WO2013031399A1

WO2013031399A1 - Multicolor-development laser marking sheet for card, and laser marking method

Info

Publication number: WO2013031399A1
Application number: PCT/JP2012/068155
Authority: WO
Inventors: 俊規阪上; 章橋本; 善之寺司
Original assignee: 日本カラリング株式会社
Priority date: 2011-09-02
Filing date: 2012-07-18
Publication date: 2013-03-07
Also published as: JPWO2013031399A1

Abstract

A multicolor-development laser marking sheet for cards which is capable of being clearly marked with characters, symbols, images, or the like in two or more different color tones and which comprises a sheet constituted of a laser-marking resin composition that comprises a thermoplastic resin, a chromatic colorant, and a black substance, wherein the thermoplastic resin is, for example, an acrylic resin, the chromatic colorant is a colorant that contains at least one framework selected from the group consisting of a phthalocyanine framework, a diketopyrrolopyrrole framework, a dioxazine framework, a quinacridone framework, a quinophthalone framework, a perylene framework, and metal complex frameworks and that, in a differential thermal analysis, has an exothermic peak in the range of 360-590ºC, and the black substance is a substance that itself disappears or changes in color upon reception of laser light. The sheet has an overall thickness of 100-300 µm.

Description

Multicolored laser marking sheet for card and laser marking method

The present invention relates to a multicolor coloring laser marking sheet and a laser marking method for cards that are suitably used for various types of cards, particularly plastic IC cards such as contact type and non-contact type IC cards, and more specifically, marking with a laser beam is possible. The present invention relates to a multicolor coloring laser marking sheet for a card and a laser marking method capable of clearly marking characters, symbols, images and the like in two or more different color tones.

¡Plastic cards such as credit cards, bank cards, ID cards, and transportation cards are now widely used all over the world, and the number is increasing. Plastic cards are on an increasing trend due to an increase in the number of cards issued in developing countries.

The manufacturing method of these plastic cards is to first print a pattern by offset printing or the like in advance on a specific sheet, and after stacking other multiple sheets and heat-sealing between each sheet by a vacuum press machine, A card is obtained by punching into a card with a punching machine. Alternatively, a plurality of sheets on which nothing is printed are stacked and heat-sealed between the sheets with a vacuum press machine, and then punched into a card shape with a punching machine to obtain a card. Thereafter, printing is performed on the outermost surface of the card using a card printer. In this way, a plastic card was manufactured.

However, in these plastic cards, a laser marking method for marking characters, images, etc. by irradiating a laser beam as soon as possible in Europe and the United States has been widely adopted due to an increase in security requirements.

A plastic card that can be marked by the laser marking method is manufactured by a method similar to the above card manufacturing method, using a single layer sheet (laser marking sheet) containing a polycarbonate resin in many cases. Specifically, after first printing a light-colored background pattern on a specific white sheet in advance by offset printing, etc., and then stacking a plurality of other sheets and heat-sealing each sheet with a vacuum press machine A punching card is obtained in a card shape by a punching machine. Thereafter, the outermost surface of the card is irradiated with laser light to mark dark characters such as black and images. In this way, marking with high visibility of “black / white contrast” is basically made up of a light-colored background pattern, dark-colored characters, images, and the like (see, for example, Patent Documents 1 to 5).

Japanese Patent Laid-Open No. 5-92657 JP 2002-273732 A Japanese Patent No. 3889431 JP-A-6-297828 JP-A-8-127175

However, these laser marking technologies are only technologies for marking black characters and monocolor images, and there is still room for improvement. That is, recently, further differentiation of plastic cards is desired, and there is an increasing demand for improving color laser marking technology in order to achieve differentiation. Specifically, development of a color laser marking sheet on which characters, symbols, images and the like of two or more different colors are clearly marked is desired.

Patent Document 1 discloses that marking is performed by irradiating a thermoplastic resin containing carbon black with laser light. However, only a polyacetal resin and a polybutylene terephthalate resin are substantially disclosed as thermoplastic resins. Furthermore, in patent document 1, only description about the injection molded product is made.

Patent Documents 2 and 3 disclose the technology of a laser marking multilayer sheet. In addition, a “black / white contrast” sheet is basically described in which a light-colored background pattern and dark-colored characters, images, and the like are obtained.

Patent Documents 4 and 5 disclose laser marking resin compositions and molded products other than white or black. However, all of them have the problem that the color and the color produced by the laser light are monochromatic, so that the visibility and design are limited. Patent Document 4 only discloses a technique in an injection-molded article that substantially uses a polyacetal resin or a thermoplastic polyester resin as a thermoplastic resin. Patent Document 5 describes aromatic polycarbonate resins, aromatic polyester resins, polyamide resins, and styrene resins as thermoplastic resins. However, Patent Document 5 only discloses a technique for an injection molded product. That is, Patent Documents 4 and 5 do not specifically describe the sheet.

The present invention has been made to solve the above-described problems of the prior art. That is, by irradiating two or more different wavelengths of laser light onto different positions on the surface of the “card sheet exhibiting a black or dark ground color”, characters, symbols, images, etc. of two or more different colors are obtained. Provided are a multicolor laser marking sheet for a card to be marked clearly and a laser marking method.

As a result of diligent investigations to achieve the above-mentioned object, the present inventors have determined that "from a specific thermoplastic resin," a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton. Black color that contains at least one selected skeleton and has an exothermic peak in the range of 360 ° C. or higher and 590 ° C. or lower by differential thermal analysis and “disappears or discolors itself by receiving laser light” By irradiating two or more laser beams having different energies to a “predetermined layer in a single layer sheet or a multilayer sheet” comprising a “resin composition containing a substance”, two or more characters and symbols having different colors It was found that images and the like are clearly marked.

According to the present invention, the following multicolor coloring laser marking sheet for a card and a laser marking method are provided.

[1] A sheet comprising a laser marking resin composition containing a thermoplastic resin, a chromatic colorant, and a black substance, and two or more different color tones including white and chromatic colors when irradiated with laser light At least one thermoplastic selected from the group consisting of acrylic resins, polycarbonate resins, styrene resins, and non-crystalline aromatic polyester resins A resin, wherein the chromatic colorant comprises at least one skeleton selected from the group consisting of a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton. And has an exothermic peak in the range of 360 to 590 ° C. in differential thermal analysis. The black material is a substance which changes color or itself disappears by receiving the laser beam, the total thickness of 100 ~ 300 [mu] m multicolor laser marking sheet cards.

[2] The multicolor coloring laser marking sheet for cards according to [1], wherein the black substance is at least one selected from the group consisting of carbon black, titanium black, and black iron oxide.

[3] The blending amount of the chromatic colorant is 0.001 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and the blending amount of the black substance is with respect to 100 parts by mass of the thermoplastic resin. The multicolor coloring laser marking sheet for cards according to the above [1] or [2], which is 0.01 to 2 parts by mass.

[4] The card multiplicity according to any one of [1] to [3], wherein the resin composition contains 0.001 to 1 part by mass of a white material with respect to 100 parts by mass of the thermoplastic resin. Color development laser marking sheet.

[5] The multicolor coloring laser marking sheet for cards according to any one of [1] to [4], which is a single layer sheet.

[6] A multilayer sheet comprising a surface layer and an inner layer, wherein the surface layer is at least one selected from the group consisting of acrylic resins, polycarbonate resins, styrene resins, and amorphous aromatic polyester resins. The card layer according to any one of [1] to [4], wherein the transparent layer is a transparent layer comprising a thermoplastic resin composition and the inner layer is a layer comprising the laser marking resin composition. Multicolor laser marking sheet.

[7] The multicolor coloring laser marking sheet for cards according to [6], wherein the ratio of the thickness of the inner layer to the total thickness of the multilayer sheet is 30 to 85%.

[8] The multicolor laser marking sheet for cards according to any one of [1] to [7], wherein the average surface roughness (Rz) is 1 to 10 μm.

[9] The multicolor coloring laser marking sheet for cards according to any one of [1] to [8], wherein the L value in the measurement of the lightness of the fabric color is less than 50.

[10] The multicolor coloring laser marking sheet for cards according to any one of [1] to [9], wherein the whiteness of the laser-marked portion is 20 or more.

[11] The multicolor laser marking sheet for cards according to any one of [1] to [10], wherein the contrast between the fabric color and the color of the laser-marked portion is 2 or more.

[12] When irradiating the multicolor laser marking sheet for cards according to any one of [1] to [11] with two or more different wavelengths, the wavelength of the low energy laser light and the high energy The laser marking method whose difference with the wavelength of the laser beam is 100 nm or more.

The multicolor coloring laser marking sheet for a card of the present invention includes a sheet made of a laser marking resin composition containing a thermoplastic resin, a chromatic colorant, and a black substance, and is irradiated with laser light. A sheet marked in two or more different color tones including white and chromatic colors, wherein the thermoplastic resin is an acrylic resin, a polycarbonate resin, a styrene resin, and an amorphous aromatic polyester resin At least one selected from the group consisting of a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton. 360-59 in differential thermal analysis comprising at least one selected skeleton In order to satisfy “having an exothermic peak in the range of ° C. and the black substance is a substance that itself disappears or changes color by receiving laser light” and “the total thickness is 100 to 300 μm”, Marking with a laser beam is possible, and characters, symbols, images, etc. of two or more different colors are marked clearly. Moreover, in order to satisfy | fill the said conditions, the multicolor coloring laser marking sheet | seat for cards of this invention is excellent in the characteristic of heat-fusability, sheet | seat cutting property, and sheet moldability.

The laser marking method of the present invention is described as follows: “When the multicolored laser marking sheet for cards of the present invention is irradiated with two or more different wavelengths of laser light, the wavelength of the low energy laser light and the wavelength of the high energy laser light Therefore, it is possible to clearly mark two or more characters, symbols, images, etc. having different color tones.

It is a schematic diagram which shows the cross section of one Embodiment of the multicolor coloring laser marking sheet for cards of this invention. It is a schematic diagram which shows the cross section of other embodiment of the multicolor coloring laser marking sheet for cards of this invention. It is a figure which shows the color solid of a Lab color system.

Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments are also within the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should be.

[1] Multicolor laser marking sheet for cards:
The multicolor coloring laser marking sheet for cards of the present invention is from a laser marking resin composition (hereinafter sometimes referred to as “resin composition”) containing a thermoplastic resin, a chromatic colorant, and a black substance. It is equipped with a sheet. And it is a sheet | seat marked by two or more different color tones including white and a chromatic color by irradiating a laser beam. In this multicolor coloring laser marking sheet for card, the thermoplastic resin is at least one selected from the group consisting of an acrylic resin, a polycarbonate resin, a styrene resin, and an amorphous aromatic polyester resin. It is a thermoplastic resin. Further, the chromatic colorant includes “at least one skeleton selected from the group consisting of a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton. And having an exothermic peak in the range of 360 to 590 ° C. in the differential thermal analysis ”. Furthermore, the black substance is a substance that disappears or changes its color upon receiving laser light. The multicolor coloring laser marking sheet for cards of the present invention has a total thickness of 100 to 300 μm.

