing on the multilayer sheet B, In other words, if the skin layer is too thin, the transparent laser marking sheet A (“ Heat fusion cannot be secured between the “single-layer sheet” and the so-called “three-layer sheet” and the multilayer sheet B. On the other hand, if the thickness of the skin layer is too large, the thickness of the core layer described later However, since it is inevitably thinned, it is impossible to ensure the compatibility when printing on the multilayer sheet B. Furthermore, when no colorant is added to the skin layer, the transparent laser marking sheet which is the outermost layer In addition, there is a problem that the contrast when black marking is performed by laser light irradiation cannot be secured, and the visibility and clearness of the marking portion cannot be secured. There is no properly.

  Thus, by setting the thickness of the entire three-layer sheet to a desired thickness, not only the local characteristics such as the characteristics of the multilayer sheet B can be easily drawn, but also the entire laser marking laminate for an electronic passport of the present embodiment. It becomes easy to draw out the characteristics. Furthermore, not only the total thickness of the entire three-layer sheet, but also the ratio of the thickness of the skin layer and the core layer constituting the three-layer sheet in the three-layer sheet is set to the above-described desired ratio, thereby providing three layers. This is preferable because the effect of the present invention can be further exhibited, for example, by making the thickness of the entire sheet within the desired range easier to improve the contrast.

  It should be noted that the adhesiveness and imperviousness of the multilayer sheet, and the contrast with the laser marking part (of the transparent laser marking sheet A) are extremely important, such as whether the multilayer sheet can be put into practical use, productivity, and market needs. Since it becomes an element, the relationship between the total thickness of the entire three-layer sheet and the thicknesses of the skin layer and the core layer will be described in detail later.

[B-1] Skin layer in multilayer sheet B:
The skin layer in the multilayer sheet B is configured as both outermost layers arranged on the outside of the three-layer sheet. That is, this skin layer plays a role as a surface layer (both outermost layers) of a three-layer sheet disposed so as to be sandwiched from both end surfaces (outside) of the core layer in the multilayer sheet B described later.

  The thicknesses of the skin layers are preferably the same. When the multilayer sheet B is composed of skin layers having different thicknesses, it becomes a factor of variation in the heat fusion property between the outermost transparent laser marking multilayer sheet A and the multilayer sheet B at the time of heat fusion in the multilayer sheet lamination process. Not only is this not preferred, but “swarf” may occur in the laminate after heating and pressing (laser marking laminate for electronic passport), which is not preferred. In addition, for example, when the multilayer sheet B is composed of three layers of skin layer (PETG) / core layer (PC) / skin layer (PETG), the thickness of the core layer is 30% or more and less than 85%. In this case, the skin layer is 15% or more and less than 70% on both sides. If the thickness of the skin layer is too thin, the heat-sealability will be lowered. On the other hand, if the thickness of the skin layer is too thick, the thickness of the core layer described later will inevitably become thin. End up. In this case, if the colorant is blended only in the core layer, it is only necessary to feed the resin containing the colorant into only one extruder, so cleaning is more extreme than when the colorant is blended in the skin layer and the core layer. In other words, half the labor is required, but the incompatibility when partially or fully printed on the multilayer sheet B is insufficient. In addition, when the coloring agent is blended in the skin layer and the core layer, the above-described problem of the incompatibility does not occur. For example, two extruders are used for three-layer sheet melt extrusion molding with two kinds of resins. The two extruders will be charged with a resin containing a colorant, and cleaning up the colorant will take a considerable amount of time to clean up after the production of a sheet formed by two-type three-layer melt extrusion molding. Productivity and cost issues are likely to arise. Therefore, it is preferable that the total thickness (total thickness) of the three-layer sheet (multilayer sheet B) and the ratio of the thickness of the core layer to the total thickness are formed within the desired range as described above. .

  As a material for forming this skin layer, a polyester resin composition, that is, a copolymer polyester resin described later, and a substantially non-crystalline aromatic polyester resin composition described later prepared with these materials. It is preferably formed as a layer made of a material.

[B-1-1] Copolyester resin:
The copolyester resin used in the present embodiment is preferably blended as a main component of the amorphous aromatic polyester resin composition. The polyester resin here means a dehydration condensation product of an aromatic dicarboxylic acid and a diol, and the substantially non-crystalline aromatic polyester resin used in the present invention is a crystalline resin among aromatic polyester resins. Low thing. These do not cause white turbidity due to crystallization or decrease in fusing property even if heat molding is frequently performed with a hot press or the like. As specific examples of the copolymer polyester resin, the skin layer has a dicarboxylic acid unit mainly composed of a terephthalic acid unit and an ethylene glycol unit (I) [hereinafter referred to as “ethylene glycol unit (I)”], and 1 , 4-cyclohexanedimethanol unit (II) is a polyester comprising a glycol unit, and ethylene glycol unit (I) and 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = copolymerized polyester resin of 90-30 / 10 to 70 mol% is used. The reason for preparing the component amounts of ethylene glycol and 1,4-cyclohexanedimethanol contained in this copolymerized polyester resin is that the amount of substitution of the ethylene glycol component in the copolymerized polyester resin is less than 10 mol%. This is because the obtained resin does not become sufficiently amorphous, and recrystallization proceeds in the cooling step after heat fusion, resulting in poor heat fusion. Moreover, it is because the resin obtained exceeding 70 mol% is not sufficiently amorphous, and recrystallization proceeds in the cooling step after heat fusion, resulting in poor heat fusion. Therefore, as in this embodiment, the resin obtained by adjusting the component amounts of ethylene glycol and 1,4-cyclohexanedimethanol becomes sufficiently amorphous, and is excellent in terms of heat fusibility. Therefore, it can be said to be a preferable resin.

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

[B-2] Core layer in multilayer sheet B:
The core layer is configured as a so-called core layer disposed in the center of the three-layer sheet. That is, this core layer is formed as a core layer of a three-layer sheet so as to be sandwiched between two skin layers disposed on the outermost side. The thickness of the core layer is preferably formed so that the ratio of the thickness in the entire sheet is 30% or more and less than 85%. More preferably, it is 40% or more and less than 80%. When the thickness ratio of the core layer is 85% or more, since the total thickness of the multilayer sheet B is as thin as 100 to 300 μm, the skin layer is relatively thin, and is the outermost layer at the time of heat-sealing in the multilayer sheet laminating process. This is not preferable because it causes variations in heat-fusability between the transparent laser marking sheet A (including both “single-layer sheet” and so-called “three-layer sheet”) and the multilayer sheet B. The thickness ratio of the core layer is 30%. If it is less than the above, it is impossible to secure the compatibility when printing on the multilayer sheet B, and furthermore, the laser beam irradiation is applied to the transparent laser marking sheet A (including both “single layer sheet” and so-called “three layer sheet”) which is the outermost layer. As a result, there is a problem in that the contrast when black marking is performed cannot be secured, and the visibility and clarity of the marking portion cannot be secured. Not properly.

  As a material (raw material) constituting the core layer, a polycarbonate resin, particularly a transparent polycarbonate resin is used. However, the polycarbonate resin to be used is not particularly limited, but those having a melt volume rate of 4 to 20 can be suitably used. If the melt volume rate is less than 4, it is meaningful in that the toughness of the sheet is improved, but the molding processability is inferior. On the other hand, a melt volume rate exceeding 20 is not preferable because the sheet has poor toughness.

[B-2-1] Coloring agents for resins such as dyes and pigments:
The multilayer sheet B is a colored multilayer sheet, and the skin layer and / or the core layer of the multilayer sheet B are dyes, pigments, etc. with respect to 100 parts by mass of the copolyester resin and / or 100 parts by mass of the polycarbonate resin. It is preferable to contain 1 part by mass or more of at least one of the resin colorants. This is different from the transparent laser marking sheet A. In this way, 1 part by mass or more of the colorant of the resin such as a coloring dye or a pigment is blended after laminating the laminate sheet of the transparent laser marking sheet A and the colored multilayer sheet B as described later. This is because the contrast is good when marking is performed by irradiating the film, and the incompatibility when printing on the colored multilayer sheet B is ensured.

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

  More preferably, a resin colorant such as a white dye or a pigment, which is conspicuous in contrast, is added.

[B-3] Lubricant, antioxidant and / or anti-coloring agent:
The core layer and / or skin layer of the multilayer sheet B including the single-layer sheet and multilayer sheet (so-called three-layer sheet) described above is an antioxidant and / or an anti-coloring agent with respect to 100 parts by mass of the thermoplastic resin. It is also one of the preferable forms to contain 0.1-5 mass parts and 0.1-5 mass parts of ultraviolet absorbers and / or light stabilizers. When an antioxidant and / or an anti-coloring agent is added (blended), it effectively acts on physical property reduction and hue stabilization due to molecular weight reduction during molding, and an ultraviolet absorber and / or light stabilizer is added ( In the case of blending), it is effective because it effectively acts to suppress light deterioration resistance during storage of the laser marking laminate for electronic passport and during actual use of the electronic passport as the final product. That is, by adopting such a configuration, in addition to being able to contain a desired amount of an antioxidant and / or an anti-coloring agent, and an ultraviolet absorber and / or a light stabilizer appropriately and appropriately, Since the area | region to contain can be selected, the effect of this invention can be show | played more synergistically as the whole sheet | seat.

