JPWO2015178378A1 - Laser transfer marking film and laser marking product using the same - Google Patents

Abstract

The film for laser transfer marking 11 includes a glass frit 12, a copper oxide 13, and a resin 14.

Description

  The present invention relates to a film for laser transfer marking and a laser marking product using the same.

  A method of marking using laser light is widely known as a method of notifying various information such as a production number and a production date for identifying various products. As a method of marking in this way, a method for marking various information using a film on a substrate on which product marking is performed, and a method for marking various information by directly cutting the surface of the substrate on which product marking is performed with a laser beam. And how to do it.

  Furthermore, as a method of marking various information using a film as described above, a method in which a film in which various information is marked using a laser beam is attached to various base materials, a film and various products are stacked, and a laser is provided there. There is known a method of marking by irradiating light and transferring various information from a film to a substrate on which product marking is performed. The film used in the latter method is called a film for laser transfer marking or a laser transfer film.

  When marking a glass substrate using such a laser transfer marking film, for example, a laser transfer marking film including a resin layer containing a glass frit and an adhesive layer may be used.

  As an example of a method for marking on a glass substrate using a film for laser transfer marking, the following Patent Document 1 describes the discriminability of a marking portion using a laser transfer film containing a glass flux pigment and a laser sensitive pigment. An improved laser marking technique is disclosed.

  Patent Document 2 listed below discloses a laser marking technique in which the visibility of a marking portion is improved by using a laser transfer film containing a titanium donor and a carbon donor in a pigment layer.

JP 2005-520715 A JP 2011-1260 A

In recent years, the design of laser marking is being replaced from a one-dimensional code such as a barcode to a two-dimensional code such as a QR code (registered trademark) having a larger amount of information. Such a two-dimensional code (two-dimensional barcode) is used for production management in the automobile industry, for example. The technology for laser marking two-dimensional codes requires more precision than one-dimensional codes. However, in the method using the laser transfer marking film described in Patent Document 1 and Patent Document 2, when the output of the laser beam is increased in order to improve transferability, the substrate around the marking portion is made of a resin such as carbide. There is a tendency to get dirty with decomposition products. For this reason, a marking part and a base material become unclear, visibility falls, and the situation where a two-dimensional code cannot be read easily arises. Therefore, in the same method, when the output of the laser beam is lowered in order to improve the visibility, the glass frit is not sufficiently melted during the irradiation of the laser beam, so that the marking portion tends to be difficult to be transferred.
Therefore, the laser transfer is designed so that the glass frit melts and the resin decomposes and burns at the laser light irradiation site, while the glass frit hardly melts and the resin does not decompose and burn outside the laser irradiation site. There is a need for marking films. A laser marking product that has been marked using such a film is excellent in both the transferability of the marking portion to the substrate upon irradiation with laser light and the visibility of the marking portion after irradiation with laser light.

  Accordingly, an object of the present invention is to provide a film for laser transfer marking excellent in both transferability and visibility, and a laser marking product using the same.

  Means for achieving the above-described object are as follows.

  That is, this invention is a film for laser transfer marking containing glass frit, copper oxide, and resin.

  In the film for laser transfer marking, the mass ratio of the glass frit and the copper oxide may be in the range of 100 / 0.5 to 100/100.

  In the film for laser transfer marking, the mass ratio of the glass frit and the resin may be in the range of 100/1 to 100/300.

  In the laser transfer marking film, the resin may include at least one of a vinyl butyral resin and a (meth) acrylic resin.

Moreover, this invention is a laser marking product to which laser marking was given using the film for laser transfer markings as described in any one of the above.

  ADVANTAGE OF THE INVENTION According to this invention, the film for laser transfer markings which was excellent in both transferability and visibility, and a laser marking goods using the same can be provided.

It is a figure which shows the example of the cross section of the film for laser transfer markings. It is a figure which shows the example of the aspect at the time of the transportation of the film for laser transfer markings shown in FIG. It is a figure which shows the example of the aspect at the time of use of the film for laser transfer markings shown in FIG. It is a figure which shows a mode that a laser beam is irradiated in the laser marking method using the film for laser transfer markings shown in FIG. It is a figure which shows an example of a laser marking product.

  Hereinafter, a laser transfer marking film according to the present invention and a laser marking product using the same will be described in detail with reference to the drawings, taking an embodiment as an example.