Such a multicolor coloring laser marking sheet for a card (hereinafter sometimes simply referred to as “sheet”) is “from a laser marking resin composition containing a thermoplastic resin, a chromatic colorant, and a black substance. The sheet is marked with two or more different colors including white and chromatic colors by irradiating laser light, and the thermoplastic resin is an acrylic resin, polycarbonate resin, styrene resin, And at least one thermoplastic resin selected from the group consisting of non-crystalline aromatic polyester resins, and the chromatic colorant is a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, or a quinophthalone skeleton , At least one skeleton selected from the group consisting of a perylene skeleton and a metal complex skeleton In addition, it has an exothermic peak in the range of 360 to 590 ° C. in the differential thermal analysis, and the black substance is a substance that itself disappears or changes color by receiving laser light ”and“ total thickness is In order to satisfy “100 to 300 μm”, marking with a laser beam is possible, and it is possible to clearly mark characters, symbols, images, etc. of two or more different colors. Moreover, in order to satisfy | fill the said conditions, the multicolor coloring laser marking sheet | seat for cards of this invention is excellent in the characteristic of heat-fusability, sheet | seat cutting property, and sheet moldability.

Note that whether a character, a symbol, an image, or the like is clear can be determined based on whether or not the contrast between the laser irradiation portion and the fabric portion is good for a colored portion that is colored white. About a chromatic color irradiation part, it can be judged by whether the same color as the used chromatic colorant can be confirmed. The multicolor coloring laser marking sheet for cards according to the present invention “has a sheet made of the above-mentioned laser marking resin composition and has a total thickness of 100 to 300 μm”, so that characters, symbols, images, etc. of two or more different colors are provided. It can be marked clearly and has excellent properties in heat-fusibility, sheet cutting properties, and sheet formability.

The multicolor coloring laser marking sheet for cards of the present invention can be used as an oversheet for cards (plastic cards such as credit cards). As described above, the thickness of the sheet of the present invention needs to be 100 to 300 μm, preferably 100 to 200 μm, and more preferably 100 to 150 μm. When the thickness is within the above range, it is possible to clearly mark characters, symbols, images, and the like having two or more different colors. If the sheet thickness is less than 100 μm, clear characters, symbols, images and the like cannot be obtained. If it exceeds 300 μm, the regulation of the thickness of the entire card to be satisfied by the card cannot be satisfied. Further, the cutting property is not sufficient, and defects such as burrs and cracks occur when cutting.

The color development mechanism of the multicolor laser marking sheet for cards of the present invention is presumed to be based on the following phenomenon.

When the multicolor coloring laser marking sheet for cards according to the present invention is irradiated with laser light, the black material disappears or changes color depending on the energy of the laser light.

Here, in the portion where the disappearance or discoloration of the black material has occurred, the color of the material other than the black material (for example, a chromatic colorant) appears stronger than the portion where the disappearance, discoloration or the like does not occur. Specifically, a low-energy laser beam (a laser beam having an energy that causes the black material to disappear, but does not cause decomposition of the chromatic colorant, etc.) on a sheet exhibiting a black or dark fabric color (ground color) ), The part irradiated with laser light (laser light irradiation part (or irradiation part)) has a strong influence of the substance derived from the chromatic colorant (for example, the black substance disappears) Hereinafter, the color develops to “color derived from a chromatic colorant”. After that, further irradiation of laser light (laser light with energy causing decomposition of the chromatic colorant) to the part where the black material disappeared, discolored, etc. causes decomposition, scattering, etc. of the chromatic colorant. Will occur. As a result, the portion where the chromatic colorant was decomposed, scattered, etc., “the concentration of the color derived from the chromatic colorant relative to the portion where the chromatic colorant was not decomposed, scattered, etc. ( Color with a reduced intensity) or white.

As described above, the degree of color change varies depending on the energy of the irradiated laser beam. Therefore, it is considered that two or more different color tones are marked by irradiating two or more laser beams having different energies.

The sheet of the present invention is for a plastic card. Plastic cards are classified into various cards according to information handling. For example, there are a card that handles simple information such as a member name and a member number, a magnetic card that records various information such as personal information on a magnetic stripe, and an IC card that writes information on an IC chip.

IC cards are classified into contact type IC cards that exchange information with an IC module disposed on the surface thereof, and non-contact type IC cards in which an IC chip and an antenna are disposed inside the card. In recent years, IC cards are spreading rapidly because they are far superior to magnetic cards in terms of protection of personal information and the like (that is, in terms of security).

The dimensions of these cards are specified in ISO / IEC7810 for credit cards, bank cards, and IC cards, and specifically, specified as 54.0 mm long × 85.6 mm wide × 0.76 mm thick. . On the other hand, the dimensions of magnetic cards such as domestic commuter passes and passnets are defined as 57.5 mm long × 85.0 mm wide × 0.25 mm thick. In general, the thickness of the card (excluding the magnetic card) is generally in the range of about 0.76 to 0.83 mm.

Here, as an example of the basic configuration of the contact IC card, oversheet (transparent) 100 μm / core sheet (white) 150 μm / core sheet (white) 310 μm / core sheet (white) 150 μm / oversheet (transparent) 100 μm is there. Also, as an example of the basic configuration of the non-contact type IC card, oversheet (transparent) 100 μm / core sheet (white) 120 μm / inlet sheet (white) 380 μm / core sheet (white) 120 μm / oversheet (transparent) 100 μm is there. However, the inlet sheet refers to a sheet on which an IC chip and an antenna are arranged.

The above-mentioned "oversheet (transparent) 100μm" uses an oversheet that can be laser-marked, and the IC card that has improved security by laser marking on this oversheet is often used overseas, especially in Europe and America. Yes. More recently, it has been used in Asia.

Another example of the basic configuration of the contact IC card is as follows: oversheet (transparent) 50 μm / oversheet (laser marking) 100 μm / core sheet (white) 150 μm / core sheet (white) 200 μm / core sheet (white) 150 μm / Oversheet (laser marking) 100 μm / oversheet (transparent) 50 μm. As another example of the basic configuration of the non-contact type IC card, oversheet (transparent) 50 μm / oversheet (laser marking) 100 μm / core sheet (white) 100 μm / inlet sheet (white) 380 μm / core sheet (white) ) 100 μm / oversheet (transparent) 100 μm.

As described above, the IC card is a laminated body composed of 5 to 7 sheets as a basic structure, and the total thickness of the IC card is generally 760 to 830 μm. Therefore, the thickness of each sheet is generally 50 to 310 μm. The main performance required for such an IC card or the like is heat resistance, strength, chemical resistance, scratch resistance, and the like.

The main performance required for the sheets used in these cards is that they are thin (thickness is about 50 to 310 μm) and can be manufactured by melt extrusion. In manufacturing a card, in the process of laminating 5 to 7 sheets, these sheets are generally stacked and compression molded (also referred to as “press molding”) (that is, by heating and pressurizing each of the sheets). This is for performing an operation of punching (referred to as “punching”) after producing a card-like laminate by heat-sealing the sheets.

The temperature in this compression molding varies depending on the sheet material, but is about 100 to 140 ° C. for polyvinyl chloride resin (PVC resin) and amorphous polyester resin (PETG resin), and 170 to 190 ° C. for polycarbonate resin (PC resin). It is. Therefore, it is required that the sheets are heat-sealed and no separation occurs within the heating temperature range.

Also, since the card core sheet is printed with fixed information and the like, it is often lightly colored (generally white) and is required to have excellent whiteness. Furthermore, it is required that offset printing, silk screen printing, and inkjet printing are possible. Since the card oversheet constitutes the surface of the card, colorless transparency, surface gloss and scratch resistance (scratch resistance) are required.

In addition to these required performances, the sheet is required to have repeated bending / torsion fatigue strength, impact strength strength, etc. as strength properties required for the card.

The resin constituting the sheet satisfying the above required performance was limited to PVC resin, PETG resin, PC resin, or polymer alloy composed of PC resin and PETG resin.

[1-1] Thermoplastic resin:
The thermoplastic resin is at least one selected from the group consisting of acrylic resins, polycarbonate resins, styrene resins, and amorphous aromatic polyester resins. By using these specific resins, it is possible to obtain a laser marking sheet capable of marking clear characters, symbols, images and the like even when the sheet is thin (100 to 300 μm).

Examples of acrylic resins include acrylic resins such as (co) polymers and rubber-reinforced acrylic resins using one or more of (meth) acrylic esters such as polymethyl methacrylate (PMMA). . Among these, it is preferably at least one selected from the group consisting of acrylic rubber and acrylic elastomer reinforced acrylic resin, and a viewpoint that a sheet having good impact resistance, surface hardness, surface gloss, and transparency can be obtained. Therefore, those composed of acrylic rubber and acrylic elastomer reinforced acrylic resin are more preferable.

Examples of the polycarbonate resin include aromatic polycarbonate resin, aliphatic polycarbonate resin, aromatic-aliphatic polycarbonate resin copolymer, and the like. Among these, from the viewpoint of obtaining a sheet having good heat resistance, impact resistance, and transparency, and from the viewpoint of not increasing the cost, an aromatic polycarbonate resin or an aromatic polycarbonate resin and an amorphous aromatic polyester are used. It is preferably a polymer alloy resin composed of a resin.

Examples of the styrene resin include polystyrene, styrene / acrylonitrile copolymer, styrene / maleic anhydride copolymer, (meth) acrylic acid ester / styrene copolymer, acrylonitrile / butadiene / styrene (ABS) copolymer resin, and the like. Can be mentioned. Among these, a transparent acrylonitrile / butadiene / styrene copolymer resin is preferable from the viewpoint of obtaining a sheet having good impact resistance and transparency.

[1-2] Chromatic colorant:
A chromatic colorant causes decomposition, scattering, and the like by energy higher than the energy that causes the black material to disappear, change color, or the like. Therefore, when irradiated with high-energy laser light (laser light with energy that causes decomposition of the chromatic colorant, etc.), the irradiated part is "color with a reduced color density derived from the chromatic colorant" Or it turns white.

As described above, the chromatic colorant includes “a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton. And having an exothermic peak in the range of 360 to 590 ° C. in the differential thermal analysis ”.