  The lubricant, antioxidant and / or anti-coloring agent of the multilayer sheet B are the same as the lubricant, antioxidant and / or anti-coloring agent contained in the transparent laser marking sheet A. Therefore, see the description of the transparent laser marking sheet A (lubricant, antioxidant and / or anti-coloring agent).

[2-4] Relationship between transparent laser marking sheet A and multilayer sheet B:
As described above, by laminating the transparent laser marking sheet A and the multilayer sheet B, the effects of the present invention can be achieved. That is, when the transparent laser marking sheet A is configured as a PC (laser mark compatible) transparent single layer sheet or a PC / PC (laser mark compatible) / PC transparent laser mark three layer sheet (multilayer sheet 2). In addition, by laminating a colored multilayer sheet B made of PETG / PC (containing a white colorant) / PETG on the surface opposite to the laser-irradiated surface of the transparent laser marking sheet A, the upper layer This is because when the laser beam is irradiated on the (transparent laser marking sheet A) and the core layer PC develops a black color, the contrast is ensured and the visibility and sharpness of the marking portion are exhibited. Furthermore, since images, characters, etc. are generally printed on the colored multilayer sheet B, the clarity of the printed part and the protection of the printed part, that is, when printing is performed on the outermost layer, When some kind of friction or wear occurs, the printed part is worn down and the visibility is greatly reduced, but it is important because printing can be solved by printing on the surface of the multilayer sheet B, which is the lower layer of the transparent laser marking sheet A. is there.

  In addition, when the multilayer sheet A is configured as a transparent laser mark three-layer sheet made of PETG / PC (corresponding to a laser mark) / PETG, the surface of the multilayer sheet A opposite to the surface irradiated with the laser is Furthermore, by laminating a colored laser mark multilayer sheet B made of PETG / PC (corresponding to a colored laser mark) / PETG, even if the core layer PC is colored black by irradiating the upper layer (multilayer sheet A) with a laser, The laser light further passes, and the core layer PC in the lower layer (multilayer sheet B) also produces a black color. Thereby, the blackening degree of the portion colored by the laser light is further improved.

  As described above, it is important to control the reflectance and contrast in order to sufficiently bring out the sharpness of an image (for example, a human face) by laser marking. For example, if the reflectivity is insufficient or the contrast is low, the sharpness of the image is deteriorated. Also, for example, the above-mentioned multilayer sheet A (PETG / PC (corresponding to laser mark) / PETG transparent laser mark three-layer sheet) is heat-sealed with a three-layer sheet of PETG / PC (white) / PETG that is not compatible with laser marks. In the case of forming a laser marking laminate for an electronic passport, since there is a PETG transparent layer in the lower three-layer sheet, the reflectance becomes insufficient, which is not preferable. Further, in consideration of reflectivity and contrast, when the PC (white) sheet is used as a lower layer of the multilayer sheet A instead of the above-described PETG / PC (white) / PETG 3 layer sheet, the reflectivity is PETG / PC ( White) / PETG 3 layer sheet is improved, and the contrast between the black color formed by the laser marking of the upper layer (multilayer sheet A) and the white color of the lower layer (PC sheet) is improved. However, when the lower layer is a PC (white) sheet, a problem of heat-fusibility with the upper layer occurs, and the heat-fusibility at a low temperature of about 120 to 150 ° C. is poor. When the temperature is raised to 210 to 240 ° C., heat fusion is performed. However, in this case, the upper PETG layer is softened and melted, and a laser marking laminate for an electronic passport cannot be obtained.

  Accordingly, by making the lower layer compatible with laser marking, even if the upper layer is irradiated with laser and the core layer PC develops black color, the laser light further passes and the lower core layer PC also produces black color. As a result, the degree of blackening of the portion colored by the laser beam is further improved, so that the same contrast as when a PC (white) sheet is used for the lower layer can be obtained, and the image can be sharpened. I tried not to cause any problems in sex. Thus, the present invention synergistically exhibits the effects of the present invention by combining the desired multilayer sheet A and multilayer sheet B.

  In the above description, the arrangement pattern in which the multilayer sheet B is laminated on the lower layer of the transparent laser marking sheet A in the laser marking laminate for the electronic passport of the present embodiment has been described. However, the arrangement is not limited thereto. . That is, the transparent laser marking sheet A is not necessarily disposed in the upper layer, and the multilayer sheet B is disposed in the lower layer. For example, the transparent laser marking sheet A may be disposed in the lower layer, and the multilayer sheet B may be disposed in the upper layer. As described above, the transparent laser marking sheet A (or the multilayer sheet B) may be disposed in the upper layer or the lower layer because the position (direction) for viewing the laser-marked image or the like is not limited to the vertical direction. It is. In other words, for example, when the laser marking laminate for electronic passports in the present embodiment is used in the form of a booklet such as a passport, the transparent laser marking sheet A is formed on the upper layer when viewed in a plan view and in plan view. Even if the multi-layer sheet B is arranged in the lower layer, when the next page is opened and viewed in plan, the arrangement position of the transparent laser marking sheet A and the multi-layer sheet B is just the multi-layer sheet B in the upper layer. This is because the transparent laser marking sheet A is disposed in the lower layer. Therefore, the upper layer and the lower layer here are used for convenience of explanation, and mean that the transparent laser marking sheet A is arranged on the laser irradiation side. By arranging in this way, the clear laser marking sheet A and the multilayer sheet B after laser marking can obtain clearness and high contrast of images and the like, and the effects of the present invention can be achieved. .

  Furthermore, the laser marking laminate for electronic passports in the present embodiment is not limited to the case where the transparent laser marking sheet A / multilayer sheet B is laminated. For example, after performing various printing on the surface of the multilayer sheet B, it is laminated with the transparent laser marking sheet A / (printed) multilayer sheet B / laminated hinge sheet C / (printed) multilayer sheet B / transparent laser marking sheet A. When laminating with transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A, the laminated sheet of multilayer sheet B / laminated hinge sheet C / multilayer sheet B is heated. The case where the transparent laser marking sheet A / the laminated sheet / transparent laser marking sheet A is further laminated after being fused and printed on the surface of the laminated sheet is also widely included. It becomes possible to respond flexibly according to the purpose and method of use, and the effects of the present invention can be achieved.

[3] Method for forming transparent laser marking sheet A and multilayer sheet B:
In the present invention, in order to obtain the transparent laser marking sheet A and the colored multilayer sheet B, for example, a method of laminating the resin composition of each layer by melt extrusion molding, a method of forming each layer into a film, and laminating this, There is a method of laminating two layers by melt extrusion and laminating a film separately formed thereon, but it is more preferable to laminate by melt extrusion from the viewpoint of productivity and cost.

  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 ° C. to 300 ° C. A three-layer laminate can be formed by melting in the range of ° C., three-layer T-die melt extrusion molding, and cooling and solidifying with a cooling roll or the like. In addition, the transparent laser marking sheet A and the colored multilayer sheet B in the present invention are not limited to the above methods, and can be formed by a known method, for example, JP-A-10-71763 (6). To (7).

  After cutting the transparent laser marking sheet A, the multilayer sheet B, and the laminated hinge sheet C obtained as described above into predetermined dimensions, they are laminated, using a rotary vacuum press machine, etc., at a desired time and at a desired pressure. A laser marking laminate for electronic passports, which is laminated by heating fusion at a desired temperature and laminating five layers of transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A Can be obtained. Further, after forming the transparent laser marking sheet A and the multilayer sheet B by melt coextrusion molding, for example, the transparent laser marking sheet A / multilayer sheet B is heated by a heating roller, and is elongated by pressure lamination. A laminate sheet is produced. A method of manufacturing a laser marking laminate for an electronic passport in which five layers are laminated by heat fusion after being cut into a predetermined size and laminated on a laminate sheet / laminated hinge sheet C / laminate sheet. The laser marking laminate for electronic passports can also be manufactured.

  Here, the desired time, the desired pressure, and the desired temperature are not particularly limited. The desired time, desired pressure, and desired temperature are preferably selected as appropriate. In addition, as a general thing, desired time is about 10 second-about 6 minutes, desired pressure 1-20 MPa, desired temperature 130-170 degreeC, and 140-160 degreeC can be mentioned as an example as a more preferable desired temperature.

[4] Other laminates:
As described above, the laser marking laminate for electronic passports of the present invention is configured as a five-layer laminate comprising transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A. It is preferable. That is, by configuring as a laminate of transparent laser marking sheet A / multilayer sheet B, it is possible to improve the clarity of images and the like. Also, in the electronic passport, specific fixed information such as the country is printed on one side of the multilayer sheet B (on the transparent laser marking layer side), but in that case, printing on the white multilayer sheet B is an image. The sharpness such as is outstanding. For example, the former is preferable to printing on a multilayered sheet B of dark color such as brown or black because clear printing can be performed without being affected by the background color. Furthermore, after printing this fixed information on the multilayer sheet B, the fixed information printing has many white portions even when the variable information such as personal information or personal image is black-colored by laser marking on the transparent laser marking layer. By using light colors, the contrast with the background light colors is increased, and clear images and characters can be obtained. Therefore, the color of the colored multilayer sheet B (colored sheet B) is more preferably a pale color such as white.