FIG. 1 is a diagram showing an example of a cross section of the laser transfer marking film 11 of the present embodiment.
A laser transfer marking film 11 shown in FIG. 1 includes a glass frit 12, a copper oxide 13, and a resin 14.

FIG. 2 is a diagram showing an example of an aspect of the laser transfer marking film 11 shown in FIG.
As shown in FIG. 2, the laser transfer marking film 11 may be laminated on a process film 21 used in the process of manufacturing the laser transfer marking film 11 and transported. However, in this embodiment, when using the film 11 for laser transfer marking, the said process film 21 is peeled. The process film 21 is a film that is used in a process of manufacturing a laser transfer marking film and supports the laser transfer marking film 11.

FIG. 3 is a diagram showing an example of a mode when the laser transfer marking film 11 shown in FIG. 1 is used.
As shown in FIG. 3, the laser transfer marking film 11 is used by being installed on a base material 41. The base material 41 is an object to be laser marked by irradiating the laser transfer marking film 11 with laser light. At this time, it is possible to fix the laser transfer marking film 11 on the base material 41 more appropriately by fixing the laser transfer marking film 11 on the base material 41 using a jig or the like (not shown). preferable.

FIG. 4 is a diagram showing a state in which laser light is irradiated in the laser marking method using the laser transfer marking film 11 shown in FIG.
When marking the base material 41, the laser transfer marking film 11 is irradiated with the laser beam 31 in a state where the laser transfer marking film 11 is placed on the base material 41 as shown in FIG. .

FIG. 5 is a diagram illustrating an example of the laser marking product 51 of the present embodiment.
As shown in FIG. 4, the laser transfer marking film 11 placed on the base material 41 is irradiated with the laser light 31, and then the laser transfer marking film 11 is removed to provide the marking portion 52 on the base material 41. It will be a thing. Therefore, the laser marking product 51 in the present embodiment is laser-marked using the laser transfer marking film 11.

  Next, the structure of the film 11 for laser transfer marking of this embodiment is demonstrated.

The glass frit 12 included in the film for laser transfer marking 11 is sodium, lithium, potassium, calcium, barium, magnesium, aluminum, titanium, silicon, vanadium, bismuth, boron, phosphorus, tellurium, iron, lead, manganese, zinc, tungsten Metal oxides such as molybdenum and antimony.
The glass frit 12 may contain these metal oxides alone, or may contain two or more kinds.

Examples of the glass frit containing an alkali metal oxide include Asahi Glass Co., Ltd. product names LS-5-300M (softening temperature 553 ° C.), 1991Y10 (softening temperature 524 ° C.), and DL828 (softening temperature 861 ° C.).
As the glass frit 12 containing an oxide of an alkaline earth metal, product names ASF1702 (softening temperature 807 ° C.), ASF1898 (softening temperature 527 ° C.), ASF1939 (softening temperature 716 ° C.), ASF1941B (softening) manufactured by Asahi Glass Co., Ltd. Temperature 683 ° C.).
As the glass frit 12 containing vanadium oxide, trade names VBZ-2 (softening temperature 361 ° C.), VBP-8 (softening temperature 409 ° C.), V-35 (softening temperature 411 ° C.), VBP manufactured by Okamoto Glass Co., Ltd. -12 (softening temperature 422 ° C.), VBPZ-6 (softening temperature 535 ° C.), product name TNS031 (softening temperature 362 ° C.) manufactured by Asahi Glass Co., Ltd.
As the glass frit 12 containing phosphorus oxide, trade names P-9 (softening temperature 508 ° C.), P-6 (softening temperature 576 ° C.), P-5 (softening temperature 585 ° C.) manufactured by Okamoto Glass Co., Ltd., Asahi Glass The product name KP312 (softening temperature 325 degreeC) made by Corporation | Co., Ltd. is mentioned.
Examples of the glass frit 12 containing lead oxide include Asahi Glass Co., Ltd. product names 2502 (softening temperature 316 ° C.), ASF 1370 (softening temperature 615 ° C.), and ASF 1380 (softening temperature 690 ° C.).
As the glass frit 12 containing a bismuth oxide, product name ASF1100 (softening temperature 440 ° C.) manufactured by Asahi Glass Co., Ltd. may be mentioned.
As the glass frit 12 containing zinc and lead oxide, Asahi Glass Co., Ltd. product name ASF1550 (softening temperature 540 ° C.) can be mentioned.
As the glass frit 12 containing zinc oxide, product name ASF1700F (softening temperature 810 ° C.) manufactured by Asahi Glass Co., Ltd. may be mentioned.
As the glass frit 12 containing oxides such as boron, silicon, aluminum, and titanium, trade names BSZ-3 (softening temperature 646 ° C.), BS-1 (softening temperature 690 ° C.), CAS-9F (made by Okamoto Glass Co., Ltd.) Product name ZX-1 (softening temperature 875 ° C), CB001 (softening temperature 770 ° C), HHR0704 (softening temperature 924 ° C), HHR1010 (softening temperature 970 ° C), 1928 (softening temperature) 560 ° C), K-836 (softening temperature 774 ° C), AP5762D (softening temperature 925 ° C), AP5316A (softening temperature 720 ° C), K-303 (softening temperature 373 ° C).