The lower limit temperature of the exothermic peak range is more preferably 380 ° C., particularly preferably 400 ° C., and the upper limit temperature is more preferably 585 ° C. When the exothermic peak temperature is less than the lower limit value, the marking of the color derived from the chromatic colorant becomes unclear when irradiated with low energy laser light. On the other hand, when the exothermic peak temperature is higher than the upper limit value, when a high-energy laser beam is irradiated, the marking of the color having a reduced color density derived from the chromatic colorant becomes unclear. The differential thermal analysis can be performed by an apparatus such as “TG-DTA320 (horizontal furnace)” manufactured by Seiko Denshi.

The chromatic colorant may be a pigment or a dye as long as it satisfies the above conditions.

The color of the chromatic colorant is not particularly limited as long as it is other than black and white, and can be, for example, red, yellow, blue, purple, and green.

For example, a pigment or dye having a phthalocyanine skeleton is “blue to green”, a pigment or dye having a diketopyrrolopyrrole skeleton is “orange to red”, a pigment or dye having a dioxazine skeleton is “purple”, and a pigment having a quinacridone skeleton Or the dye is “orange to purple”, the pigment or dye having a quinophthalone skeleton is “yellow to red”, the pigment or dye having a perylene skeleton is “red to purple”, and the pigment or dye having a metal complex skeleton is “yellow to purple” Is.

[1-2-1] Chromatic colorant having a phthalocyanine skeleton:
Examples of the chromatic colorant having the phthalocyanine skeleton include compounds represented by the following general formula (I). The chromatic colorant having a phthalocyanine skeleton is a pigment or a dye.

(In the general formula (I), M is a coordination metal atom or two hydrogen atoms, and R ¹ to R ¹⁶ are each independently an arbitrary functional group.)

In the above general formula (I), M is preferably copper (Cu), aluminum (Al), zinc (Zn), tin (Sn) or two hydrogen atoms, copper (Cu), aluminum (Al). Alternatively, zinc (Zn) is more preferable, and copper (Cu) or aluminum (Al) is particularly preferable. In addition, when M is a metal, you may have ligands, such as a halogen atom and OH.

In the general formula ^{^{(I), R 1 ~ R}} 16 is a hydrogen atom; a fluorine, chlorine, bromine, halogen atom such as iodine; sulfonic acid amide group _{_{(-SO 2 NHR), - SO}} 3 - · NH 3 A substituent such as R ⁺ (wherein R is an alkyl group having 1 to 20 carbon atoms) is preferable, and a plurality of adjacent Rs out of R ¹ to R ¹⁶ are connected to form an aromatic ring. Groups are also preferred. Particularly preferred is a hydrogen atom or a sulfonic acid amide group.

Specific structures preferable as a chromatic colorant having a phthalocyanine skeleton are listed in the following (1) to (6). Among these, the thing of the specific structure enumerated in (1), (3), (4) is preferable.

(1) A copper phthalocyanine pigment (compound represented by the following formula (II)) in which M in the general formula (I) is Cu and R ¹ to R ¹⁶ are hydrogen atoms.

The crystal of the copper phthalocyanine pigment may be α type or β type. The average secondary particle diameter of the β-type copper phthalocyanine pigment is generally more than 20 μm and not more than 30 μm, but in the present invention, the upper limit is preferably 20 μm, more preferably 10 μm. The lower limit is preferably 1 μm. The average secondary particle size is a value measured by a laser scattering method, and can be measured by a laser scattering method particle size distribution measuring device or the like.

(2) A halogen-containing copper phthalocyanine pigment in which M in the general formula (I) is Cu, and R ¹ to R ¹⁶ are each independently a hydrogen atom or a halogen atom. In addition, as a halogen atom, a chlorine atom and a bromine atom are preferable.

(3) is M in the above general formula (I) is ^Cu, R 1 ^~ 4 ^~ 8 pieces of ^{R 16} (preferably four), the above-mentioned sulfonic acid amide group or _-SO ³ - · NH ₃ A solvent-soluble copper phthalocyanine dye which is R ⁺ , preferably a sulfonic acid amide. A particularly preferable solvent-soluble copper phthalocyanine dye is a compound represented by the following general formula (III).

(In the general formula (III), each R is independently an alkyl group having 1 to 20 carbon atoms.)

In the general formula (III), each R is particularly preferably an alkyl group having 4 to 8 carbon atoms.

(4) An aluminum phthalocyanine pigment in which M in the above general formula (I) is Al and R ¹ to R ¹⁶ are hydrogen atoms. Al preferably has —OH or —Cl as a ligand, and more preferably has —OH. A particularly preferred aluminum phthalocyanine pigment is a compound represented by the following formula (IV).

(5) A tin phthalocyanine pigment in which M in the general formula (I) is Sn, and R ¹ to R ¹⁶ are each independently a hydrogen atom or a halogen atom.

(6) A zinc phthalocyanine pigment in which M in the general formula (I) is Zn, and R ¹ to R ¹⁶ are each independently a hydrogen atom or a halogen atom. This zinc phthalocyanine pigment is a compound represented by the following general formula (V).

(In the general formula (V), R ¹ to R ¹⁶ are each independently a hydrogen atom or a halogen atom.)

As the zinc phthalocyanine pigment, those in which R ¹ to R ¹⁶ in the general formula (V) are all hydrogen atoms are particularly preferable.

[1-2-2] Chromatic colorant having a diketopyrrolopyrrole skeleton:
Examples of the chromatic colorant having a diketopyrrolopyrrole skeleton include compounds represented by the following general formula (VI). The chromatic colorant having a diketopyrrolopyrrole skeleton is usually a pigment.

(In the general formula (VI), Ar and Ar ′ are each independently an aromatic ring which may have a substituent.)

The aromatic ring constituting Ar and Ar ′ may be any ring as long as it has aromaticity, but is usually an aromatic ring consisting of a 5- or 6-membered monocyclic ring or a 2-6 condensed ring. . Hetero atoms such as O, S, and N may be included. Specifically, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, pyridine ring, thiophene ring, pyrrole ring, furan ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, imidazole ring, quinoline ring, isoquinoline Ring, carbazole ring, thiazole ring, dibenzothiophene ring and the like. Among these, a 6-membered ring is preferable, a 6-membered monocycle is more preferable, and a benzene ring is particularly preferable.

The aromatic ring preferably has a substituent, and preferred substituents include a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, an amino group, —NHCOR ′, —COR. 'And -COOR' (where R 'is an alkyl group having 1 to 12 carbon atoms or a (hetero) aryl group having 12 or less carbon atoms). Of these, a halogen atom is preferable, and a chlorine atom is particularly preferable.

[1-2-3] Chromatic colorant having a dioxazine skeleton:
Examples of the chromatic colorant having a dioxazine skeleton include compounds containing a skeleton represented by the following formula (VII). The chromatic colorant having a dioxazine skeleton is usually a pigment.

The chromatic colorant containing the skeleton represented by the general formula (VII) may be a compound having a substituent or a compound having no substituent, but is a compound having a substituent. It is preferable. As a compound which has a substituent, the compound represented by the following general formula (VIII) can be mentioned, for example.

(In the above general formula (VIII), R ¹⁷ to R ²² are each independently a halogen atom, —NHCOR ′ (where R ′ is an alkyl group having 1 to 12 carbon atoms, or (hetero An aryl group), an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms.)

The chromatic colorant having a dioxazine skeleton particularly preferably has substituents R ¹⁷ and R ¹⁸ in the general formula (VIII). R ¹⁷ and R ¹⁸ are preferably a halogen atom or —NHCOR ′, more preferably —NHCOR ′. R ¹⁹ to R ²² are preferably a halogen atom, —NHCOR ′, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and more preferably an alkoxyl group having 1 to 12 carbon atoms or —NHCOR ′. preferable.

[1-2-4] Chromatic colorant having quinacridone skeleton:
Examples of the chromatic colorant having a quinacridone skeleton include compounds containing a skeleton represented by the following formula (IX). The chromatic colorant having a quinacridone skeleton is usually a pigment.

The chromatic colorant containing a skeleton represented by the above general formula (IX) may be a compound having a substituent or a compound having no substituent. As a compound which has a substituent, the compound represented by the following general formula (X) can be mentioned, for example.

(In the general formula (X), R ²³ to R ²⁶ are substituents.)

Examples of the substituent in the general formula (X) include a halogen atom or an alkyl group having 1 to 12 carbon atoms.

[1-2-5] Chromatic colorant having a quinophthalone skeleton:
Examples of the chromatic colorant having a quinophthalone skeleton include compounds containing a skeleton represented by the following general formula (XI). The chromatic colorant having a quinophthalone skeleton is a pigment or a dye.

The chromatic colorant containing a skeleton represented by the general formula (XI) may be a compound having a substituent or a compound having no substituent. As a compound which has a substituent, the compound represented by the following general formula (XII) can be mentioned, for example.

(In the general formula (XII), R ²⁷ to R ³⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms or a group containing a ring structure. R ³¹ represents a hydrogen atom, a halogen atom, an alkoxyl group having 1 to 12 carbon atoms, an aryloxy group having 5 to 12 carbon atoms, a heteroaryloxy group having 1 to 12 carbon atoms, or an alkylthio having 1 to 12 carbon atoms. Group, an arylthio group having 5 to 12 carbon atoms or a heteroarylthio group having 1 to 12 carbon atoms, R ³² is a hydrogen atom or a hydroxyl group, and R ³³ to R ³⁶ are each independently a hydrogen atom, A halogen atom, a carboxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, —COOR ′ or —CONR ′ ₂ (where R ′ is an alkyl group having 1 to 12 carbon atoms) Or a (hetero) aryl group having 12 or less carbon atoms.) R ²⁸ and R ²⁹ , R ³¹ and R ³² , R ³³ and R ³⁴ , R ³⁴ and R ³⁵ , and R ³⁵ And R ³⁶ may be connected to each other to form a ring.)

In the above general formula (XII), when R ²⁷ to R ³⁰ are groups containing a ring structure, examples of this group include substituents represented by the following general formula (XIII).

(In the general formula (XIII), X ¹ to X ⁴ are each independently a hydrogen atom or a halogen atom.)

The chromatic colorant in the case where R ²⁷ in the general formula (XII) is a substituent represented by the general formula (XIII) is a compound represented by the following general formula (XIV).

(In the general formula (XIV), R ²⁸ to R ³⁶ are the same as described above, and X ⁵ to X ⁸ are each independently a hydrogen atom or a halogen atom.)