  In addition, laser marking can be performed from either the front surface and / or the back surface by configuring the transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A. Can do. In addition, when these five-layer laminates are heat-sealed by hot press molding, it can be said that the obtained five-layer laminate hardly warps. The thickness of each layer is preferably 50 to 200 μm for the transparent laser marking sheet A, 100 to 300 μm for the multilayer sheet B, and 80 to 250 μm for the laminated hinge sheet C.

  Preferred is a five-layer laminate structure of transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A, where the laminated hinge sheet C and the thermoplastic resin sheet P It is a laminated hinge sheet with a plastic resin sheet R, and is characterized by a three-layer structure consisting of a thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P. By adopting such a three-layer structure, a laminated hinge sheet having flatness can be obtained, and it is excellent in transportability and flexibility of a sheet cut into a predetermined size, and further, heat fusion with the multilayer sheet B is achieved. It has excellent wearability and can suppress the occurrence of abnormal appearance such as wrinkles at the sticking part in the heat lamination process, and the breaking strength of the sewing part when using this sticking part together with the cover and other sheets. An excellent five-layer laminate can be produced.

  Here, the five-layer laminate as in this embodiment can be manufactured by various methods. For example, after laminating transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A, a five-layer laminate is obtained by heat-sealing (thermal lamination) with a hot press. Can be manufactured.

  In addition, when printing on the laminate as described above, after printing and curing with light or thermosetting ink on one side of the multilayer sheet B, the transparent laser marking sheet A / printing multilayer sheet B / laminate Hinge sheet C / printed multilayer sheet B / transparent laser marking sheet A are laminated and then heat-sealed (heat lamination) with a hot press, or multilayer sheet B / laminated hinge sheet C / multilayer sheet B is hot-pressed After laminating by thermal fusion at, and then printing on the surface of this laminate, transparent laser marking sheet A is transparent laser marking sheet A / (multilayer sheet B / laminate hinge sheet C / multilayer sheet B) laminate / transparent laser It can also be manufactured by laminating with the marking sheet A and hot pressing.

  Further, after printing / curing on one side of the multilayer sheet B with light or thermosetting ink, a thin varnish, which is one type of adhesive, is applied to the printed surface, and after drying, if necessary, the transparent laser marking sheet A It is possible to heat and fuse firmly by laminating / pressing burnishing coated multilayer sheet B / laminated hinge sheet C / burnishing coated multilayer sheet B / transparent laser marking sheet A.

  Further, a heat-active adhesive is applied to one side of the transparent laser marking sheet A (the surface to be heat-sealed with the printed surface of the multilayer sheet B) in a dry thickness of 3 to 20 μm, preferably 3 to 10 μm, more preferably 5 to 10 μm. As previously described, transparent laser marking sheet A (single-sided thermally activated adhesive layer) / multilayer sheet B / laminated hinge sheet C / multilayered sheet B / transparent laser marking sheet A (single-sided thermally activated adhesive layer) ), And then heat-sealing (heat lamination) with a heating press can be firmly heat-sealed.

  Further, when printing on such a laminate, it is more preferable to print and cure on one side of the multilayer sheet B with light or thermosetting ink, and then transparent laser marking sheet A / print multilayer sheet B / laminate. Hinge sheet C / printing multilayer sheet B / transparent laser marking sheet A are laminated and then heat-sealed (heat lamination) with a heating press, or printed on one side of multilayer sheet B with light or thermosetting ink. After curing, a thin layer of adhesive, varnish, is applied to the printed surface. After drying as necessary, transparent laser marking sheet A / burnish coating, printing multilayer sheet B / laminated hinge sheet C / burnish coating Laminate printing multilayer sheet B / transparent laser marking sheet A or as described above on one side of transparent laser marking sheet A After pre-coating the heat-active adhesive, pre-coating the heat-active adhesive Transparent laser marking sheet A / printing multilayer sheet B / laminated hinge sheet C / printing multilayer sheet B / pre-coating transparent The laser marking sheet A is laminated and heated and pressed to form a laser marking laminated body for an electronic passport. This is because not only the effects of the present invention are achieved, but also convenience such as easy molding is improved.

  However, such a thing is not limited, You may form the above-mentioned 5 layer laminated body in the range which does not deviate from the structure and effect of this invention.

  Moreover, although the heat press temperature in the case of heat sealing | fusion (thermal lamination) changes also with the kind of lamination | stacking hinge sheet | seats C, it is 130-170 degreeC, Preferably it is 140-160 degreeC. If the heating press temperature is less than 130 ° C., adhesion failure may occur. If it exceeds 170 ° C., abnormalities such as warpage of the five-layer laminate, sticking out of the sheet or sheet, or discoloration due to printing ink burning, etc. are not preferable.

[5] Matt processing:
Further, it is preferable that the surface of the transparent laser marking sheet A and / or the multilayer sheet B is subjected to mat processing 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 respective sheet surfaces as described above is, for example, that when the transparent laser marking sheet A and the multilayer sheet B are subjected to hot press molding, the mat processing is performed as described above. This is because the air between the transparent laser marking sheet A and the multilayer sheet B is easily removed. On the other hand, if these sheets are not mat processed when transported to the laminating step, they are sucked and sucked and transported, and after these sheets are aligned and stacked, air is injected to form a multilayer sheet. At the time of desorption, there is a tendency that problems such as difficulty in desorption or misalignment even if desorption can occur. Moreover, when the average roughness (Ra) of the mat processing exceeds 5 μm, the heat-fusability between the transparent laser marking sheet A and the multilayer sheet B tends to be lowered. Furthermore, it is preferable that the laser marking laminate for an electronic passport 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 / lamination tends to occur.

[6] Inlet sheet:
In addition, it is also preferable to arrange an IC chip (also referred to as “IC-Chip”) and an antenna (also referred to as “Antenna”) using an inlet sheet as necessary. For example, an IC-Chip and an antenna are usually placed on a sheet formed from a raw material such as PETG, and this is used as an inlet sheet, and this inlet sheet is placed on one side of the laminated hinge sheet. The laminated hinge sheet C may be configured as an inlet sheet combined laminated hinge sheet in which an IC-Chip and an antenna are directly arranged. This is because the IC chip and the antenna can be easily disposed, and can be used as a so-called IC chip built-in type laser marking laminate for electronic passports.

  In addition, by cutting a thermoplastic resin sheet of about 200 to 300 μm such as PETG and inserting IC-Chip and Antenna to create an inlet sheet, oversheet / inlay sheet / inlet sheet / laminated hinge sheet / inlay sheet / over You may use as a structure of a sheet | seat. Furthermore, the configuration of the oversheet / inlay sheet / laminated hinge sheet / inlet sheet / inlay sheet / oversheet may be e-Card compatible.

  In the case where the inlet sheet is configured as a separate body without being combined as the above-described inlet sheet combined laminated hinge sheet, for example, a substantially non-crystalline aromatic polyester resin, or the above A thermoplastic resin sheet comprising a resin composition, specifically, a dicarboxylic acid unit mainly comprising a terephthalic acid unit, an ethylene glycol unit (I), and a 1,4-cyclohexanedimethanol unit (II). It is a polyester composed of glycol units, and the ethylene glycol unit (I) and the 1,4-cyclohexanedimethanol unit (II) are (I) / (II) = 90 to 30/10 to 70 mol%. A sheet on which an IC chip and an antenna are arranged is arranged on a thermoplastic resin sheet made of a copolyester resin, and an inlet is provided. After forming the sheet and laminating the inlet sheet E on one side of the laminated hinge sheet so as to cover the IC chip and the antenna to form the inlet sheet, each of the transparent laser marking sheet A and the multilayer sheet B is formed. When laminated and heated and pressed, a laminate can be formed. Furthermore, after constituting like transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet / inlet sheet E / multilayer sheet B / transparent laser marking sheet A, a laminate by heating press may be formed. Note that it is preferable to adopt the configuration as described above because the IC chip and the antenna can be prevented from being damaged due to stress, heat, or the like at the time of hot pressing.

  However, the present invention is not limited to this example, and those that are appropriately changed and modified within the scope of the present invention are also included in the present invention.

  In addition, when laminating the inlet sheet, at one end of the laminated hinge sheet C (or the inlet sheet combined hinge sheet) is provided with an overhang portion that is 5 to 100 mm longer than the transparent laser marking sheet A and the multilayer sheet B, It is also a preferred embodiment that the inlet sheet is assembled and / or bonded to the electronic passport by using (via) the overhang portion.

  As the material of the inlet sheet, the substantially non-crystalline aromatic polyester-based resin described above or a thermoplastic resin sheet made of the resin composition, specifically, “dicarboxylic acid mainly composed of terephthalic acid unit”. A polyester comprising a glycol unit mainly comprising a unit, an ethylene glycol unit (I), and a 1,4-cyclohexanedimethanol unit (II), and the ethylene glycol unit (I) and 1,4-cyclohexanedi It is also preferable to use, for example, an adhesive sheet instead of the “copolyester resin in which the methanol unit (II) is (I) / (II) = 90-30 / 10-70 mol%”. This is because not only the subsequent heat pressing process for forming the inlet sheet can be omitted, but also damage to the IC chip and the antenna can be reduced due to stress, heat, etc. 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, Aron Melt PES-111EE sheet manufactured by Toa Gosei Co., Ltd.). It is not limited. In addition, also when using the above-mentioned copolymerization polyester resin or an adhesive sheet, although the thickness of an inlet is generally 200-300 micrometers, it is preferable that it exists in the above-mentioned desired range as a whole.