The metal oxide contained in the glass frit 12 is in the form of powder, flakes, or a mixture thereof. Further, the volume average particle diameter of the metal oxide contained in the glass frit 12 that can be suitably used for the laser transfer marking film 11 is not particularly limited, but, for example, D50 is in the range of 0.1 μm to 100 μm.
The volume average particle diameter of the metal oxide contained in the glass frit 12 can be measured by a laser diffraction / scattering particle size analysis method.

  The glass frit 12 is preferably colored. In this case, when the base material 41 to be marked is colorless such as soda lime glass, the contrast between the marking portion 52 and the base material 41 is increased by using the colored glass frit 12, and the visibility of the marking portion 52 is improved. Can be good.

  Thus, when the contrast of the marking part 52 and the base material 41 becomes high, the visibility is excellent. For example, when the design of the marking part is a barcode, the readability of the barcode is good.

  The softening temperature of the glass frit 12 is preferably 300 ° C to 1000 ° C. If the softening temperature of the glass frit is 300 ° C. or higher, melting of the glass frit due to laser light irradiation can be suppressed, so that visibility and contrast are hardly lowered. Moreover, if the softening temperature is 1000 ° C. or lower, the output of laser light can be suppressed while maintaining transferability, so that the resin at the part adjacent to the laser light irradiation part in the laser transfer marking film 11 is decomposed. Is less likely to occur.

  In the present specification, the softening temperature is an inflection point temperature in differential thermal analysis (DTA) measurement.

As described above, the laser transfer marking film 11 includes the copper oxide 13. Copper oxide 13 includes copper oxide (II) and copper oxide (I). The copper oxide 13 included in the laser transfer marking film 11 can be suitably used regardless of whether it is composed of any of copper (II) oxide, copper (I) oxide, and mixtures thereof.
In the laser transfer marking film 11, in order to improve both the transferability of the marking portion to the base material during laser light irradiation and the visibility of the marking portion after laser light irradiation, a laser light irradiation site In this case, the glass frit is melted and the resin is decomposed and burned. On the other hand, it is preferable that the glass frit is not melted and the resin is not decomposed and burned except at the laser irradiation site. For example, at the time of laser light irradiation, it is preferable that the laser transfer marking film 11 includes a material having a high thermal conductivity at the laser light irradiation portion and a material having a low heat conductivity at a portion other than the laser light irradiation portion.
Further, the metal oxide at the site irradiated with laser light is reduced by heat when irradiated with laser light.
Therefore, in the laser transfer marking film 11 containing copper oxide according to the present embodiment, the copper oxide is reduced to copper having a high thermal conductivity by the heat of the laser light at the laser light irradiation portion, and the laser is irradiated at a portion other than the laser light irradiation portion. The copper oxide has a low thermal conductivity.
The thermal conductivity of copper oxide is about 3.22 to 3.74 W / m · K, and the thermal conductivity of copper is about 401 W / m · K. That is, the ratio of thermal conductivity between the oxide (copper oxide) and the reduced product (copper) is 100 times or more.
Therefore, the film 11 for laser transfer marking according to the present embodiment has a large difference in thermal conductivity between the laser beam irradiation site and the laser beam irradiation site. For this reason, the glass frit is easily melted and the resin is easily decomposed and burned at the laser beam irradiation site. On the other hand, the glass frit is difficult to melt and the resin is difficult to be decomposed and burned outside the laser irradiation part. For this reason, the marking using the film 11 for laser transfer marking is excellent in transferability.
Further, when the laser transfer marking film 11 is irradiated with laser light, as described above, the copper oxide 13 at the irradiated portion is reduced to change to copper, and heat is sufficiently transmitted at the irradiated portion of the laser light. The glass frit 12 is melted at the irradiated portion, the resin 14 is decomposed and burned, and the heat is sufficiently transmitted to the base material 41 in contact with the marking portion. For this reason, a marking part and a base material show favorable transferability. On the other hand, except for the portion irradiated with the laser beam, since the copper oxide 13 having a low thermal conductivity remains as described above, it is difficult for heat to be transmitted, and glass frit softening, resin decomposition, and combustion are difficult to occur. Is hard to be contaminated. For this reason, the visibility of the marking part 52 in the laser marking product 51 is excellent.