As the chromatic colorant having a quinophthalone skeleton represented by the above general formula (XIV), R ²⁸ to R ³⁰ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxyl having 1 to 12 carbon atoms. A compound in which R ³¹ and R ³² are hydrogen atoms and R ³³ to R ³⁶ are halogen atoms is preferred.

More preferably, the chromatic colorant is such that R ²⁸ and R ²⁹ are hydrogen atoms or halogen atoms, R ³⁰ to R ³² are hydrogen atoms, R ³³ to R ³⁶ are halogen atoms, and X ⁵ to A compound in which X ⁸ is a halogen atom. The chromatic colorant having a quinophthalone skeleton represented by the above general formula (XIV) is usually a pigment.

Particularly preferred chromatic colorants are those in which R ²⁸ and R ²⁹ are hydrogen atoms, R ³⁰ to R ³² are hydrogen atoms, R ³³ to R ³⁶ are halogen atoms (X ⁹ to X ¹² ), and , X ⁵ to X ⁸ are a halogen atom (compound represented by the following general formula (XV)).

(In the general formula (XV), X ⁵ to X ¹² are each independently a halogen atom.)

In the above general formula (XII), R ²⁷ and R ³⁰ are hydrogen atoms, and R ²⁸ and R ²⁹ are halogen atoms, alkyl groups having 1 to 12 carbon atoms or alkoxyl groups having 1 to 12 carbon atoms. (Compound represented by the following general formula (XVI)) is usually a dye.

(In the general formula (XVI), R ²⁸ and R ²⁹ are each independently a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and R ³¹ is a hydrogen atom, A halogen atom, an alkoxyl group having 1 to 12 carbon atoms, an aryloxy group having 5 to 12 carbon atoms, a heteroaryloxy group having 1 to 12 carbon atoms, an alkylthio group having 1 to 12 carbon atoms, and an arylthio group having 5 to 12 carbon atoms Or a heteroarylthio group having 1 to 12 carbon atoms, R ³² is a hydrogen atom or a hydroxyl group, and R ³³ to R ³⁶ are each independently a hydrogen atom, a halogen atom, a carboxyl group, a carbon number of 1 to 12 alkyl group, an alkoxyl group having 1 to 12 carbon _{atoms, -COOR ', - CONR' 2} ( where, R 'is of 1 to 12 carbon atoms alkyl group or having 12 or less carbon ( Hetero) aryl group.) Is. In ^{addition, R 28} and ^R ^{29, R 31} and ^R ^{32, R 33} and ^R ^{34, R 34} and ^{R 35,} ^{and, R 35} and ^{R 36,} are connected to each other To form a ring.)

[1-2-6] Chromatic colorant having a perylene skeleton:
Examples of the chromatic colorant having a perylene skeleton include compounds represented by the following general formula (XXI). The chromatic colorant having a perylene skeleton is usually a pigment.

(In the general formula (XXI), R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 5 to 12 carbon atoms, or a heteroaryl group having 1 to 12 carbon atoms. , —COR ′ or —COOR ′ (where R ′ is an alkyl group having 1 to 12 carbon atoms and a (hetero) aryl group having 12 or less carbon atoms).

As the compound represented by the general formula (XXI), those in which R ⁴⁷ and R ⁴⁸ are alkyl groups having 1 to 12 carbon atoms are preferable, and those in which R ⁴⁷ and R ⁴⁸ are alkyl groups having 1 to 3 carbon atoms are more preferable.

[1-2-7] Chromatic colorant having metal complex skeleton:
Examples of the chromatic colorant having a metal complex skeleton include compounds in which metal ions are coordinated to an organic dye skeleton. Examples of the organic dye skeleton include those having an azo group and those having an azomethine group. And these may have a hydroxyl group, an amino group, an imino group, etc. in the ortho position or peri position of an azo group or an azomethine group. Examples of the metal ion include ions of copper, nickel, cobalt, zinc and the like.

The content of the chromatic colorant is preferably 0.001 to 3.0 parts by mass, more preferably 0.002 to 1.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Particularly preferred is 0.005 to 0.8 part by mass. When the content is less than 0.001 part by mass, marking of a color derived from the chromatic colorant is difficult to be performed, and the contrast between the laser beam irradiation part and the cloth part may be reduced, and the visibility may be reduced. is there. On the other hand, if it exceeds 3.0 parts by mass, white marking is difficult to be performed, and the contrast between the laser beam irradiation part and the cloth part may be lowered, and the visibility may be lowered.

[1-3] Black material:
The black material is not particularly limited as long as it is a material that itself disappears or changes color by receiving the laser beam. That is, if the laser beam energy is extinguished or discolored by the energy of the laser beam, and the color of the laser beam irradiation part in the sheet of the present invention becomes a color in which the influence of the color of the substance other than the black substance appears strongly. Any black material may be used.

In this specification, “annihilation” means that the black substance does not exist due to vaporization, volatilization, or decomposition, and “discoloration” means that at least a part of the substance has a color different from that before light reception due to decomposition or the like (preferably White) (for example, from black to light blue or white). Further, “black” in the black substance means a dark color including black, for example, red-black (brown-black), green-black, blue-black, purple-black, gray -Black colors such as black are included.

As the black material, the following are preferable. That is, when a black test piece consisting only of 100 parts by mass of polymethyl methacrylate and 0.1 part by mass of black material is irradiated with laser light having an output of 31 A, a frequency of 5.5 kHz, and a wavelength of 1,064 nm, Are preferably white or a color other than black.

The black material may be an inorganic material or an organic material. And it may be a pigment or a dye. Furthermore, unless the effects of the present invention are impaired, compounds or minerals not included in these may be included.

Specific examples of the black substance include inorganic pigments such as carbon black, titanium black, and black iron oxide, graphite, and activated carbon. You may use these individually or in combination of 2 or more types. Among these, those containing as a main component a substance (carbon black, titanium black, black iron oxide) that is easily foamed by laser light irradiation are preferable, and those containing carbon black as the main component are more preferable.

Examples of carbon black include acetylene black, channel black, and furnace black. The average particle size (primary particle size) of carbon black is preferably 0.1 to 1000 nm, more preferably 1 to 500 nm, and particularly preferably 5 to 100 nm. Further, the nitrogen adsorption specific surface area of carbon black is preferably 1 to 10000 m ² / g, more preferably 5 to 5000 m ² / g, and particularly preferably 10 to 2000 m ² / g.

Carbon black absorbs laser beam energy and vaporizes. Therefore, the influence of the color derived from carbon black (black or dark color) is reduced or eliminated in the laser light irradiation part, and the color is generated in “color derived from components other than carbon black”.

Titanium black is generally obtained by reducing titanium dioxide. Titanium black changes to white titanium dioxide by laser light irradiation. For this reason, the laser beam irradiating portion has a small or no black color derived from titanium black and develops white color. The average particle size of titanium black is preferably 0.01 to 2 μm, more preferably 0.05 to 1.5 μm, and particularly preferably 0.1 to 1 μm.

Black iron oxide is generally represented by Fe ₃ O ₄ or FeO · Fe ₂ O ₃ . Black iron oxide turns reddish white by laser light irradiation. For this reason, the laser beam irradiating portion has a small or no black level and develops a white color. The average particle diameter of black iron oxide is preferably 0.01 to 2 μm, more preferably 0.05 to 1.5 μm, and particularly preferably 0.1 to 1 μm.

The content of the black substance is preferably 0.01 to 2.0 parts by weight, more preferably 0.03 to 1.0 parts by weight, with respect to 100 parts by weight of the thermoplastic resin. It is particularly preferred that the amount be from 05 to 0.8 parts by mass. When the content of the black material is less than 0.01 parts by mass, the color of the fabric part of the sheet of the present invention becomes light (that is, it does not become a blackish dark color), and the fabric part and the laser beam irradiation part There is a possibility that the contrast is small and the visibility is poor. On the other hand, if it exceeds 2.0 parts by mass, the laser light irradiation part is darkened, the contrast between the fabric part and the laser light irradiation part is lowered, and the visibility may be lowered.

[1-4] White substance:
In the present invention, the resin composition may further contain a white material. The white material is preferably one that is not easily affected by the reception of laser light. By including such a white substance, the brightness of the ground color in the sheet of the present invention can be adjusted, and the whiteness of the color developed by laser marking can be improved.

The white substance is preferably at least one selected from the group consisting of white dyes and white pigments. The white dye and the white pigment are not particularly limited as long as they do not hinder color development by laser marking, and examples thereof include titanium dioxide, zinc oxide, zinc sulfide, and barium sulfate. You may use these individually or in combination of 2 or more types.

The average particle size of the white substance is preferably 0.05 to 3.0 μm, and more preferably 0.1 to 2.0 μm. The content of the white substance is preferably 0.001 to 1.0 part by weight, more preferably 0.01 to 0.5 part by weight, with respect to 100 parts by weight of the thermoplastic resin. Particularly preferred is 0.02 to 0.1 parts by mass. If the content of the white substance is less than 0.001 part by mass, the effect of blending the white substance may not be obtained. On the other hand, if it exceeds 1.0 part by mass, the contrast between the fabric part and the laser beam irradiation part may not be obtained satisfactorily.

[1-5] Additive:
Depending on the purpose and application, the resin composition may further contain additives such as UV absorbers, antioxidants, antistatic agents, hydrophilicity imparting agents such as surfactants, and lubricants. Among these additives, when a hydrophilicity imparting agent such as an antistatic agent or a surfactant is blended, charging during sheet conveyance can be suppressed and the handling property of the sheet can be improved. Further, printability can be improved by preventing charging during offset printing and improving compatibility with printing ink.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts, and the like. These may be used alone or in combination of two or more. The content of the ultraviolet absorber is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

Examples of the antioxidant include hindered amines, hydroquinones, hindered phenols, and sulfur-containing compounds. These may be used alone or in combination of two or more. The content of the antioxidant is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

Examples of the antistatic agent include a low molecular antistatic agent and a high molecular antistatic agent. These may be ion conduction type or electron conduction type.

Examples of the low molecular weight antistatic agent include an anionic antistatic agent; a cationic antistatic agent; a nonionic antistatic agent; an amphoteric antistatic agent; a complex compound; a metal such as alkoxysilane, alkoxytitanium, and alkoxyzirconium. Examples thereof include alkoxides and derivatives thereof; coated silica, phosphates, phosphates, and the like. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the polymer type antistatic agent include a vinyl copolymer having a sulfonic acid metal salt in the molecule, an alkylsulfonic acid metal salt, an alkylbenzenesulfonic acid metal salt, and betaine. Furthermore, a polyamide elastomer, a polyester elastomer, etc. can also be used. These can be used individually by 1 type or in combination of 2 or more types.

The content of the antistatic agent is preferably 0.5 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin.