  In addition, it is a laser marking laminated body for electronic passports described above, and after printing on the surface of the multilayer sheet B, the transparent laser marking sheet A / multilayer sheet B / laminate hinge sheet C / multilayer sheet B / transparent laser marking sheet It is preferably formed as a 5-layer laminate of A 1 or a 6-layer laminate of transparent laser marking sheet A / multilayer sheet B / inlet sheet E / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A. By forming a laser marking laminate for an electronic passport in this way, the laser marking properties are excellent, and the contrast between the fabric color and the printed portion is high, and clear characters, symbols, and images can be obtained. There is an effect.

  For example, in an e-card (e-Card) in which an IC-Chip and an antenna are arranged, when the inlet sheet E in which the IC-Chip and the antenna are arranged is used, the transparent configuration which is the basic configuration in the above-described data page. Laser marking sheet A / Multilayer sheet B / Hinge sheet C / Multilayer sheet B / Transparent laser marking sheet A 5-layer laminate (5 layers laser marking laminate for electronic passports) placed on one side of the hinge sheet become. More specifically, a 6-layer laminate of transparent laser marking sheet A / multilayer sheet B / inlet sheet E / hinge sheet C / multilayer sheet B / transparent laser marking sheet A (laser marking laminate for electronic passport comprising 6 layers) ). Further, in the case of using hinge sheet C (hereinafter referred to as hinge sheet C (2) as appropriate) in which an IC-Chip and an antenna are arranged on the hinge sheet and both the inlet sheet and the hinge sheet are used, transparent laser marking sheet A / multilayer A five-layer laminate of sheet B / inlet sheet E / hinge sheet C (2) / multilayer sheet B / transparent laser marking sheet A may be used.

[7] Electronic passport:
Further, the electronic passport is formed by using the above-described laser marking laminate for electronic passport, and the overhang portion of the laminated hinge sheet C is bound and / or bonded to the front cover or back cover of the electronic passport. It is preferable to mold as an electronic passport. Such a configuration is preferable because the electronic passport can be easily formed. For example, the above-mentioned laser marking laminate for electronic passport is used, and a transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A A / multilayer sheet B / inlet sheet / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A When configured as a 6-layer laminate, an electronic passport cover or It can be formed into an electronic passport by sewing and / or adhering to the back cover.

  Specifically, a passport as shown in FIG. 4 can be exemplified. As this passport, a laser marking laminate for electronic passports as shown in FIGS. 2A to 2C is prepared, and as shown in FIG. 3, a sewing machine binding portion 27 and the like are formed as necessary, and further FIG. The cover 49, the laminate 51 using the present embodiment, the visa sheet 53, the IC chip 55, and the like are arranged as shown in FIG. However, this is only an example, and the present invention is not necessarily limited to such a configuration and a creation method.

[8] Anti-counterfeit forming part:
Furthermore, it is preferable that a forgery prevention forming portion is formed. This is because by providing (providing) the forgery prevention forming portion, it is possible to reliably prevent forgery and the like in combination with the above-described features. Here, the forgery prevention forming unit includes, for example, holograms, micro characters, microwave characters, embossed characters, oblique printing (diagonal characters, etc.), lenticular, black light printing, as well as characters and images (person images) by laser irradiation. Examples include pearl printing or the like applied to at least one of the transparent laser marking sheet A, the multilayer sheet B, the laminated hinge sheet C, and the inlet sheet.

[9] Laser marking method:
The laser marking laminate for an electronic passport in this embodiment is one that develops color by irradiating a laser beam. As the laser beam, a gas laser such as a He—Ne laser, an Ar laser, a CO ₂ laser, and an excimer laser, 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 addition, as described above, the above resin composition may include other additives such as a mold release agent, a stabilizer, an antioxidant, an ultraviolet absorber, and a reinforcing agent as long as the characteristics thereof are not impaired. Etc. can be added.

  In the laser marking method of the present embodiment, the laser beam may be a single mode or a multimode as the laser beam, and the beam diameter is as wide as 80 to 100 μm in addition to a beam diameter of 20 to 40 μm. Although a single mode and a beam diameter of 20 to 40 [mu] m are preferable, the contrast between the print coloring portion and the background is set to 3 or more, and the print quality with good contrast is obtained.

  In this way, when the laser marking laminate for an electronic passport of this embodiment is irradiated with a laser beam, in the case of a single layer sheet or a multilayer sheet 2, the transparent laser marking sheet A constituting the laser marking multilayer sheet is colored, Since this transparent laser marking sheet A is mainly composed of a polycarbonate resin having high heat resistance, it is possible to irradiate a high-power laser beam, whereby an image or the like can be drawn easily and more clearly. In particular, in the case of the multilayer sheet 2 in which the transparent laser marking sheet A is composed of three layers of PC / PC (laser coloring layer) / PC, the PC laser coloring layer is provided by providing a PC transparent skin layer on the PC laser coloring layer. In the case of a single layer, even under conditions in which “blowing” occurs on the surface of the sheet due to “foaming” by irradiation with a higher-power laser beam, the “swelling” phenomenon is suppressed by the PC transparent skin layer effect, so it becomes clearer. Images can be drawn. This PC transparent skin layer effect is not limited to this. In the case of a single layer of the PC laser coloring layer, the marking portion of the sheet is directly scraped by friction with the outside, whereas a PC transparent skin layer is added. Even if the PC transparent skin layer is shaved, the laser marking part is not shaved, so it can be said that the abrasion resistance of the laser marking part is more excellent.

  Furthermore, since a sheet made of polycarbonate resin has high heat resistance, it is necessary to increase the heat-sealing temperature to 200 to 230 ° C. in the multilayer laminate of the resin sheet, which causes a problem in the productivity of the hot press process. However, in the electronic passport plastic data sheet, it is common to perform various printings on an intermediate layer called an inlay layer. When the heating and fusing temperature is set to a high temperature of 200 to 230 ° C., printing is often “yake”, and printed characters and images may cause discoloration, which is not preferable.

  To solve this problem, the PETG / PC (colored) / PCG of the present invention is applied to an inlay which is an underlay of a PC laser color developing layer transparent single layer sheet or PC / PC (laser color developing layer) / PC transparent three layer sheet. Since the glass transition temperature of PETG is about 80 ° C. and about 60 to 70 ° C. lower than that of polycarbonate resin by laminating the PETG colored three-layer sheet, the heat fusion temperature is 130 to 170 ° C., preferably 140 to 160 ° C. The temperature can be lowered by about 60 to 70 ° C. For this reason, it is possible to suppress the discoloration of characters and images printed on the print layer. Therefore, the laser marking laminate for an electronic passport of the present embodiment is excellent in laser markability, and the surface layer, or the core layer of the surface layer, is colored black by laser light irradiation to mark images and characters, but the underlayer Because of the white color, it is possible to draw clear characters and images with black / white contrast.

  Moreover, by using a PETG / PC (laser coloring layer) / PETG three-layer coextruded sheet (multilayer sheet 1) for the transparent laser marking oversheet (overlay), the core layer PC (laser coloring layer) by the PETG skin layer is used. In addition to excellent marking scratch resistance and abrasion resistance, heat fusion with a printed inlay layer using a PETG skin layer, especially heat fusion at a relatively low heating temperature of 150 to 170 ° C. There is an effect that it is excellent. As described above, by using the transparent laser marking single layer and the multilayer sheet of the present embodiment, it is excellent in laser mark property and can be deeply marked on the transparent laser marking layer itself, and the print density and the scratch resistance and abrasion resistance of the marking portion. Marking that is superior to the above becomes possible.

  More preferable is a method of laser marking on the laser marking laminate for electronic passport described above, which is laminated on the laser marking laminate for electronic passport as shown in FIGS. 2A and 2C (laser marking lamination for electronic passport). Laminated from the transparent laser marking sheet A side (from the A side of the single-layer sheet or multilayer sheet 2) or on the electronic passport laser marking laminate as shown in FIG. 2B From the multilayer sheet A side (from the A side of the multilayer sheet 1) constituting the marking laminate, printing is performed by irradiating a laser beam. Thus, by irradiating the desired laser beam 7 from the transparent laser marking (multilayer) sheet side of the present embodiment, an image or the like can be drawn easily and clearly. Therefore, it can be excellent in laser marking property and heat fusion property, and also in the abrasion resistance of the marking portion. Moreover, by using the multilayer sheet 1, it is excellent in laser mark property in combination with the multilayer sheet B, and / or the laminated hinge sheet C, and / or the inlet sheet E, and its surface, or support and covering. White characters, white symbols, white symbols, etc. can be drawn more easily and clearly on the black base with a laser beam at the interface portion of the screen, and in particular, information codes such as barcodes can be marked with high resolution.

[10] Application:
Moreover, the laser marking laminated body for electronic passports in this embodiment can be used suitably for an electronic passport.