The volume average particle size of the copper oxide 13 included in the film for laser transfer marking 11 is not particularly limited, but for example, D50 is preferably 0.1 μm to 10 μm.
The volume average particle diameter of the copper oxide 13 can be measured by a laser diffraction / scattering particle size analysis method.

The mass ratio of the glass frit 12 and the copper oxide 13 [the mass of the glass frit 12 / the mass of the copper oxide 13] included in the laser transfer marking film 11 is preferably in the range of 100 / 0.5 to 100/100. 100/6 to 100/25 is more preferable. When the mass ratio between the glass frit 12 and the copper oxide 13 is 100 / 0.5 or more, heat is sufficiently transmitted to the base material 41 when the laser beam is irradiated, and the glass frit 12 can be sufficiently melted. Furthermore, if the mass ratio of the glass frit 12 and the copper oxide 13 is 100/6 or more, the amount of copper changed by reduction of the copper oxide 13 can be secured at the laser beam irradiation site. Then, heat is sufficiently transmitted by copper having a high thermal conductivity, the glass frit 12 is melted at the laser light irradiation site, the resin 14 is decomposed and burned, and the heat is sufficiently transmitted to the base material 41 in contact with the marking portion. For this reason, a marking part and a base material show more favorable transferability.
On the other hand, if the mass ratio between the glass frit 12 and the copper oxide 13 is 100/100 or less, the glass frit is sufficiently fused with the laser beam to increase the adhesion strength between the marking portion and the substrate. Can do. Furthermore, if the mass ratio between the glass frit 12 and the copper oxide 13 is 100/25 or less, the heat is not easily transmitted to the glass frit because it remains the copper oxide 13 with a low thermal conductivity except at the laser light irradiation site. Softening, resin decomposition, and combustion are difficult to occur, and the area around the marking is difficult to be contaminated. For this reason, the visibility of the marking part 52 in the laser marking product 51 is excellent.

As described above, the laser transfer marking film 11 includes the resin 14. The resin 14 is not particularly limited as long as it can sufficiently transmit the laser beam 31 and can form the film 11 for laser transfer marking.
The resin 14 included in the laser transfer marking film 11 may be either a thermoplastic resin or a thermosetting resin.

Examples of the resin 14 used for the laser transfer marking film 11 include (meth) acrylic resin, vinyl butyral resin, vinyl chloride resin, polyester, polystyrene, and polyurethane.
These resins may be used alone, or two or more kinds of resins may be used in combination.
In particular, the laser beam to be irradiated can be sufficiently transmitted, the film transferability of the film 11 for laser transfer marking is excellent, the handleability of the film is good, and when the laser beam is irradiated, the resin content hardly remains in the marking portion. At least one of vinyl butyral resin and (meth) acrylic resin can be suitably used.

  The vinyl butyral resin used for the laser transfer marking film 11 can be obtained by reacting polyvinyl alcohol and butyraldehyde under acidic conditions.

The (meth) acrylic resin used for the laser transfer marking film 11 is an acrylic resin or a methacrylic resin, and a resin containing 50% by mass or more of a polymer obtained by singly or copolymerizing an acrylic monomer or a methacrylic monomer. It is.
Examples of the acrylic monomer include monomers such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, and 2-ethylhexyl acrylate.
Examples of the methacrylic monomer include monomers such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and ethylene glycol dimethacrylate.
Examples of the functional group possessed by the acrylic monomer and methacrylic monomer include a carboxyl group, a hydroxyl group, a mercapto group, an epoxy group, an amide group, and a methylolated acrylamide group.