Examples of the lubricant include calcium stearate, fatty acid ester, hydrocarbon resin, paraffin, higher fatty acid, oxy fatty acid, fatty acid amide, alkylene bis fatty acid amide, aliphatic ketone, fatty acid lower alcohol ester, fatty acid polyhydric alcohol ester, fatty acid polyglycol. Examples include esters, aliphatic alcohols, polyhydric alcohols, polyglycols, polyglycerols, metal soaps, silicones, and modified silicones. These may be used alone or in combination of two or more. The content of the lubricant is preferably 0.1 to 5.0 parts by mass, preferably 0.01 to 5.0 parts by mass, and 0.03 to 5.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin. The amount is more preferably 1.0 part by weight, and particularly preferably 0.05 to 0.3 part by weight.

The multicolor coloring laser marking sheet for a card of the present invention may be a single layer sheet or a multilayer sheet having a surface layer and an inner layer. The single layer sheet has an advantage that the sheet can be manufactured at a relatively low cost because melt extrusion can be performed by one extruder and a single layer T die. On the other hand, in the case of a multilayer sheet, the core layer (inner layer) is a laser marking layer and the skin layer (surface layer) is a transparent protective layer. A protective layer can be formed on the laser marking layer by providing a skin layer. Therefore, depending on the material of the protective layer, there are advantages that the appearance is good, scratch resistance, chemical resistance, and printability when printing on the outermost layer is improved.

In the case of a multilayer sheet, the surface layer includes at least one thermoplastic resin selected from the group consisting of an acrylic resin, a polycarbonate resin, a styrene resin, and an amorphous aromatic polyester resin. It is preferable that the layer is a transparent layer (sheet) made of a product, and the inner layer is a layer (sheet) made of the laser marking resin composition.

In the case of a multilayer sheet, the ratio of the thickness of the inner layer to the total thickness of the multilayer sheet is preferably 30 to 85%, more preferably 50 to 85%, and further preferably 60 to 80%. preferable. When the ratio of the thickness is within the above range, characters, symbols, images and the like having two or more different color tones become clearer. On the other hand, if the thickness ratio of the core layer is less than 30%, clear characters / images may not be obtained. If it exceeds 85%, the thickness of the skin layers that are both outer layers of the three-layer sheet becomes too thin, and it may be difficult to control the thickness of each skin layer. Therefore, a three-layer sheet with a uniform thickness of each skin layer may not be obtained. Moreover, there is a possibility that a clear character / image cannot be obtained.

The average surface roughness (Rz) of the multicolor laser marking sheet for cards of the present invention is preferably 1 to 10 μm, more preferably 2 to 8 μm, and particularly preferably 3 to 6 μm. By setting the average surface roughness (Rz) in the above range, the air bubble removal property between layers is improved in the heating lamination process with a press machine during the production of the card laminate. Furthermore, a smooth surface is obtained by the heating press in the above process, and a good surface gloss is obtained by this smooth surface. Therefore, a sheet having excellent clarity of characters, symbols, images and the like can be obtained. Further, the sheet transportability is improved. If the average surface roughness (Rz) is less than 1 μm, the sheet transportability may not be sufficiently obtained. On the other hand, if it exceeds 10 μm, there is a possibility that good surface gloss cannot be obtained. That is, there is a possibility that a sheet with excellent clarity such as characters, symbols, images, etc. cannot be obtained. The average surface roughness (Rz) can be measured by various surface roughness measuring instruments. In this specification, the average surface roughness (Rz) is a contact surface roughness meter (manufactured by TAYLOR HOBSON). It is a value measured by “FORM TALYSURF SERIES II”).

The L value in the lightness measurement of the fabric color (color of the fabric portion) of the multicolor coloring laser marking sheet for cards of the present invention is preferably less than 50, and more preferably less than 30. When the L value is in the above range, the laser light irradiation portion is lightly colored in the sheet of the present invention, and the contrast between the laser irradiation portion and the fabric portion is good. If the contrast is good in this way, characters, symbols, images, etc. are marked more clearly. Here, in this specification, “L value in lightness measurement of fabric color” is a value measured by a colorimeter.

The whiteness of the laser-marked portion of the multicolor coloring laser marking sheet for cards of the present invention is preferably 20 or more, and more preferably 30 or more. When the whiteness is in the above range, the contrast between the fabric color and the laser light irradiation part is excellent, and thus characters, symbols, images, etc. having two or more different colors can be obtained more clearly. The “laser-marked portion” refers to a portion where a change (disappearance or the like) of a black material has occurred due to laser light irradiation. Here, in this specification, “whiteness” is a value measured according to JIS K7105.

The contrast between the fabric color of the multicolor coloring laser marking sheet for cards of the present invention and the color of the laser-marked portion is preferably 2 or more, and more preferably 3 or more. When the contrast is in the above range, characters, symbols, images and the like are marked more clearly, and thus visibility is further improved. Here, the “contrast between the fabric color and the color of the laser-marked portion” in this specification is a value measured by a luminance meter.

[2] Laser marking method:
In the laser marking method of the present invention, the multicolor coloring laser marking sheet for cards of the present invention is irradiated with laser light of the same wavelength under different irradiation conditions or by irradiating laser light of different wavelengths. This is a method of marking in two or more different color tones by irradiating a laser beam so that the energy amount to the irradiated object (the sheet) at that time becomes two or more different energy amounts.

In the laser marking method of the present invention, when irradiating the multicolor coloring laser marking sheet for card with two or more different wavelengths of laser light, the wavelength of the low energy laser light, the wavelength of the high energy laser light, The difference is 100 nm or more. That is, in the method of laser marking by irradiating one laser beam A and another laser beam B, the laser beam A and the laser beam B have different wavelengths, and the difference between these wavelengths is 100 nm or more. According to such a method, it is possible to clearly mark characters, symbols, images, etc. having two or more different colors on the multicolor coloring laser marking sheet for cards of the present invention.

Generally, the “energy” of the laser beam depends on the irradiation condition of the laser beam. Specifically, by changing the type, wavelength, pulse width, frequency, output, irradiation time, irradiation area, distance and angle from the light source to the molded product, irradiation method, etc. Laser beams with different energy amounts can be obtained. More specifically, the amount of energy can be made different when laser light having different wavelengths is used, or when laser light having the same wavelength is used and other irradiation conditions such as irradiation time are varied. Further, when the irradiation conditions are the same, the amount of energy given to the irradiated object is different between the case of one irradiation and the case of two or more irradiations, and the latter with a longer irradiation time is “higher energy”.

As described above, the laser beam is irradiated so that the amount of energy with respect to the object to be irradiated becomes two or more different energy amounts by irradiating laser beams of the same wavelength under different irradiation conditions or by irradiating laser beams of different wavelengths. “Irradiating light” means irradiating two or more laser beams having different degrees of damage to the irradiated object. When all of the above-mentioned irradiation conditions are the same, the damage given to the irradiated object is different between the case where the irradiation is performed once and the case where the irradiation is performed in a plurality of times. Included in “Laser light”. In other words, even if the total energy to be applied is the same, if the irradiated object receives more damage than irradiated twice, the former is set to “high energy”.

In the laser marking method of the present invention, the laser light applied to the multicolor coloring laser marking sheet for card of the present invention is not irradiated unless the performance of the multicolor coloring laser marking sheet for card of the present invention is significantly impaired. It may be performed under conditions. The irradiation method may be either a scanning method or a mask method, and two or more laser beams having different energies may be irradiated simultaneously or may be irradiated one by one. Moreover, as a laser beam irradiation device, a general laser marking device or the like can be used. This device is usually equipped with a laser oscillator, laser modulator, handling unit, controller, etc., and laser light oscillated from the laser oscillator is pulse-modulated by the laser modulator and irradiated to the surface of the molded product. Marking is formed. In laser marking, two or more laser beams having different energies may be emitted from one device, or a plurality of devices may be used. As an apparatus capable of two-wavelength laser marking, for example, a laser marking system “RSM50D type”, “RSM30D type” manufactured by Roffin Basel, Inc. can be used.

The laser beam may be any of gas, solid, semiconductor, dye, excimer and free electron, but preferably has a wavelength in the range of 100 to 2,000 nm. In the present invention, the numbers indicating the “wavelength” of laser light, such as 1,064 nm and 532 nm, all mean the center wavelength, and normally include an error of ± 3%.

Examples of the gas laser include a helium / neon laser, a rare gas ion laser, a helium / cadmium laser, a metal vapor laser, and a carbon dioxide laser. Examples of the solid laser include a ruby laser, a neodymium laser, and a wavelength tunable solid laser. The semiconductor laser may be inorganic or organic, and examples of the inorganic semiconductor laser include GaAs / GaAlAs, InGaAs, and InP. Further, a semiconductor laser-excited solid laser such as Nd: YAG, Nd: YVO ₄ , or Nd: YLF can also be used. The above laser beams may be used alone or in combination of two or more.

According to the laser marking method of the present invention, when the multicolor coloring laser marking sheet for card of the present invention is irradiated with laser light, the portion where the black material change (disappearance, discoloration, etc.) occurs is the color of the material other than the black material. The portion where the chromatic colorant is changed (decomposition, scattering, etc.) becomes “a color with a reduced color density derived from the chromatic colorant” or white. When the energy of the laser beam is low, the black material vaporizes, volatilizes, disappears due to complete decomposition, or at least a part of the black material stays and discoloration that changes to a color different from the original black occurs due to decomposition or the like. Therefore, the laser beam irradiating unit develops a color derived from the chromatic colorant. On the other hand, when the energy of the laser beam is higher than that of the laser, the laser beam irradiating portion develops white color or “a color having a reduced color density derived from the chromatic colorant”.

An example of a coloring method by laser light irradiation will be briefly described with reference to FIGS. 1 and 2, but the laser marking method of the present invention is not limited to these.

As shown in FIG. 1, laser light having two different energies is irradiated to different positions on the card multicolor coloring laser marking sheet 100. By irradiating the laser beam in this way, the irradiation unit 12 of the low energy laser beam 22 is marked with a color derived from the chromatic colorant, while the irradiation unit 11 of the high energy laser beam 21 is white. Alternatively, it is possible to obtain a multicolor coloring laser marking sheet 100 for a card which is marked with “color having a reduced color density derived from a chromatic colorant” and marked in two different color tones. At this time, the laser light irradiation may be performed simultaneously or separately. FIG. 1 is a schematic view showing a cross section of an embodiment of a multicolor coloring laser marking sheet for cards of the present invention.