  For example, when used as an electronic passport, two transparent laser marking sheets A and two multilayer sheets B are prepared. Further, a laminated hinge sheet C is prepared. When the laminated hinge sheet C is arranged in the order of the transparent laser marking sheet A, the multilayer sheet B, the transparent laser marking sheet A, and the multilayer sheet B, the transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C is arranged. / Multilayer sheet B / transparent laser marking sheet A are arranged in this order. Thus, by laminating and integrating, a laser marking laminate for an electronic passport is obtained. Thus, by using the laminated hinge sheet C, it is possible to easily bind the laser marking laminated body for electronic passports. In addition to forming a sewing binding portion or the like as necessary, a cover 49, a laminate 51 using the present embodiment, a visa sheet 53, an IC chip 55, etc. are arranged as shown in FIG. You may create a passport. However, this is an example, and the present invention is not necessarily limited to such a configuration.

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

[1] Laminated hinge sheet:
About the following Examples 1-3 and Comparative Examples 1-4, [1-1] Cut sheet workability, [1-2] Sheet flexibility, [1-3] Sewing machine strength, [1-4] Heating The following experiments were conducted on the fusibility and [1-5] heat resistance.

[1-1] Cut sheet workability:
The cut sheet workability was evaluated by evaluating the cutability at the time of cutting with a punching blade of 110 × 300 mm and the workability at the time of carrying into the subsequent heating and laminating process according to the following criteria.
<Criteria>
○: Good cutability and workability.
Δ: Good cutting performance, but there is a problem in workability.
X: There is a problem in cutting properties. There is no problem with workability.
XX: There is a problem in cutability and workability.

[1-2] Sheet flexibility:
A cut sheet having a width of 1 cm and a length of 10 cm was prepared. After the cut sheet was pasted to a length of 5 cm from the table as shown in FIG. 5A, the extent to which the sticking portion of the cut sheet as a test piece hangs was measured. The flexibility of the sheet was evaluated based on the following criteria. More specifically, as shown in FIG. 5A, the cut sheet 61 is placed on the horizontal base 63, the upper portion of the cut sheet 61 is pressed by the support plate 65, and the cut sheet 61 is cut as shown in FIG. 5B. The degree to which the sticking part 61a of the sheet 61 hangs was measured.
<Criteria>
A: The “sag” of the sheet is 2 cm or more, which is excellent.
○: “Sagging” of the sheet is less than 1 to 2 cm, which is favorable.
(Triangle | delta): The "dripping" of a sheet | seat becomes less than 0.4-1cm, and it is easy to produce a malfunction.
×: “Sag” of the sheet is less than 0.4 cm, which is bad.

[1-3] Sewing machine strength:
As shown in FIG. 6, after preparing a 2 × 10 cm hinge sheet test piece, laying paper underneath it, making a machine hole 67 at a pitch = 5 mm with an industrial sewing machine, and then removing the paper A tensile test was performed by pulling in the directions of arrows X and Y shown in the figure at a test speed = 300 mm / min, and the strength of the sewing machine (N / cm) was measured and evaluated according to the following criteria.
<Criteria>
A: The strength of the sewing machine portion is 40 (N / cm) or more, or breakage occurs at other parts than the sewing machine portion, and the strength is extremely excellent with the strength of 40 (N / cm) or more.
○: Sewing machine strength = 20 (N / cm) or more and less than 40 (N / cm).
(Triangle | delta): Sewing machine part intensity | strength = 10 (N / cm) or more and less than 20 (N / cm), and it is easy to produce a malfunction.
X: Machine part strength = less than 10 (N / cm), which is bad.

[1-4] Heat-fusibility:
The transparent laser marking sheet A and the multilayer sheet B were cut to 100 × 300 mm, and the hinge sheet was cut to 110 × 300 mm. Next, after applying a release agent to one end of the transparent laser marking sheet A and the multilayer sheet B, five sheets of transparent laser marking sheet A / multilayer sheet B / hinge sheet / multilayer sheet B / transparent laser marking sheet A Was sandwiched between two chrome-plated steel plates, and preheated at 100 ° C. for 90 seconds using a rotary vacuum press (manufactured by Nissei Plastic Industrial Co., Ltd.) and then pressurized at 160 ° C. for 90 seconds at an actual pressure of 20 kgf / cm ² . . Further, after cooling for 90 seconds, the laminate sheet was taken out, a test piece having a width of 20 mm including the part to which the release agent was applied was cut out, and a peel test was performed at a test speed of 300 mm / min. The heat fusibility was evaluated according to the following criteria. In addition, transparent laser marking sheet A used later (Production Example 1) transparent laser marking sheet A [1], and multilayer sheet B used later (Production Example 11) multilayer sheet B [1].
<Criteria>
A: Peeling strength is 50 N / cm or more or material destruction of the sheet is observed, which is very good.
○: The peel strength is 20 N / cm or more and less than 50 N / cm, which is favorable.
Δ: Peeling strength is 10 N / cm or more and less than 20 N / cm, and problems are likely to occur.
X: Poor strength is less than 10 N / cm.
XX: It is not heated and fused (because it can be easily peeled by hand) and cannot be manufactured.

[1-5] Heat resistance:
In the laminate after the heat fusion test, the appearance of the portion where the hinge sheet extends 10 mm at one end of the laminate from the transparent laser marking sheet A and the multilayer sheet B is visually evaluated, and the heat fusion lamination step. The heat resistance of the hinge sheet was evaluated.
<Criteria>
(Double-circle): Wrinkle generation | occurrence | production is not seen but it is favorable.
○: Slight wrinkles are observed, but there is no problem.
Δ: Wrinkles are observed.
X: Wrinkle generation is large or partly softened and dripping is bad.
XX: Very bad because it is softened and drooped.

(Example 1) Laminated hinge sheet C [1]:
As the thermoplastic resin sheet P, a thermoplastic polyurethane elastomer (TPU), a non-yellowing type “Milactolan XN-2004” manufactured by Nippon Milactolan Co., Ltd., and a hardness (Shore-A) 95, polyester as the thermoplastic resin sheet R is used. A film (hereinafter also referred to as “PET film” as appropriate) having a tensile elastic modulus of 4 GPa and a glass transition temperature (film) of 110 ° C., “Lumirror U12” manufactured by Toray Industries, Inc., having a thickness of 50 μm was used. Furthermore, TPU was melt-extruded from a T-die extruder at 185 ° C. and roll-pressed with a PET film at the T-die outlet to produce a laminated film made of TPU / PET film. Thereafter, further, TPU was melt-extruded from the T-die extruder at 185 ° C. on the PET film side of this laminated film and roll-pressed at the T-die outlet, and the laminated hinge made of TPU / PET film / TPU having a total thickness of 110 μm. A sheet was formed.

(Example 2) Laminated hinge sheet C [2]:
As the thermoplastic resin sheet P, a hydrogenated styrene-based elastomer (SEPS), “Kuraray Co., Ltd.” “Septon 2104” hardness (Shore-A) 98 is used instead of the TPU of Example 1, and the thermoplastic resin sheet R is used. Using the same PET film as in Example 1, it was melt-extruded from a T-die extruder at 230 ° C. and roll-pressed with the PET film at the T-die outlet to produce a laminated film made of PETG / PET film. Thereafter, PETG is melt-extruded from a T-die extruder at 270 ° C. on the PET film side of this laminated film and roll-pressed at the T-die outlet, and a laminated hinge made of SEPS / PET film / SEPS having a total thickness of 110 μm. A sheet was formed.

(Example 3) Laminated hinge sheet C [3]:
As the thermoplastic resin sheet R, instead of the PET film of Example 1, a PEN film having a tensile modulus of 6 GPa and a glass transition temperature (film) of 155 ° C. “Teonex Q51DW” with a thickness of 38 μm manufactured by Teijin Limited The TPU of Example 1 was used as the thermoplastic resin sheet P. Further, in the same manner as in Example 1, a laminated hinge sheet made of TPU / PEN film / TPU having a total thickness of 110 μm was formed.

(Comparative Example 1) Hinge sheet C [4]:
As a thermoplastic polyurethane elastomer (TPU), a non-yellowing type “Milactolan XN-2004” manufactured by Nippon Milactolan Co., Ltd. and hardness (Shore-A) 95 are used, and the thickness is 150 μm with a T-die extruder at 185 ° C. The hinge sheet of the TPU single sheet (TPU film) was obtained.

(Comparative Example 2) Hinge sheet C [5]:
As a polyester film (PET film), a hinge sheet obtained by molding “Lumirror U12” manufactured by Toray Industries, Inc. having a tensile elastic modulus of 4 GPa and a glass transition temperature (film) of 110 ° C. to a thickness of 125 μm was used.

(Comparative Example 3) Hinge sheet C [6]:
Hardness (Shore-D) 80, copolyester resin (PETG), “Easter Copolyester 6863” manufactured by Eastman Chemical Co., Ltd., and the polyester film (PET film) of Example 1 were used. Further, in the same manner as in Example 1, a hinge sheet made of PETG / PET film / PETG having a total thickness of 110 μm was molded by a T-die extruder at 270 ° C.