  The mass ratio of the glass frit 12 and the resin 14 included in the laser transfer marking film 11 [the mass of the glass frit 12 / the mass of the resin 14] is preferably in the range of 100/1 to 100/300, and 100/10. More preferably, it is ~ 100/160. When the mass ratio of the glass frit 12 and the resin 14 is 100/1 or more, the film-forming property of the film 11 for laser transfer marking is excellent. If the mass ratio is 100/300 or less, the glass frit 12 is easily transmitted between the adjacent glass frits when the laser beam is irradiated, and the glass frit 12 is sufficiently softened. The adhesion strength of the base material 41 can be increased. That is, transferability is improved.

The film 11 for laser transfer marking can contain a laser absorber. In this specification, the laser absorber is a material that promotes the absorption of the energy of the laser beam 31 when it is irradiated with the laser beam and promotes the conversion into heat, and promotes the melting of the glass frit 12 and the decomposition of the resin 14. It shows the action to do. When the film 11 for laser transfer marking contains a laser absorber, since the output of the laser beam at the time of laser beam irradiation can be made small and the visibility of the obtained laser marking product increases more, it is preferable.
Such a laser absorber can be appropriately selected depending on the type of laser light to be irradiated.
Examples of the laser absorbent that can be suitably used in the present invention include iron, magnesium, molybdenum, nickel, tin, titanium, zinc and oxides thereof, carbon black, mica, phthalocyanine, naphthalocyanine, and azo dyes.

  The film for laser transfer marking 11 can contain a colorant. By including the colorant, the hue and contrast of the marking portion 52 shown in FIG. 5 can be adjusted. As the colorant, various organic and inorganic pigment dyes can be suitably used. Specifically, carbon black and titanium oxide can be exemplified as the colorant. The colorant can be appropriately selected according to the hue of the base material 41 so that the contrast with the marking portion 52 is increased.

The film for laser transfer marking 11 can contain various additives as long as the visibility of the marking portion 52 is not impaired. Examples of such additives include a dispersant, a light stabilizer, a heat stabilizer, a plasticizer, an infrared absorber, a low glass transition point (Tg) resin, a tackifier, and a filler. For example, by including a plasticizer and a low glass transition point (Tg) resin, cracks and the like are less likely to occur during film formation, marking, and storage. Moreover, since the adhesiveness of a film and a base material goes up at the time of the lamination | stacking with the base material 41 by including a plasticizer, a low glass transition point (Tg) resin, and a tackifier, the film 11 for laser transfer marking at the time of marking Handleability is improved.
The low glass transition point (Tg) resin that can be used for the film 11 for laser transfer marking is particularly preferably one having a glass transition point of 0 ° C. or lower.

  The thickness of the film 11 for laser transfer marking is not particularly limited, but is preferably in the range of 2 μm to 200 μm. If the thickness of the laser transfer marking film 11 is 2 μm or more, the transfer amount of the laser transfer marking film 11 can be ensured, the contrast is high, and the marking with excellent visibility can be performed. 11 can be used. Moreover, if the thickness of the film 11 for laser transfer marking is 200 μm or less, it is possible to suppress raising the output of laser light or lengthening the irradiation time in order to obtain adhesion between the marking portion 52 and the substrate 41, It is possible to suppress the generation of a resin decomposition product around the marking portion when the laser beam is irradiated, the carbide is not excessively generated, and the contamination around the marking portion is reduced, so that the visibility of the marking portion is further improved.

  The manufacturing method of the laser transfer marking film 11 is preferably a casting method because the thickness is uniform. In an example of the casting method, the glass frit 12, the copper oxide 13, and the resin 14 are dispersed in an organic solvent to form a dope, and then the dope is coated on the process film 21 and then dried to form a film. A method is mentioned.

  Moreover, as a manufacturing method of the film 11 for laser transfer marking, the method of forming into a film by printing on a process film etc. can be mentioned, for example, the method of forming into a film by the calendar method and the extrusion method other than the casting method.