In addition, as shown in FIG. 2, a laser beam of “color derived from a chromatic colorant” having a large area can be obtained by irradiating the multicolor coloring laser marking sheet 101 for a card with a low-energy laser beam. An irradiation part is formed. Thereafter, a laser beam is further irradiated to a part of the laser beam irradiation unit. When the laser beam is irradiated a plurality of times in this way, a part of the laser beam irradiation part of the color derived from the chromatic colorant is marked with white or a color having a reduced density of “color derived from the chromatic colorant”. be able to. FIG. 2 includes a laser light irradiation unit 11 having a color with a reduced density of white or “color derived from a chromatic colorant” inside the laser light irradiation unit 12 of “color derived from a chromatic colorant”. It is an example which shows the multicolor coloring laser marking sheet 101 for cards. FIG. 2 is a schematic view showing a cross section of another embodiment of the multicolor coloring laser marking sheet for cards of the present invention.

When laser light is irradiated in multiple times, the laser light irradiation unit 12 of “color derived from a chromatic colorant” and the laser light of a white color or a color whose concentration of “color derived from a chromatic colorant” has decreased Laser marking in which the irradiation unit 11 is adjacent can be realized. The energy of the laser light irradiated for the second time may be the same as or different from the first time, and is not particularly limited.

When two-color clear marking is obtained by the laser marking method of the present invention, normally, low-energy laser light tends to have a clear color derived from a chromatic colorant. It is preferable that the laser beam is remarkably generated. Moreover, it is preferable that a high energy laser beam is a laser beam which remarkably reduces the density of the color derived from the chromatic colorant.

When a clear marking of three or more colors is obtained by the laser marking method of the present invention, a sheet containing only one chromatic colorant may be used, or a sheet containing two or more chromatic colorants may be used. However, the latter is preferable from the viewpoint that a clearer marking can be easily formed.

In the case where multicolor coloring is performed on a sheet containing only one kind of chromatic colorant, the fact that the sheet of the present invention can change the color of the marking depending on the energy of the irradiated laser beam is utilized. Specific examples include a method of obtaining markings of three or more colors by irradiation of three or more laser beams having different energies. More specifically, the method of irradiating a total of three types of laser light, that is, two types of energy having different degrees of change of the black material and energy of decreasing the color density derived from the chromatic colorant, and the black material changes. Examples include a method of irradiating a total of three types of laser beams of energy and two types of energy having different degrees of change in the chromatic colorant.

For example, in the case of using a sheet containing only one kind of red chromatic colorant, by irradiating a low energy laser beam, a part of the black material is extinguished or discolored to make the color derived from the black material lighter. The color can be changed to “dark red”, then “red” by irradiation with high-energy laser light, and then colored “white” or “light red” by irradiation with higher-energy laser light. In this way, shading can be formed.

Further, a case where a composition containing two kinds of chromatic colorants is colored in three colors, for example, a case where chromatic colorants of red and blue are used will be described. By irradiating the low-energy laser light, the black material is extinguished or discolored, and the color derived from the black material is reduced to “purple, which is a mixed color of red and blue”, and then the high-energy laser light is irradiated. Reduce the density of the color derived from the red chromatic colorant to “blue”, and then reduce the density of the color derived from the blue chromatic colorant by irradiating with a high-energy laser beam to “white” or It can be colored “light blue”.

As described above, a laser marking having a desired color can be obtained by appropriately selecting the irradiation condition of the laser light and the chromatic colorant.

A simple method for obtaining laser beams having different energies is to use laser beams having different wavelengths. For example, when laser marking is performed by irradiating laser beams having different wavelengths only, the difference in wavelength of each laser beam is preferably 100 nm or more, more preferably 200 nm or more, and particularly preferably 500 nm or more. The upper limit is usually 1,500 nm. In the laser marking method of the present invention, in order to clearly mark a color derived from a chromatic colorant and a white color or a “color having a reduced color density derived from a chromatic colorant”, a wavelength of 1,064 nm It is preferable to use laser light and laser light having a wavelength of 532 nm. That is, a color derived from a chromatic colorant is developed by irradiation with a laser beam having a wavelength of 1,064 nm, and white or “a color having a reduced color density derived from a chromatic colorant” by irradiation with a laser beam having a wavelength of 532 nm. When the color is developed, a clear marking can be formed.

In the present specification, the “color derived from a chromatic colorant” mainly refers to a color obtained by the disappearance, discoloration, etc. of a black substance by laser light irradiation. For example, (a) the color of the chromatic colorant itself (hereinafter also simply referred to as “colorant's original color”), which appears when the influence of the color of the black material is reduced due to the disappearance or discoloration of the black material, b) Black color of the original color of the colorant (mixed color of the original colorant and the color of the black material, mixed color of the original colorant and the color changed from the black material), (c) present A color in which the color tone is changed by changing the color of the coloring agent, (d) a color in which the color of (c) is blackish, and the like are included.

In this specification, “a color having a reduced color density derived from a chromatic colorant” refers to a color having a reduced density of the above-mentioned “color derived from a chromatic colorant”. This color is mainly obtained by changing the chromatic colorant by irradiation with laser light. For example, the influence of the color of the chromatic colorant is reduced by the decomposition or scattering of the chromatic colorant. The color which appears by this, the color etc. which the chromatic colorant discolored and the color tone changed are included. The “color having a reduced color density derived from the chromatic colorant” is more preferable as it is closer to white because it is easier to distinguish from the “color derived from the chromatic colorant” described above.

In the present specification, “white” usually includes mainly the color of the thermoplastic resin itself contained in the sheet of the present invention, and includes not only pure white but also white-based colors mixed with other colors. In addition to this color, when titanium black is included as a black substance, the color derived from titanium dioxide or the color of the thermoplastic resin after being changed to titanium dioxide by laser light irradiation. A mixed color, a color derived from a white material blended as necessary, or a mixed color of this color and the color of the thermoplastic resin are included. When the thermoplastic resin contained in the sheet of the present invention is easily foamed by the reception of laser light, the color of the irradiated portion by the high-energy laser light becomes higher in whiteness.

The whiteness of the above “white” can be evaluated according to JIS K7105. Whiteness means the degree of whiteness of a color. The whiteness can also be evaluated based on the reflectance when the object is irradiated with a certain amount of light. The reflectance can be measured with a hunter whiteness meter or the like. Here, the reflectance varies depending on the type of light to be irradiated (wavelength or the like). In the case of a hunter whiteness meter, measurement is performed with blue light that is the three primary colors of light.

The whiteness (%) of the white marking obtained in the sheet of the present invention can also be expressed as a ratio of the intensity of magnesium oxide to the reflected light. The whiteness (%) in this case is preferably 55 to 100%, more preferably 60 to 100%, still more preferably 70 to 100%, and particularly preferably 80 to 100%. In addition, since the whiteness by human vision and the whiteness by the whiteness meter may not necessarily match, the white irradiation portion in the sheet of the present invention may be white as long as it is visible to the human eye even if the whiteness is low.

In the present invention, ΔE1 calculated by the following formula (1) has an upper limit of preferably 3 and more preferably from the viewpoint of being able to form a marking having a high whiteness with respect to a black or dark ground color. Is 2.5, particularly preferably 2. The lower limit is usually 0. In addition, it shows that whiteness is so high that the value of (DELTA) E1 is small.
(1): ΔE1 = √ {(L1-L2) ² + (a1-a2) ² + (b1-b2) ² }

ΔE1 is the Lab value (L1: brightness, a1: redness, b1: yellowness) of the irradiated part when the sheet of the present invention is irradiated with high energy laser light (for example, laser light with a wavelength of 532 nm), and Except for not containing a chromatic colorant, the Lab value (L2; brightness, a2) of the irradiated portion when the same sheet as the sheet of the present invention is irradiated with low energy laser light (for example, laser light having a wavelength of 1064 nm) ; Redness, b2; yellowness), a value calculated by the formula (1).

Further, in the present invention, ΔE2 calculated by the following formula (2) is preferably a lower limit of 3, more preferably 3.5, particularly from the viewpoint that the color tone difference of each irradiation part can be clarified. Preferably it is 4. The upper limit is usually 50. In addition, it shows that a color difference is clear, so that the value of (DELTA) E2 is large.
(2): ΔE2 = √ {(L1-L3) ² + (a1-a3) ² + (b1-b3) ² }

ΔE2 is the Lab value (L1; brightness, a1; redness, b1; yellowness) of the irradiated part when the sheet of the present invention is irradiated with high energy laser light (for example, laser light with a wavelength of 532 nm), and Based on the Lab value (L3: brightness, a3: redness, b3: yellowness) of the irradiated part when the sheet of the present invention is irradiated with low energy laser light (for example, laser light having a wavelength of 1,064 nm). This is a value calculated by (2).

Note that the Lab value is Richard S., known as a numerical expression of color. L. by Hunter. a. b Indicates the value of the color system. According to such a Lab value, a difference due to visual sensation can be eliminated. The Lab value is obtained by measuring the target color tone with a colorimeter and then converting the color of the laser light irradiated part into lightness (L) and hue (a, b) and plotting it on a graph as shown in FIG. Is a numerical value. A color difference meter is an instrument that measures various quantities for displaying color, and measures the spectral distribution of light or the spectral reflectance (transmittance) of an object.

3 In the graph showing the color solid in FIG. 3, the lightness (L) is defined by a numerical value in the range of 0 to 100 on the vertical axis shown on the left, and the larger the value of L, the brighter. a is a scale on the left and right in the graph, and indicates that the degree of red is strong on the (+) side and the degree of green is strong on the (−) side. On the other hand, b is an upper and lower scale in the graph, indicating that the degree of yellow is strong on the (+) side and the degree of blue is strong on the (−) side. FIG. 3 is a diagram illustrating a color solid of the Lab color system.

Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. In addition, the following methods were employ | adopted as the method of various measurements and evaluation in an Example.

[1] Exothermic peak temperature:
The exothermic peak temperature of the chromatic colorant was measured by differential thermal analysis. As a measuring device, “TG-DTA320 type (horizontal furnace)” manufactured by Seiko Electronics Co., Ltd. was used.

As a specific measurement method, 3 mg of a sample is uniformly and densely packed in an aluminum-made dish having a diameter of 5 mm and a height of 2.5 mm, and the heating rate is 10 ° C./min. Per minute. Note that temperature calibration in the measuring apparatus was performed using indium and tin. Moreover, mass calibration was performed using a weight at room temperature, and further using calcium oxalate. The exothermic peak temperature was determined by the peak top in the temperature rise curve. Table 1 shows the measurement results of the exothermic peak temperature.