(Comparative Example 4) Hinge sheet C [7]:
A hydrogenated styrene-based elastomer (SEPS) manufactured by Kuraray Co., Ltd., “Septon 4033” hardness (Shore-A) 76 was used, and the same PET film as in Example 1 was used. Further, in the same manner as in Example 2, a hinge sheet made of SEPS / PET film / SEPS having a total thickness of 110 μm was molded with a T-die extruder at 230 ° C.

(Discussion 1)
As shown in Tables 1 and 2, Examples 1 to 3 are excellent in tearing and tensile strength, have light resistance and heat resistance of the binding portion, and further excellent in resistance to repeated bending. Met.

  On the other hand, since the hinge sheet of Comparative Example 1 was a TPU single sheet, the strength of the sewing machine part was weak, and problems were likely to occur, and wrinkles were greatly generated in the heat resistance test, and partly softened. Dripping was observed. Further, it was confirmed that the workability of the cutting property was extremely poor and the productivity was low. In Comparative Example 2, it was confirmed that the flexibility of the hinge sheet was poor and the strength of the sewing machine part was also poor. In Comparative Example 3, it was confirmed that the hinge sheet was not flexible enough. When such a hinge sheet is used, it is possible to cause problems in normal use, such as folding the page normally associated with a passport, and it has been confirmed that this is not feasible. It was. Furthermore, in Comparative Example 4, it was confirmed that the cut workability was poor and the productivity was low. A problem was also confirmed in terms of heat resistance. As described above, in any comparative example, there is a problem in putting it to practical use, and from this point, it was proved that any of the examples has an excellent effect.

[2] Laser marking laminate for electronic passport and electronic passport:
Next, the following experiment was conducted on Examples 4 to 10 and Comparative Examples 5 to 13 using the above-described laminated hinge sheet, transparent laser marking sheet A and multilayer sheet B described later.

[2-1] Transparency of the transparent laser marking sheet A:
The total light transmittance of the transparent laser marking sheet A was measured using a spectrophotometer (trade name “EY7000” manufactured by Macbeth Co.).
<Criteria>
○: Good with a total light transmittance of 80% or more. Δ: Total light transmittance of 60% or more and less than 80%, x: Total light transmittance of less than 60%, which is bad.

[2-2] Sheet transportability:
After the transparent laser marking sheet was cut to 100 × 300 mm, it was conveyed by a sheet conveying machine, and when the sheet was placed on a predetermined position on a heating press machine die, the sheet conveyance property was evaluated according to the following criteria.
<Criteria>
○: No problem.
Δ: At the time of adsorbing the sheet → conveying → desorbing, the sheet is difficult to desorb from the adsorbing portion and the sheet is displaced.
X: The sheet is difficult to remove from the adsorbing part and is bad.

[2-3] Release property after lamination heating press molding:
Using a vacuum press machine (manufactured by Nissei Plastic Industries), the laminated sheets are sandwiched between two chrome-plated steel plates, preheated at a press temperature of 100 ° C. for 2 minutes, and then 170 ° C. and an actual pressure of 12 kgf / cm ^{2 for} 2 minutes. Retained. Then, after cooling to room temperature, the sample pinched | interposed with the chromium plating steel plate was taken out with the chromium plating steel plate, and the mold release property at the time of peeling a chromium plating steel plate from a sample was evaluated as follows.
<Criteria>
○: Can be easily peeled, Δ: Slightly adheres to the mold and can be peeled off, but cannot be used due to scratches on the sheet surface, ×: Adheres to the mold.

[2-4] Air bubble releasing property:
As described above, the state of remaining bubbles in the laminated body after the hot pressing was observed, and the bubble releasing property was evaluated as follows.
<Criteria>
○: No bubbles in the laminate, Δ: slight bubbles remaining in the laminate, ×: a large amount of bubbles remaining in the laminate.

[2-5] Heat-fusibility:
After applying a release agent to one end of the transparent laser marking sheet A and the multilayer sheet B, two sheets of transparent laser marking sheet A / multilayer sheet B / hinge sheet C / multilayer sheet B / transparent laser marking sheet A The sheet was sandwiched between two chrome-plated steel sheets, preheated at a press temperature of 100 ° C. for 2 minutes using a vacuum press machine (manufactured by Nissei Plastic Industry), and then held at 160 ° C. and an actual pressure of 12 kgf / cm ^{2 for} 2 minutes. Then, after cooling to room temperature, the laminate sheet was taken out and manually peeled off from the part where the release agent was applied, and the heat-fusibility between the laminates was evaluated as follows.
<Criteria>
A: There is no peeling, and the heat fusion property is excellent. B: A very small part can be peeled, but the sheet breaks. (Material destruction), △: Can be peeled with a fairly strong force. X: The entire surface was peeled, xx: The surface of the entire surface was peeled off by heat generation or with a very small force.

[2-6] Laser marking property:
Using the heated laminate sheet, laser marking properties are evaluated using an Nd / YVO ₄ laser (trade name “LT-100SA”, manufactured by Laser Technology Co., Ltd., and trade name “RSM103D”, manufactured by Roffin Sinar Co., Ltd.). did. Specifically, laser marking was performed at a laser irradiation speed of 400 mm / sec, and was determined as follows from the sharpness of the image and the surface state of the marking portion.
<Criteria>
A: Excellent in sharpness, no abnormalities such as blistering in the laser light irradiation part,
○: Sharpness is good, there is no abnormality such as blistering in the laser light irradiation part,
Δ: Insufficient sharpness or slight bulge in the laser light irradiation part,
X: Poor clarity or large swelling of laser light irradiation part.

[2-7] Contrast property:
After printing on the multilayer sheet B, the process steps [2-5] and [2-6] were performed, and the contrast between the image by laser marking and the image by printing was determined by visual evaluation.
<Criteria>
○: There is no change in the sharpness and visibility of the image by laser marking and the image by printing,
Δ: The sharpness and visibility of the image by laser marking and the image by printing are lowered.
X: The sharpness and visibility of the image by laser marking and the image by printing deteriorate.

[2-8] Abrasion resistance of laser marking laminate for electronic passport:
The wear resistance of the heat-sealed laminate [2-6], which was irradiated with laser light to form a black laser marking portion, was tested. Specifically, using a rubbing tester (manufactured by Imoto Seisakusho), it was performed 50 times (25 reciprocations) with # 00 steel wool (load: 500 gr), and the state before and after the test was determined by visual evaluation.
<Criteria>
◎: Marking part is not abnormal, there is no change in image clarity and visibility,
○: Marking part is scraped, but image clarity and visibility are good.
Δ: Sharpening of the marking part is progressing, and the sharpness and visibility of the image are reduced.
X: The marking portion is greatly scraped, and the sharpness and visibility of the image are remarkably lowered.

(Production Example 1) Transparent laser marking sheet A [1]:
As the skin layer, polycarbonate (trade name "TARFLON FN2500A" produced by Idemitsu Kosan Co., melt volume rate ⁼ 8cm 3 / 10min) using, as a core layer, the above polycarbonate, carbon black (manufactured by Mitsubishi Chemical Corporation as an energy absorber for absorbing a laser beam # 10, 0.0015 parts by mass of average particle diameter 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 of 4-hydroxyphenyl) propionate (trade name “Irganox 1076”, manufactured by Ciba Specialty Chemicals) and 2- (2′-hydroxy-3 ′, 5 ′) as an ultraviolet absorber -Di-t-butylphenyl) -5-chlorobenzotriazole (product) "Tinuvin 327", manufactured by Ciba Specialty Chemicals), and blending 0.2 parts to obtain a transparent laser marking sheet A three-layer skin layer / core layer / skin layer by T-die melt extrusion. The total thickness of the sheet is 100 μm, the thicknesses of the skin layers on the front and back sides are the same, and the layer structure is a skin layer (18 μm) / core layer (64 μm) / skin layer (18 μm), The thickness ratio of the core layer was 64%. Furthermore, about the average surface roughness (Ra) of both surfaces, the 3 layer transparent laser marking sheet A [1] by which the mat | matte process was given so that it might be set to 0.5-1.8 micrometers was obtained.

(Production Example 2) Transparent laser marking sheet A [2]:
The total thickness of the sheet is 100 μm, the thicknesses of the skin layers on the front and back sides are the same, and the layer structure is configured as skin layer (28 μm) / core layer (44 μm) / skin layer (28 μm). A transparent laser marking sheet A [2] was obtained in the same manner as in Production Example 1 except that the layer thickness ratio was 44%.

(Production Example 3) Transparent laser marking sheet A [3]:
The total thickness of the sheet is 100 μm, the thicknesses of the skin layers on the front and back sides are the same, and the layer structure is a skin layer (45 μm) / core layer (10 μm) / skin layer (45 μm). A transparent laser marking sheet A [3] was obtained in the same manner as in Production Example 1 except that the layer thickness ratio was 10%.