The laser marking product 51 using the laser transfer marking film 11 can be typically produced as follows.
Usually, the process film 21 is laminated on the film 11 for laser transfer marking as shown in FIG.
Therefore, as shown in FIG. 2, a laser transfer marking film 11 laminated on the process film 21 is prepared. Subsequently, after peeling off the laser transfer marking film 11 from the process film 21, the laser transfer marking film 11 and the substrate 41 are overlapped as shown in FIG. At this time, it is preferable to overlap the laser transfer marking film 11 and the base material 41 so that the laser transfer marking film 11 is directly disposed on the base material 41. This is because if an adhesive layer or the like is interposed between the laser transfer marking film 11 and the substrate 41, the marking may be hindered depending on the material of the adhesive layer. Therefore, when the adhesiveness of the laser transfer marking film 11 is small, it is preferable to fix the laser transfer marking film 11 on the substrate 41 with a jig or the like (not shown) as described above.
Next, as shown in FIG. 4, the laser transfer marking film 11 of this laminate is irradiated with a laser beam 31 so as to have a desired marking pattern. At that time, the copper oxide 13 included in the laser transfer marking film 11 is reduced at the irradiated portion of the laser beam, and copper having a high thermal conductivity is generated. The produced copper can sufficiently transfer heat to the glass frit 12 and the resin 14 at the irradiation site of the laser beam 31. Further, heat is sufficiently transmitted to the portion of the base material 41 to be marked, whereby the melt of the laser transfer marking film 11 and the base material 41 are in close contact with each other. When the melt of the laser transfer marking film 11 is in close contact with the base material 41, the marking portion 52 is formed. Furthermore, the resin 14 in the laser transfer marking film 11 is decomposed and burned at the laser light irradiation site. On the other hand, except for the laser beam irradiation part (part that becomes the marking part), it contains copper oxide with a low thermal conductivity, so that heat is not easily transmitted, and the softening of the glass frit and the decomposition of the resin are suppressed. Is less susceptible to contamination.
Next, the excess laser transfer marking film 11 that has not contributed to the marking is removed from the substrate 41. Finally, laser marking was performed using the film for laser transfer marking shown in FIG. 5 by rubbing the periphery of the marking portion 52 with cotton or cloth as necessary, and removing a decomposition product of the resin. A laser marking product 51 is obtained. The laser marking product 51 thus obtained has good transferability because the marking part is difficult to peel off even when the marking part 52 is rubbed with a nail.

  Further, the film for laser transfer marking 11 may be a backing film in order to improve the handling during the marking operation.

  The base material 41 to be laser-marked using the laser transfer marking film 11 is typically made of glass, ceramic, polycarbonate, PET, or the like. In particular, when the film for laser transfer marking 11 is used, a laser marking product 51 having a high contrast between the marking portion and the base material and excellent visibility can be obtained even for a glass base material that has been difficult to mark conventionally. .

The laser transfer marking film 11 can be applied to a substrate other than a planar substrate. For example, the present invention can also be applied to a substrate having a curved surface, such as an electric appliance such as a fluorescent lamp and various light bulbs, a chemical container, a medical glass appliance, and an optical appliance such as a lens.
Furthermore, it can be applied to the surface of a substrate having irregularities such as frosted glass.

  If the substrate 41 to be laser-marked is a glass capable of sufficiently transmitting laser light and the surface thereof is smooth, the laser transfer marking film 11 is laminated on the substrate 41 after the laser transfer marking film 11 is overlaid. You may irradiate the laser beam 31 from the material 41 side (not shown).

  Examples of the laser beam that can be used to manufacture the laser marking product 51 include a fiber laser, a carbon dioxide gas laser, and a YAG laser.

  Hereinafter, the effects of the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

  The transferability of the marking part to the substrate, the contrast between the substrate and the marking part, and the visibility of the marking part were confirmed by the following methods.

(1) Transferability Transferability of the marking portion to the substrate was determined by the following procedure.
The marking part of each Example and Comparative Example is rubbed with a nail three times, and the end of the printed character is observed from the surface on the marking part side using an optical microscope (OLYMPUS BX51), and visually observed according to the following criteria Judged by. ○ and ◎ were passed, and among the passes, the following were particularly excellent as ◎.
A: The end of the character is sharp and clean.
○: The character edge is clean.
(Triangle | delta): The burr | flash is seen in the character edge part, or one part is peeling.
X: 50% or more of the characters in the marking portion are peeled off.