The chemical formula of each chromatic colorant used in Examples and Comparative Examples is shown below. Formula (XXII) represents a β-type copper phthalocyanine pigment, Formula (XXIV) represents an aluminum phthalocyanine pigment, Formula (XXV) represents a diketopyrrolopyrrole pigment, and Formula (XXVI) represents a dioxazine pigment. Formula (XXVII) represents a quinacridone pigment, Formula (XXVIII) represents a quinophthalone pigment, Formula (XXIX) represents a perylene pigment, Formula (XXX) represents a metal complex pigment, and Formula (XXXI) Represents an anthraquinone dye, formula (XXXII) represents a perinone dye, formula (XXXIII) represents an iron phthalocyanine pigment, and formula (XXXIV) represents perylene black.

[2] Card fabric color:
The fabric color of the laser marking sheet of the produced card was evaluated by the following criteria after measuring the brightness with a colorimeter and calculating the L value of the colorimeter. The case where the L value was less than 30 was “A”, the case where the L value was 30 or more and less than 50 was “B”, and the case where the L value was 50 or more was “C”. The lightness was measured using a trade name “Color-Eye 7000A” manufactured by Gretag Machbeth.

[3] Laser color development (chromatic color):
For laser color development, a laser beam having a wavelength of 1,064 nm was used using “Laser Marker RMS103D” and “Power Line [E / SHG type]” manufactured by Roffin Basel. Visual evaluation of the color developability of the irradiated part (color developing part) after laser light irradiation was performed according to the following criteria. “A” is used when “the same color as the used chromatic colorant can be confirmed”, and “B” is used when “slightly inferior chromatic color is viable but practical”. When it is a color different from the chromatic colorant and is inferior in vividness and difficult to be practically used, “C” is given.

[4] Whiteness of laser coloring portion:
The whiteness of the colored portion that developed white (the portion colored by laser light irradiation) was measured according to JIS K7105, and the measurement results were evaluated according to the following criteria. The case where the whiteness was 30 or more was “A”, the case where the whiteness was 20 or more and less than 30 was “B”, and the case where the whiteness was less than 20 was “C”. In addition, the laser beam irradiation was performed using “Nd: YVO ₄ laser RMS103D laser marker” manufactured by Roffin Sinar. In Tables 2 to 5, “Laser Colorability (White)” is shown.

[5] Contrast:
The contrast between the fabric color and the color-developing portion that developed white was measured using a luminance meter “LS100” manufactured by Minolta, and the measurement results were evaluated according to the following criteria. The case where “contrast is 3 or more and excellent in visibility” is “A”, and the case where “contrast is 2 or more and less than 3 and is slightly inferior but is practically usable” is “B”. The case where it was less than 2 and inferior in visibility and unsuitable for practical use was designated as “C”.

[6] Heat fusion property:
The card-like laminate is heated and pressurized (0.1 to 1.0 MPa) at 160 to 180 ° C. using a vacuum press. Thereafter, the adhesion between the oversheet and the core sheet was evaluated according to the following criteria. The case where “peeling was not observed” was designated as “A”, the case where “slightly exfoliation was observed” was designated as “B”, and the case where “peeling was observed” was designated as “C”.

[7] Sheet cutting property:
After the sheet was cut to a predetermined size, the cut sheet was observed, and the cutting property was evaluated according to the following criteria. “A” indicates that there is no problem (no defects such as burrs or cracks are observed), and “B” indicates that “burrs occur on the cut end face”. "C" is defined as the case where a malfunction such as the occurrence of the problem cannot be put into practical use.

[8] Sheet formability:
A sheet having a predetermined thickness was formed and observed, and whether or not a sheet having a uniform thickness was formed was evaluated according to the following criteria. When “no problem (a sheet having a uniform thickness) is obtained”, “A” is set, and when “the thickness variation is slightly large” is set “B”, “a thickness variation is large or a smooth sheet is obtained. “C” was assigned to the case where it was not practical.

[9] Sheet transportability:
After the sheets are cut to a predetermined size, 200 to 300 sheets are stacked and packed and stored. Thereafter, in the step of heating and laminating the card-like laminate, this packaging is unpacked and the stacked sheets are conveyed one by one to a vacuum press. In this case, the sheet transportability was evaluated according to the following criteria. “A” indicates that “there is no problem in taking out and conveying the sheet”, and “B” indicates that “the sheet is slightly difficult to take out but is practical”, and “the sheets are stuck together and taken out one by one. The “difficult” case was designated as “C”.

[10] Surface gloss of card-like laminate after heat lamination:
Each sheet constituting the card-like laminate is laminated, heated at 160 to 180 ° C. using a vacuum press, and pressurized (0.1 to 1.0 MPa) to produce a card-like laminate. Thereafter, the surface gloss of the manufactured card-like laminate was visually observed and evaluated according to the following criteria. The case where “surface gloss is good” is “A”, and the case where “slightly inferior gloss is practical but can be used as a card” is “B”. "C" is a case where it is difficult to use as a simple card. In Tables 2 to 6, “laminated surface gloss” is shown.

(Example 1)
First, 100 parts by mass of an acrylic resin composed of 30% by mass of a product name “Acripet MF (standard grade, manufactured by Mitsubishi Rayon Co.)” and 70% by mass of a product name “Acrypet VRL40 (impact resistant grade, manufactured by Mitsubishi Rayon Co., Ltd.)” In addition, 0.2 part by mass of β-type copper phthalocyanine pigment and 0.1 part by mass of carbon black “# 45 (manufactured by Mitsubishi Chemical Corporation)” are blended as a chromatic colorant (1), and matted by an extruder with a T-die. While processing, a black sheet single layer sheet A (multicolored laser marking sheet for card) was produced. The single-layer sheet A had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.5 μm.

Next, 40 parts by mass of an amorphous polyester resin (trade name “EASTAR Copolyester 6763”, manufactured by Eastman Chemical Co., Ltd.) and 60 parts by mass of an aromatic polycarbonate resin (trade name “Taflon A2200 (produced by Idemitsu Kosan Co., Ltd.)” 20 parts by weight of titanium oxide “CR-60-2 (manufactured by Ishihara Sangyo Co., Ltd.)” and 0.2 part by weight of fatty acid monoglyceride as a lubricant were blended, and a sheet (white single-layer sheet Q) was processed with a mat using an extruder with a T-die. The white monolayer sheet Q had a sheet thickness of 250 μm and an average surface roughness (Rz) on both sides of the sheet of 3.6 μm.

Next, each sheet is laminated so that the monolayer sheet A, the white monolayer sheet Q, the white monolayer sheet Q, and the monolayer sheet A are laminated, and the card-like laminate is heated and pressed by a vacuum press. (Thickness 800 μm; hereinafter may be referred to as “card”). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

Each of the above evaluations (card cloth color, laser colorability (chromatic color), whiteness of the laser color development portion, contrast, heat fusion property, sheet cutting property, sheet formability) was performed on the produced laser marking sheet. The evaluation results are shown in Table 2.

In Tables 2 to 6, in the column of “card layer structure”, for example, “A / Q / Q / A” is single layer sheet A, white single layer sheet Q, white single layer sheet Q, single layer sheet. It shows that cards are configured in the stacking order of A.

(Example 2)
A single-layer sheet B (multi-color coloring laser marking for card) in the same manner as in Example 1 except that the aluminum phthalocyanine pigment as the chromatic colorant (2) was used instead of the chromatic colorant (1). Sheet). The single layer sheet B had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.8 μm.

Next, a white single-layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single-layer sheet B, the white single-layer sheet Q, the white single-layer sheet Q, and the single-layer sheet B. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

Each of the above evaluations was performed on the produced card. The evaluation results are shown in Table 2.

(Example 3)
A single-layer sheet C (multicolor coloring for cards) in the same manner as in Example 1 except that the diketopyrrolopyrrole pigment, which is the chromatic colorant (3), was used instead of the chromatic colorant (1). Laser marking sheet) was produced. Single-layer sheet C had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.4 μm.

Next, a white single-layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the stacking order of the single-layer sheet C, the white single-layer sheet Q, the white single-layer sheet Q, and the single-layer sheet C. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Example 4)
A single-layer sheet D (multicolor coloring laser marking for card) in the same manner as in Example 1 except that the dioxazine pigment as the chromatic colorant (4) was used instead of the chromatic colorant (1). Sheet). Single-layer sheet D had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.8 μm.

Next, a white single-layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single-layer sheet D, the white single-layer sheet Q, the white single-layer sheet Q, and the single-layer sheet D. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Example 5)
Single-layer sheet E (multicolor coloring laser marking for card) in the same manner as in Example 1 except that the quinacridone pigment as the chromatic colorant (5) was used instead of the chromatic colorant (1). Sheet). Single-layer sheet E had a sheet thickness of 150 μm and an average surface roughness (Rz) of both sides of the sheet of 3.8 μm.

Next, a white single layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single layer sheet E, the white single layer sheet Q, the white single layer sheet Q, and the single layer sheet E. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Example 6)
Single-layer sheet F (multicolor coloring laser marking sheet for cards) in the same manner as in Example 1 except that a quinophthalone pigment that is a chromatic colorant (6) was used instead of the chromatic colorant (1) ) Was produced. The single-layer sheet F had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.8 μm.

Next, a white single-layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the stacking order of the single-layer sheet F, the white single-layer sheet Q, the white single-layer sheet Q, and the single-layer sheet F. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Example 7)
A single-layer sheet G (multicolored color laser marking sheet for cards) in the same manner as in Example 1 except that a perylene pigment as the chromatic colorant (7) was used instead of the chromatic colorant (1). ) Was produced. The single-layer sheet G had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.8 μm.

Next, a white single layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single layer sheet G, the white single layer sheet Q, the white single layer sheet Q, and the single layer sheet G. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Example 8)
Single-layer sheet H (multicolored laser marking for cards) in the same manner as in Example 1 except that the metal complex pigment which is the chromatic colorant (8) was used instead of the chromatic colorant (1). Sheet). The single layer sheet H had a sheet thickness of 150 μm and an average surface roughness (Rz) of both sides of the sheet of 3.8 μm.

Next, a white single-layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single-layer sheet H, the white single-layer sheet Q, the white single-layer sheet Q, and the single-layer sheet H. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

Example 9
A single-layer sheet in the same manner as in Example 1 except that a transparent ABS resin (transparent acrylonitrile / butadiene / styrene copolymer resin) (trade name “Techno ABS810”, manufactured by Technopolymer Co., Ltd.) was used instead of the acrylic resin. I (multicolored laser marking sheet for card) was produced. Single-layer sheet I had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.6 μm.