(Production Example 4) Transparent laser marking sheet A (single layer sheet A) [4]:
Polycarbonate (trade name "TARFLON FN2500A" produced by Idemitsu Kosan Co., melt volume rate ⁼ 8cm 3 / 10min) with carbon black (manufactured by Mitsubishi Chemical Corporation # 10 as an energy absorber for absorbing a laser beam, the average particle diameter of 75 nm, DBP oil absorption 86ml / 100gr) in an amount of 0.0015 parts by mass, and (n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ("Irganox 1076") as a phenolic antioxidant. 0.1 parts of Ciba Specialty Chemicals Co., Ltd., and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole (as UV absorber) (Product name "Tinubin 327", manufactured by Ciba Specialty Chemicals) 0 2 parts, a transparent laser marking single-layer sheet F having a total sheet thickness of 100 μm was obtained by T-die melt extrusion, and the average surface roughness (Ra) on both sides was 0.5 to 1.8 μm. A transparent laser marking single layer sheet A [4], which was matted so as to be, was obtained.

(Production Example 5) Transparent laser marking sheet A [5]:
As a skin layer, 100 parts by mass of amorphous polyester (trade name “Easter GN071” manufactured by Eastman Chemical Co., Ltd., EG / CHDM = 70/30 mol%) was mixed with 0.3 parts by mass of calcium stearate as a lubricant. Polycarbonate as the core layer (trade name "TARFLON FN2500A" produced by Idemitsu Kosan Co., melt volume rate ⁼ 8cm 3 / 10min) with carbon black (manufactured by Mitsubishi Chemical Corporation # 10 as an energy absorber for absorbing a laser beam, the average particle diameter of 75 nm, DBP In addition to blending 0.0015 parts by mass of an oil absorption of 86 ml / 100 gr), (n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“ Irganox 1076 "manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 parts, and 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro as an ultraviolet absorber Benzotriazole (trade name “Tinubin 327”, Ciba Specialty Chemica 0.2 parts of a transparent laser marking sheet A [6] of skin layer / core layer / skin layer was obtained by T-die melt extrusion molding. The thickness of the core layer is the same as the thickness of the skin layers on the front and back sides, and the layer configuration is the skin layer (18 μm) / core layer (64 μm) / skin layer (18 μm). Further, the three-layer transparent laser marking sheet A [5], which has been matted so as to have an average surface roughness (Ra) of both sides of 0.5 to 1.8 μm, is 64%. Obtained.

(Production Example 6) Transparent laser marking sheet A [6]:
In the same manner as in Production Example 5, the total thickness of the sheet is set to 100 μm, the thicknesses of the skin layers on the front and back sides are the same, and the layer structure is skin layer (40 μm) / core layer (20 μm) / skin layer (40 μm) and the thickness of the core layer was 20%. Furthermore, about the average surface roughness (Ra) of both surfaces, the 3 layer transparent laser marking sheet A [6] by which the mat | matte process was performed so that it might become 0.5-1.8 micrometers was obtained.

(Production Example 7) Transparent laser marking sheet A [7]:
The same as in Production Example 5, except that the construction of the layer was Skin layer (5 μm) / Core layer (90 μm) / Skin layer (5 μm) and the thickness of the core layer was 90% in Production Example 5. The transparent laser marking sheet A [7] was manufactured as described above. However, since the skin layer was too thin, it was difficult to control the thickness of the skin layer. In particular, it was difficult to control the skin layers on both sides in the same manner. It was.

(Production Example 8) Transparent laser marking sheet A [8]:
In Production Example 5, a transparent laser marking sheet A [8] was obtained in the same manner as in Production Example 5 except that the lubricant was not added to the amorphous polyester.

(Production Example 9) Transparent laser marking sheet A [9]:
In Production Example 5, a transparent laser marking sheet A [9] was obtained in the same manner as in Production Example 5 except that the core layer of the three-layer sheet was not blended with the laser light energy absorber carbon black.

(Production Example 10) Transparent laser marking sheet A [10]:
In Production Example 5, a transparent laser marking sheet A [10] was obtained in the same manner as in Production Example 5, except that 5 parts by mass of the laser light energy absorber carbon black was blended in the core layer of the three-layer sheet.

(Production Example 11) Multilayer sheet B [1]:
Non-crystalline polyester (trade name “Easter GN071” manufactured by Eastman Chemical Co., Ltd., EG / CHDM = 70/30 mol%) as the skin layer, and polycarbonate (trade name “Toughlon FN2500A”, manufactured by Idemitsu Kosan Co., Ltd., melt volume rate, as the core layer. = ^8cm 3 / 10min) with, and was blended with 0.3 part by weight of calcium stearate as a lubricant to the amorphous polyester. Further, (n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (“Irganox 1076”) manufactured by Ciba Specialty Chemicals Co., Ltd. is used as a phenolic antioxidant in the polycarbonate. ) As an ultraviolet absorber and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole (trade name “Tinuvin 327”, Ciba (Specialty Chemicals Co., Ltd.) 0.2 parts and 5 parts of titanium oxide were blended, and a multilayer sheet B of three layers of skin layer / core layer / skin layer was obtained by T-die melt extrusion molding. The thickness is 200 μm, the thickness of the skin layers on the front and back is the same, and the layer structure is skin layer (25 μm) / core layer (150 μm) / skin layer ( In addition, the core layer has a thickness of 75%, and the average surface roughness (Ra) on both sides is 0.5 to 1.8 μm. A multilayer sheet B was obtained.

(Production Example 12) Multilayer sheet B [2]:
In the multilayer sheet B, the total thickness of the sheet is 200 μm, the layer structure is a skin layer (55 μm) / core layer (55 μm) / skin layer (12 μm), and the core layer thickness is 45%. Otherwise in the same manner as in Production Example 11, a multilayer sheet B [2] was obtained.

(Production Example 13) Multilayer sheet B [3]:
In the multilayer sheet B, the total thickness of the sheet is 200 μm, the layer structure is a skin layer (12 μm) / core layer (176 μm) / skin layer (12 μm), and the core layer thickness is 88%. Otherwise, a multilayer sheet B [3] was obtained in the same manner as in Production Example 11.

(Production Example 14) Multilayer sheet B [4]:
In the multilayer sheet B, the total sheet thickness is 200 μm, the layer structure is the skin layer (80 μm) / core layer (40 μm) / skin layer (80 μm), and the core layer thickness is 20%. Otherwise, a multilayer sheet B [4] was obtained in the same manner as in Production Example 11.

(Production Example 15) Multilayer sheet B [5]:
As the skin layer, polycarbonate (trade name "TARFLON FN2500A" produced by Idemitsu Kosan Co., melt volume rate ⁼ 8cm 3 / 10min) using, as a core layer, the above polycarbonate, with blending titanium oxide 5 wt, phenolic antioxidants N-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name “Irganox 1076”, manufactured by Ciba Specialty Chemicals)), and As a UV absorber, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole (trade name “Tinuvin 327”, manufactured by Ciba Specialty Chemicals) , 0.2 part, and the total thickness of the sheet is 200 μm by T-die melt extrusion molding, The thickness of the back skin layer was the same, and the thickness of the core layer, which is the structure of the skin layer (40 μm) / core layer (120 μm) / skin layer (40 μm), was set to 60%. Furthermore, about the average surface roughness (Ra) of both surfaces, the multilayer sheet B [5] by which the mat | matte process was given so that it might be set to 0.5-1.8 micrometers was obtained.

  Various evaluations were performed on Examples 1 to 15 described above as Examples 4 to 10 and Comparative Examples 5 to 13 with the configurations shown in Tables 3 and 4. The results are shown in Tables 3 and 4.

(Discussion 2)
As shown in Tables 3 and 4, all of Examples 4 to 10 using the hinge sheets of Examples 1 to 3 are sheet transportability, releasability after laminating and heating press, bubble release property, and heat fusion. In addition, it has excellent laser marking properties.

  On the other hand, in Comparative Example 5, since the thickness ratio of the core layer of the transparent laser marking sheet A [3] (Production Example 3) was 10%, the laser marking property and the contrast property were poor. Since the core layer thickness is extremely thin at this core layer thickness ratio, it is difficult to obtain a stable three-layer sheet by controlling the thickness ratio, and industrial production is considered difficult. In Comparative Example 6, since the thickness of the core layer of the transparent laser marking sheet A [6] (Production Example 6) was 20%, the laser marking property and the contrast property were poor. In Comparative Example 7, the co-extrusion of the transparent laser marking sheet A [7] (Production Example 7) with a core layer thickness of 90% was attempted, but the skin layer was too thin. Since the structure including this layer stably could not be manufactured sufficiently, “−” is shown in Table 4 as being unmeasurable. Furthermore, in Comparative Example 8, since the lubricant was not added to the transparent laser marking sheet A [8], the releasability was poor. Similarly, in Comparative Example 9, carbon black was not blended as a laser light energy absorber in the transparent laser marking sheet A [9], so that the laser marking property and the contrast property were inferior. Further, in Comparative Example 10, since 5 parts by mass of the laser light energy absorber carbon black was blended in the core layer of the transparent laser marking sheet A [10], the sheet itself exhibited a black color, and as a result, the transparency decreased. The laser irradiation causes the PC resin to burn and foam, which is not very practical.