(2) Contrast The contrast between the base material and the marking portion was measured and determined by the following procedure.
A white film (HiS-Cal5010 made by Nippon Carbide Industries Co., Ltd.) is applied under the marking part of the laser marking product of each Example and Comparative Example, and a colorimeter (CM-3600D made by Konica Minolta Co., Ltd.) is used as a basis. The material and the marking portion were measured, their color difference (ΔE) was determined, and judged according to the following criteria. ◎ and ○ were accepted.
A: ΔE is 15 or more.
○: ΔE is less than 15 to 10 or more.
X: ΔE is less than 10.

(3) Visibility The visibility of the marking portion was determined by laser marking a two-dimensional barcode having the same pattern as in FIG. 1 of JIS X0510: 2004 in a 10 mm square, and determining the marking performance.
The visibility of the marking part was measured and determined by the following procedure.
A white film (HiS-Cal5010 made by Nippon Carbide Industries Co., Ltd.) is applied under the marking part of the laser marking product of each Example and Comparative Example, and the marking part is a two-dimensional barcode reader (Product name SR-, made by Keyence Corporation). 600), the marking part was read 10 times and judged according to the following criteria. ○ and ◎ were passed, and among the passes, the following were particularly excellent as ◎.
A: Can be read 10 times.
○: Read 9 times.
X: Can be read 8 times or less.

Example 1
100 parts by mass of product name BS-1 (softening temperature 690 ° C.) manufactured by Okamoto Glass Co., Ltd., which is a glass frit, is dispersed in 100 parts by mass of a methyl ethyl ketone solvent. Oreate trade name Sorgen 30V 0.50 parts by mass, plasticizer Sumitomo Chemical Co., Ltd. triethylene glycol 2.0 parts by mass and Wako Pure Chemical Industries, Ltd. copper oxide (II) 6.0 Next, 7.0 parts by mass of Sekisui Chemical Co., Ltd. vinyl butyral resin product name S-REC BM-S, which is a resin, was mixed and then filtered using a 200-mesh wire mesh to obtain a dope. The dope was applied on a process film, which was a PET film having a thickness of 38 μm, using an applicator, and then dried at 100 ° C. for 3 minutes to obtain a film for laser transfer marking having a thickness of 100 μm.

  The obtained film for laser transfer marking was peeled off from the process film, and the surface that was in contact with the process film was stacked on a soda-lime glass substrate having a thickness of 1.8 mm so as to be in contact with the substrate to obtain a laminate. Next, this laminate was irradiated with laser light in a predetermined pattern from the laser transfer marking film side using a fiber laser product name fiber laser marker LP-Z manufactured by Panasonic Corporation. The laser light irradiation conditions were a wavelength of 1064 nm, an output of 6 W, and a scan speed of 50 mm / second. After irradiating the laser beam, the film for laser transfer marking was peeled off from the substrate, and the marking portion was rubbed with cotton to remove the decomposition product of the resin. Furthermore, even if the marking part was rubbed with a nail, it was confirmed that the marking part did not peel off and adhered.

(Example 2)
The same as Example 1 except that the product name VBP-12 (softening temperature 422 ° C.) manufactured by Okamoto Glass Co., Ltd. was used as the glass frit instead of the product name BS-1 (softening temperature 690 ° C.) manufactured by Okamoto Glass Co., Ltd. The film for laser transfer marking and the laminate of Example 2 were obtained by the procedure described above. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate.

(Example 3)
The same procedure as in Example 1 was used except that product name HHR1010 (softening temperature 970 ° C.) manufactured by Asahi Glass Co., Ltd. was used instead of product name BS-1 (softening temperature 690 ° C.) manufactured by Okamoto Glass Co., Ltd. as the glass frit. A film for laser transfer marking and a laminate of Example 3 were obtained. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

(Example 4, Example 5, Example 6 and Example 7)
Except that vinyl butyral resin was blended in parts by mass shown in Table 1, films for laser transfer marking and laminates of Example 4, Example 5, Example 6 and Example 7 were used in the same procedure as Example 1. Got the body. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

(Example 8, Example 9, Example 10 and Example 11)
Sekisui Chemical Co., Ltd. vinyl butyral resin as resin Resin product name: (meth) acrylic resin product name KP-2341 manufactured by Nissetsu Co., Ltd. instead of ESREC BM-S The film for laser transfer marking and the laminate of Example 8, Example 9, Example 10 and Example 11 were obtained in the same procedure as in Example 1. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