Next, a white single layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single layer sheet I, the white single layer sheet Q, the white single layer sheet Q, and the single layer sheet I. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Example 10)
A single-layer sheet J (multicolor coloring laser marking sheet for card) in the same manner as in Example 1 except that an aromatic polycarbonate resin (trade name “Toughlon A2200”, manufactured by Idemitsu Kosan Co., Ltd.) was used instead of the acrylic resin. ) Was produced. The single layer sheet J had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.5 μm.

Next, a white single layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single layer sheet J, the white single layer sheet Q, the white single layer sheet Q, and the single layer sheet J. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Example 11)
First, 100 parts by mass of an amorphous polyester resin (trade name “Eastman Tritan Copolyester FX100” manufactured by Eastman Chemical Co., Ltd.), 0.2 parts by mass of β-type copper phthalocyanine pigment as a chromatic colorant (1), carbon black (“ # 45 (manufactured by Mitsubishi Chemical Co., Ltd.))) 0.1 part by weight and 0.1 part by weight of calcium stearate as a lubricant, and a single-layer sheet K (multiple for cards) while matting with an extruder with a T-die A color-developing laser marking sheet) was prepared. The single-layer sheet K had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.5 μm.

Next, a white single-layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single-layer sheet K, the white single-layer sheet Q, the white single-layer sheet Q, and the single-layer sheet K. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

Example 12
Multi-color coloring laser marking sheet for cards (hereinafter referred to as “multilayer sheet”) composed of multilayer sheets in the order of lamination of the surface layer (skin layer), inner layer (core layer), and surface layer (skin layer) by an extruder with two types and three layers T-die L ”in some cases). The produced multilayer sheet had a total sheet thickness of 150 μm, a ratio of the core layer thickness to the total sheet thickness of 73.3%, and an average surface roughness (Rz) of both surfaces of the sheet of 3.5 μm. The core layer was a black layer.

The skin layer was prepared by blending 100 parts by mass of an amorphous polyester resin (trade name “Eastman Tritan Copolyester FX100” manufactured by Eastman Chemical Co., Ltd.) and 0.1 parts by mass of calcium stearate as a lubricant. The core layer is an acrylic resin 100 composed of 30% by mass of a product name “Acripet MF (standard grade, manufactured by Mitsubishi Rayon Co.)” and 70% by mass of a product name “Acripet VRL40 (impact resistant grade, manufactured by Mitsubishi Rayon Co., Ltd.)”. As a raw material, a blend of 0.2 part by mass of β-type copper phthalocyanine pigment and 0.1 part by mass of carbon black “# 45 (manufactured by Mitsubishi Chemical Corporation)” as a chromatic colorant (1) was used.

Next, a white single layer sheet Q is produced in the same manner as in Example 1, and the respective sheets are laminated so that the multilayer sheet L, the white single layer sheet Q, the white single layer sheet Q, and the multilayer sheet L are laminated. Then, a card-like laminate (thickness: 800 μm) was produced by heating and pressing with a vacuum press. In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Examples 13 to 39)
A card (card-like laminate) was produced in the same manner as in Example 1 except that the blending amounts shown in Tables 3 to 5 were appropriately changed so as to satisfy the blending amounts. Each of the above evaluations was performed on the produced card. The evaluation results are shown in Tables 3 to 5.

(Comparative Example 1)
Single-layer sheet M (multicolored laser marking for cards) in the same manner as in Example 1 except that the anthraquinone dye, which is the chromatic colorant (9), was used instead of the chromatic colorant (1). Sheet). The single layer sheet M had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.5 μm.

Next, a white single layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single layer sheet M, the white single layer sheet Q, the white single layer sheet Q, and the single layer sheet M. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

Each of the above evaluations was performed on the produced card. The evaluation results are shown in Table 6.

(Comparative Example 2)
Single-layer sheet N (multicolored color laser marking sheet for cards) in the same manner as in Example 1 except that a perinone dye, which is a chromatic colorant (10), was used instead of the chromatic colorant (1). ) Was produced. The single-layer sheet N had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.5 μm.

Next, a white single layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single layer sheet N, the white single layer sheet Q, the white single layer sheet Q, and the single layer sheet N. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Comparative Example 3)
Single-layer sheet O (multicolored color laser marking for cards) in the same manner as in Example 1 except that instead of the chromatic colorant (1), an iron phthalocyanine pigment as the chromatic colorant (11) was used. Sheet). The single-layer sheet O had a sheet thickness of 150 μm and an average surface roughness (Rz) on both sides of the sheet of 3.5 μm.

Next, a white single layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single layer sheet O, the white single layer sheet Q, the white single layer sheet Q, and the single layer sheet O. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Comparative Example 4)
Single-layer sheet P (multicolor coloring laser marking sheet for cards) in the same manner as in Example 1 except that perylene black, which is the chromatic colorant (12), was used instead of the chromatic colorant (1). Was made. The single layer sheet P had a sheet thickness of 150 μm and an average surface roughness (Rz) of both sides of the sheet of 3.5 μm.

Next, a white single-layer sheet Q is produced in the same manner as in Example 1, and the sheets are arranged in the order of lamination of the single-layer sheet P, the white single-layer sheet Q, the white single-layer sheet Q, and the single-layer sheet P. Laminated and heated and pressurized with a vacuum press machine to produce a card-like laminate (thickness 800 μm). In addition, the thickness of each sheet | seat was 150 micrometers, 250 micrometers, 250 micrometers, and 150 micrometers in the said lamination order.

(Comparative Examples 5 to 11)
A card (card-like laminate) was produced in the same manner as in Example 1 except that the amount was appropriately changed so as to satisfy the blending amounts shown in Table 6. Each of the above evaluations was performed on the produced card. The evaluation results are shown in Table 6.

As is clear from Tables 1 to 6, the laser marking sheets of Examples 1 to 39 could be marked with laser light. In addition, the marked characters, symbols, images, and the like were clearer in the laser marking sheets of Examples 1 to 39 than in the laser marking sheets of Comparative Examples 1 to 11. Moreover, it was excellent in the characteristics of heat-fusibility, sheet cutting property, and sheet formability. That is, the laser marking sheets of Examples 1 to 39 have clearly marked characters, symbols, images, etc., and have excellent characteristics in heat-fusibility, sheet cutting properties, and sheet formability. It was.

In Examples 1 to 12, marking derived from the chromatic colorant can be clearly performed by vaporizing and changing the color of carbon black by irradiation with laser light having a wavelength of 1,064 nm, and laser light by irradiation with laser light having a wavelength of 532 nm. As a result, the chromatic colorant was also vaporized and discolored, and it was confirmed that a white marking could be formed.

In Comparative Examples 1 and 2, the chromatic colorants (9) and (10) contained in the single-layer sheets M and N do not have an exothermic peak due to differential thermal analysis. Only happened. Therefore, markings with different color tones were not formed.

In Comparative Example 3, the chromatic colorant (11) contained in the single-layer sheet O has an exothermic peak temperature of less than 360 ° C., and thus is derived from the chromatic colorant even when irradiated with lower energy laser light. The formation of the marking was insufficient.

In Comparative Example 4, since the chromatic colorant (12) contained in the single-layer sheet P has an exothermic peak temperature exceeding 590 ° C., markings having different tones were not formed.

In Comparative Examples 7 to 9, polyacetal resin, polyamide resin, or polyurethane resin was used as the resin contained in the resin composition, but it was difficult to form a uniform sheet. Further, in Comparative Examples 7 to 9, the heat-fusibility with the core sheet was very poor and peeling occurred.

The multicolor coloring laser marking sheet for cards of the present invention can be used as a sheet constituting various cards.

100, 101: Multicolor laser marking sheet for card, 21, 22: Laser light, 11, 12: Laser light irradiation part, 13: Fabric part.

Claims

A sheet made of a laser marking resin composition containing a thermoplastic resin, a chromatic colorant, and a black substance is provided. By irradiating a laser beam, marking is performed in two or more different colors including white and chromatic colors. A seat
The thermoplastic resin is at least one thermoplastic resin selected from the group consisting of an acrylic resin, a polycarbonate resin, a styrene resin, and an amorphous aromatic polyester resin;
The chromatic colorant includes at least one skeleton selected from the group consisting of a phthalocyanine skeleton, a diketopyrrolopyrrole skeleton, a dioxazine skeleton, a quinacridone skeleton, a quinophthalone skeleton, a perylene skeleton, and a metal complex skeleton, and It has an exothermic peak in the range of 360 to 590 ° C. in differential thermal analysis,
The black substance is a substance that itself disappears or discolors by receiving laser light,
Multicolored laser marking sheet for cards with a total thickness of 100 to 300 μm.
The multicolor coloring laser marking sheet for cards according to claim 1, wherein the black material is at least one selected from the group consisting of carbon black, titanium black, and black iron oxide.
The blending amount of the chromatic colorant is 0.001 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin, and the blending amount of the black substance is 0.000 with respect to 100 parts by mass of the thermoplastic resin. The multicolored laser marking sheet for cards according to claim 1 or 2, wherein the amount is 01 to 2 parts by mass.
4. The multicolor coloring laser marking for card according to claim 1, wherein the resin composition contains 0.001 to 1 part by mass of a white material with respect to 100 parts by mass of the thermoplastic resin. Sheet.
The multicolor coloring laser marking sheet for cards according to any one of claims 1 to 4, which is a single layer sheet.
A multilayer sheet comprising a surface layer and an inner layer,
The surface layer is a transparent resin layer composition comprising at least one thermoplastic resin selected from the group consisting of an acrylic resin, a polycarbonate resin, a styrene resin, and an amorphous aromatic polyester resin. Layer,
The multicolor coloring laser marking sheet for cards according to any one of claims 1 to 4, wherein the inner layer is a layer made of the laser marking resin composition.
The multicolor coloring laser marking sheet for cards according to claim 6, wherein the ratio of the thickness of the inner layer to the total thickness of the multilayer sheet is 30 to 85%.
The multicolor coloring laser marking sheet for cards according to any one of claims 1 to 7, wherein the average surface roughness (Rz) is 1 to 10 µm.
The multicolor laser marking sheet for cards according to any one of claims 1 to 8, wherein an L value in measurement of lightness of the fabric color is less than 50.
The multicolored laser marking sheet for cards according to any one of claims 1 to 9, wherein the whiteness of the laser-marked portion is 20 or more.
The multicolor coloring laser marking sheet for cards according to any one of claims 1 to 10, wherein the contrast between the fabric color and the color of the laser-marked portion is 2 or more.
When the multicolor coloring laser marking sheet for cards according to any one of claims 1 to 11 is irradiated with two or more different wavelengths of laser light, the wavelength of the low energy laser light and the high energy laser light The laser marking method whose difference with a wavelength is 100 nm or more.