  Furthermore, in Comparative Example 11, the thickness of the core layer of the multilayer sheet B [3] (Production Example 13) was set to a ratio of 88%, so that the heat-fusibility was insufficient. In the three-layer sheet, the core layer thickness ratio is as high as 88%. Therefore, even if the total thickness is 200 μm, the skin layer thickness is only 12 μm, and it is difficult to control the thickness of each layer to produce a three-layer sheet stably. Production is considered difficult. In Comparative Example 12, since the core layer thickness of the multilayer sheet B [4] (Production Example 14) was 20%, the impairing property was poor and the contrast property of the laser marking portion was inferior. In Comparative Example 13, since the multilayer sheet B [5] (Production Example 15) PC / PC / PC three-layer sheet was used, the heat-sealing property with the transparent laser marking sheet A as an oversheet and the hinge sheet The result was inferior in heat fusibility.

  The laminated hinge sheet of the present invention can be suitably used for a laser marking laminate for an electronic passport, and is excellent in heat-fusibility and dimensional accuracy of the laminate when producing a laser marking laminate for an electronic passport. As a hinge sheet that is flexible after binding and bound to the cover, etc., and has excellent resistance to repeated bending, as well as excellent tearing and tensile strength at the binding, and excellent temporal stability such as light resistance during actual use. It can be used suitably. Further, in the laser marking laminate for the electronic passport of the present invention, the transparent laser marking sheet A and the colored laser marking multilayer sheet B are non-PVC multilayer sheets, and the transparent laser marking sheet A / multilayer sheet B / sheet C / multilayer Sheet B / transparent laser marking sheet A has a laminated structure, and it has clear and excellent laser marking properties not only for letters and numbers but also for images by laser light irradiation. This is a multilayer sheet with excellent heat resistance and sheet transportability, lamination, heat fusion, and deformation without warping, and binding the laser marking laminate for electronic passports to electronic passports. Can be bound by a simple method such as sewing, Because it is highly effective in preventing forgery by Kingu, in which can be suitably used for an electronic passport.

1: Laminated hinge sheet, 3: Thermoplastic resin P, 5: Thermoplastic resin R, 11A, 11B, 11C: Laser marking laminate for electronic passport, 13: Transparent laser marking sheet A, 13a: (Transparent laser marking sheet A Skin layer, 13b: core layer (of transparent laser marking sheet A), 15: multilayer sheet B, 15a: skin layer (of multilayer sheet B), 15b: core layer (of multilayer sheet B), 17: laser beam, 23: Transparent laser marking sheet A, 23a: Skin layer (of transparent laser marking sheet A), 23b: Core layer (of transparent laser marking sheet A), 27: Sewing binding part, 29: Overhang part, 49: Cover, 51 Laminated body, 53: visa sheet, 55: IC chip, 61: cut sheet, 61a: sticking part, 3: horizontal table, 65: support plate, 67: perforations.

Claims (13)

A laminated hinge sheet in which a thermoplastic resin sheet P having flexibility and heat-fusibility and a thermoplastic resin sheet R having heat resistance and rigidity are laminated,
The thermoplastic resin sheet P is a sheet made from a thermoplastic resin X containing a thermoplastic elastomer having a hardness Shore A of 85 or more and a Shore D of less than 70,
The thermoplastic resin sheet R is a laminated hinge sheet C which is a sheet made of a thermoplastic resin Y having a tensile elastic modulus measured according to ASTM D882 of 1 GPa or more and a glass transition temperature by DSC method of 70 ° C. or more. .   The laminated hinge sheet C according to claim 1, wherein the laminated hinge sheet is formed by laminating three layers of thermoplastic resin sheet P / thermoplastic resin sheet R / thermoplastic resin sheet P and integrating them by thermal lamination. The thermoplastic resin sheet P is an outer layer, the thermoplastic resin sheet R is an inner layer,
The lamination according to claim 1, wherein the thermoplastic resin sheet P is formed by laminating the thermoplastic resin X, which is a raw material of the thermoplastic resin sheet P, on both surfaces of the thermoplastic resin sheet R by melt extrusion molding. Hinge sheet C.   The laminated hinge sheet C according to any one of claims 1 to 3, wherein the thermoplastic resin sheet P is used as an outer layer, and the thermoplastic resin sheet R is used as an inner layer and is laminated by two-type three-layer coextrusion molding. Laser marking for electronic passport formed by laminating 5 layers of transparent laser marking sheet A / multilayer sheet B / laminated hinge sheet C / multilayer sheet B / transparent laser marking sheet A according to any one of claims 1 to 4. A laminate,
The transparent laser marking sheet A is a transparent laser marking sheet formed by melt extrusion molding, and the laser light energy absorbing material is 0.0005 with respect to 100 parts by mass of the transparent thermoplastic resin mainly composed of polycarbonate resin. A single-layer sheet comprising a transparent polycarbonate resin composition containing 1 part by mass,
Alternatively, the transparent laser marking sheet A is a transparent laser marking sheet formed by melt extrusion, has a skin layer and a core layer, and is formed by laminating at least three layers by melt extrusion. The skin layers, which are both outermost layers, are made of a resin whose main component is an amorphous aromatic polyester resin, and the core layer is 100 parts by mass of a transparent thermoplastic resin whose main component is a polycarbonate resin. On the other hand, it consists of a transparent polycarbonate resin composition containing 0.0005 to 1 part by mass of a laser light energy absorber, and further, the total thickness of the transparent laser marking sheet A is 50 to 200 μm, and the core layer thickness ratio is 30 to 85%. The multilayer sheet 1, which is less than
Alternatively, the transparent laser marking sheet A is a transparent laser marking sheet formed by melt extrusion, has a skin layer and a core layer, and is formed by laminating at least three layers by melt extrusion. The skin layers that are both outermost layers are made of a transparent resin mainly composed of a polycarbonate resin, and the core layer is a laser light energy absorbing material with respect to 100 parts by mass of the transparent resin mainly composed of the polycarbonate resin. As a multilayer sheet 2 having a total thickness of the transparent laser marking sheet A of 50 to 200 μm and a core layer thickness ratio of less than 30 to 85%. Configured,
The multilayer sheet B has a skin layer and a core layer, and is a multilayer sheet formed by laminating at least three sheets by melt extrusion molding,
The skin layer, which is both outermost layers of the multilayer sheet B, is made of a resin mainly composed of an amorphous aromatic polyester resin,
The core layer of the multilayer sheet B is made of a transparent thermoplastic resin mainly composed of a polycarbonate resin,
The skin layer and / or the core layer of the multilayer sheet B contains 1 part by mass or more of at least one colorant with respect to 100 parts by mass of the copolyester resin and / or 100 parts by mass of the polycarbonate resin. And
Furthermore, the total thickness of the multilayer sheet B is 100 to 300 μm, and the thickness ratio of the thickness of the core layer to the total thickness of the multilayer sheet B is 30% or more and less than 85%. Configured as a colored multilayer sheet,
A laser marking laminate for electronic passports, wherein the thickness of the laminated hinge sheet C is 80 to 250 μm.   Further, the single layer sheet of the transparent laser marking sheet A contains 0.01 to 3 parts by mass of a lubricant with respect to 100 parts by mass of the transparent thermoplastic resin, and an antioxidant and / or an anti-coloring agent 0. The transparent laser marking sheet containing 0.1 to 5 parts by mass and the ultraviolet absorber and / or the light stabilizer 0.1 to 5 parts by mass, or the skin layer in the multilayer sheet 2 of the transparent laser marking sheet A, While containing 0.01 to 3 parts by mass of a lubricant with respect to 100 parts by mass of the transparent thermoplastic resin, 0.0005 to 1 parts by mass of a laser beam energy absorbing material, an antioxidant and / or an anti-coloring agent It is comprised as a transparent laser marking sheet containing 1-5 mass parts and 0.1-5 mass parts of ultraviolet absorbers and / or light stabilizers. Child passport for laser marking laminate.   The laser light energy absorbing material of the transparent laser marking sheet A contains at least one or two or more selected from the group consisting of carbon black, titanium black, and metal oxide. Laser marking laminate for electronic passports.   The core layer and / or skin layer of the multilayer sheet B is 0.1 to 5 parts by mass of an antioxidant and / or anti-coloring agent, and an ultraviolet absorber and / or a light stabilizer with respect to 100 parts by mass of the thermoplastic resin. The laser marking laminated body for electronic passports of any one of Claims 5-7 containing 0.1-5 mass parts.   The laser marking laminate for an electronic passport according to any one of claims 5 to 8, wherein one end of the laminated hinge sheet C has an overhanging portion that is 5 to 100 mm longer than the transparent laser marking sheet A and the multilayer sheet B.   10. The electron according to claim 5, wherein the surface of the transparent laser marking sheet A and / or the multilayer sheet B is subjected to mat processing with an average roughness (Ra) of 0.1 to 5 μm. Laser marking laminate for passports.   Furthermore, the laser marking laminated body for electronic passports of any one of Claims 5-10 in which the forgery prevention formation part is formed.   It is an electronic passport shape | molded using the laser marking laminated body for electronic passports of any one of Claims 9-11, Comprising: The overhang | projection part of the said lamination | stacking hinge sheet C is a cover or back cover of an electronic passport. An electronic passport that is formed by sewing and / or adhering. A laser marking laminate for an electronic passport according to any one of claims 5 to 11 or an electronic passport according to claim 12, wherein the laser marking method comprises:
A laser marking method for printing by irradiating a laser beam from the transparent laser marking sheet A side laminated on the electronic passport laser marking laminate.

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