(Example 12, Example 13, Example 14, Example 15, Example 16, and Example 17)
Example 12, Example 13, Example 14, Example 15, Example 16, and Example were carried out in the same procedure as Example 1 except that copper (II) oxide was blended in parts by mass shown in Table 1. The film for laser transfer marking and the laminate of Example 17 were obtained. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

(Example 18)
The procedure of Example 18 was the same as that of Example 18 except that 6.0 parts by mass of copper oxide (I) manufactured by Wako Pure Chemical Industries, Ltd. was used instead of copper oxide (II) manufactured by Wako Pure Chemical Industries, Ltd. A film for laser transfer marking and a laminate were obtained. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

(Example 19)
In Example 1, 2.0 parts by mass of Takara Mica M-101 manufactured by Shiraishi Calcium Co., Ltd. was added as a laser absorber, and the film for laser transfer marking and lamination of Example 19 were performed in the same procedure as in Example 1. Got the body. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

(Example 20)
Film for laser transfer marking and laminate of Example 20 in the same procedure as Example 1 except that 15.0 parts by mass of carbon black-containing black pigment FPGS-5910 manufactured by Dainichi Seika Kogyo Co., Ltd. was added as a colorant. Got. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1, and various determinations were made.

Example 1 of laser transfer marking film prescription, determination result of transferability of marking part to substrate, determination result of contrast between substrate and marking part, and determination result of visibility of marking part from Example 1 Example 10 is shown in Table 1 and Examples 11 to 20 are shown in Table 2.

(Comparative Example 1)
A film for laser transfer marking and a laminate of Comparative Example 1 were obtained in the same procedure as in Example 1 except that copper (II) oxide was not used. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

(Comparative Example 2)
A laser transfer marking film and a laminate of Comparative Example 3 were obtained in the same procedure as in Example 1 except that 2.0 parts by mass of Takara Mica manufactured by Shiroishi Calcium Co., Ltd. was used instead of copper (II) oxide. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

(Comparative Example 3)
Laser transfer of Comparative Example 4 in the same procedure as in Example 1 except that 15.0 parts by mass of the carbon black-containing black pigment trade name FPGS-5910 manufactured by Dainichi Seika Kogyo Co., Ltd. was used instead of copper oxide (II). A marking film and a laminate were obtained. Thereafter, the laminate was irradiated with laser light under the same conditions as in Example 1 to mark the substrate, and various determinations were made.

Prescription of the film for laser transfer marking in Comparative Example 1 to Comparative Example 3 above, determination result of transferability of marking part to base material, determination result of contrast between base material and marking part, and determination of visibility of marking part The results are shown in Table 3.

The laser marking products of the examples all had good transferability, high contrast between the marking portion and the substrate, and excellent visibility. In particular, when the range of copper oxide was 100/6 to 100/25, the transferability and visibility were more excellent.
On the other hand, the laser marking product using each film of Comparative Example 1, Comparative Example 2 and Comparative Example 3 not containing copper oxide resulted in poor visibility.

  By using the laser transfer marking film of the present invention, a laser marking product having a high contrast between the marking portion and the substrate and excellent visibility can be obtained. By performing laser marking using the film for laser transfer marking of the present invention, for example, production numbers and production dates of various products can be indicated.

DESCRIPTION OF SYMBOLS 11 ... Film for laser transfer marking 12 ... Glass frit 13 ... Copper oxide 14 ... Resin 21 ... Process film 31 ... Laser beam 41 ... Base material 51 ... Laser marking Product 52 ... Marking part

Claims (5)

  Laser transfer marking film containing glass frit, copper oxide and resin.   The film for laser transfer marking according to claim 1, wherein a mass ratio between the glass frit and the copper oxide is in a range of 100 / 0.5 to 100/100.   The film for laser transfer marking according to claim 1 or 2, wherein a mass ratio between the glass frit and the resin is in a range of 100/1 to 100/300.   The film for laser transfer marking according to any one of claims 1 to 3, wherein the resin includes at least one of a vinyl butyral resin and a (meth) acrylic resin.   A laser marking product to which laser marking is applied using the film for laser transfer marking according to any one of claims 1 to 4.

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