JP2003321616A - Resin composition for marking use, marking method and device therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly transparent resin composition for marking use, and to provide a method and a related device for easily and quickly marking a molded form of the resin composition with clear and high-precision letters or patterns such as illustrations. <P>SOLUTION: The resin composition comprises a transparent resin and an active energy ray-sensitive marking component. The method and the related device for marking the resin molded form by being irradiated with active energy rays are also provided respectively. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a marking resin composition containing a transparent resin and a marking component sensitive to active energy rays. Further, the present invention is
The resin composition is molded into a resin molded body having a desired shape,
The present invention also relates to a marking method for imparting a pattern such as letters or illustrations to the resin molded body by irradiating it with an active energy ray. Furthermore, the present invention controls (1) an active energy ray generating section, (2) a driving section for moving the irradiation section of the active energy ray, and (3) (1) and (2) to control the active energy ray. The present invention relates to a marking device for use in the method, which has a computer control unit for adjusting the irradiation amount of a line and irradiating it to a proper position.

[0002]

2. Description of the Related Art Conventionally, it has been widely practiced to mark desired characters and illustrations on the surface of a resin molded product or a resin-coated molded product, and various methods are known as the marking method. There is. For example, the method of marking with a paint is the most common, but the processing cost is high, the environmental pollution due to the solvent is a concern, and the marking accuracy is limited. Further, recently, as a method of performing marking simply and efficiently, marking by irradiation with laser light has been actively performed. In this marking method using laser light irradiation, the portion irradiated with laser light in the form of letters or illustrations is discolored by heat energy, and letters or illustrations can be identified by the scattering of light.

For example, in JP-A-9-302236, it is possible to perform laser marking by irradiating a laser beam after molding a resin composition comprising a leuco dye, a color-forming auxiliary component and a thermoplastic resin. Is disclosed. However, the heat of kneading causes the reaction of the color-forming component, so that the color-forming component is limited and the degree of freedom in color development is limited. Further, Japanese Patent Application Laid-Open No. 11-92632 discloses a technique of irradiating a laser beam on an epoxy resin containing a copper compound and a nickel compound as a color former to perform laser marking on the surface of a resin molded product. However, in this case, the marking is limited to black. JP-A-8-120133 discloses a resin composition capable of chromatic laser marking in which a compound such as titanium black is mixed with a rubber-reinforced vinyl-based resin. In this case, the resin is rubber-reinforced. It is limited to vinyl-based resins, and its application development is limited.

On the other hand, Japanese Patent Publication No. 7-69524 discloses that
A technique for irradiating a transparent resin with laser light or the like to mark the inside of the resin has been disclosed, but in this case there is a problem that it is limited to internal processing by scorching, and there is a restriction on the application development of that technology. . In general, when such a transparent resin is irradiated with laser light or the like, marking is often impossible, and it is difficult to obtain the light energy required for marking unless the output of laser light is considerably increased. In order to avoid this problem, a method of applying a chromatic color pattern to the inside of the transparent resin by two-color molding or insert molding has been proposed, but it requires sophisticated means and requires a new design for each new design. Since the mold has to be manufactured, it takes time and cost, and it is not possible to deal with various designs.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly transparent and markable resin composition. More specifically, it is intended to provide a highly transparent marking resin composition capable of marking with a low output active energy ray.

Another object of the present invention is to provide a method and apparatus for easily and quickly marking clear, high-speed and high-accuracy patterns such as letters and illustrations on a resin molded product made of the resin composition. is there.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a resin molded product comprising a resin composition containing a marking component sensitive to active energy rays and a transparent resin. In addition, the inventors have found that by irradiating with active energy rays, clear, high-speed and highly accurate marking is possible, and the present invention has been completed.

That is, the present invention is a resin composition containing a marking component sensitive to active energy rays and a transparent resin, which can be marked by irradiation with active energy rays. Is an organic transition metal compound, an organic transition metal compound and at least one
The resin composition is characterized in that it is selected from the group consisting of individual NC = S group-containing compounds, or organic transition metal compounds and inorganic oxide fine particles. More specifically, organic transition metal compounds include chromium hexacarbonyl, molybdenum hexacarbonyl, cobalt octacarbonyl, chlorobis (triphenylphosphine) nickel (II), bis (triphenylphosphine) nickel (II) bromide, and bis (triphenyl). Phosphine) dicarbonylnickel, cyclopentadienyl (triethylphosphine) copper (I),
Chlorotriphenylphosphine Gold (I), Rhodamine B
Gran 00329, Rhodamine B Base 4080
9, copper (II) i-butyrate, dichloro (triphenylphosphine) palladium (II), tetrakis (triphenylphosphine) palladium (O) and methyltrioxorhenium (VII), selected from at least one The compound having an NC = S group is selected from the group consisting of thiourea, 1,3-dimethylthiourea, 1,3-diethyl-2-thiourea and zinc dimethyldithiocarbamate, and the inorganic oxide fine particles are alumina. A marking resin composition. The present invention also includes a method and an apparatus for marking the resin composition by irradiating a resin molded product made of the resin composition with an active energy ray.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As the transparent resin used in the present invention, acrylic resin, polycarbonate, polystyrene, polyethylene terephthalate, ABS, styrene-
Acrylonitrile copolymers, thermoplastic resins such as polyamide, polyethylene, polypropylene and polybutylene terephthalate, thermosetting resins such as urea resins, epoxy resins, unsaturated polyester resins, guanamine resins and melamine resins, among these. In particular, JIS
A resin having a light transmittance of 50% or more according to -K-7105 is preferable. These resins may be used alone or in a mixture of two or more, as long as the transparency is not impaired. Further, known additives, fillers and the like can be added if necessary. Examples of the additive include an antioxidant, an antistatic agent, a flame retardant, an antiaging agent, an infrared absorber, an ultraviolet absorber and the like. Examples of the filler include known fillers such as calcium carbonate, carbon black, talc, silica, mica, clay, magnesium oxide, aluminum hydroxide, titanium oxide, alumina and glass fiber.

In the present invention, the active energy ray is an energy ray that promotes a chemical reaction or a physical change,
For example, Nd: YAG (wavelength 1064 nm), Nd: Y
AG third harmonic (wavelength 355nm), YVO4, YLF
Etc., such as solid-state lasers, semiconductor lasers, carbon dioxide lasers, and mercury lamps. In addition, in the present invention, "sensitivity to active energy rays" means that when the active energy rays are irradiated, the energy causes a chemical reaction to develop a color or a physical change to cause deformation. The marking component contained in the resin composition of the present invention is preferably one that is sensitive to active energy rays and can be melt-kneaded into a transparent resin. Examples of the marking component include an organic transition metal compound, an organic transition metal compound and a compound having at least one NC = S group, or an organic transition metal compound and inorganic oxide fine particles.

Specific examples of the organic transition metal compound used in the present invention include chromium hexacarbonyl, molybdenum hexacarbonyl, cobalt octacarbonyl, chlorobis (triphenylphosphine) nickel (II), and bis (triphenylphosphine) nickel bromide. (II), bis (triphenylphosphine) dicarbonylnickel, cyclopentadienyl (triethylphosphine) copper (I), chlorotriphenylphosphine gold (I), rhodamine B-gran 00329, rhodamine B-base 40809, copper
(II) i-butyrate, dichloro (triphenylphosphine) palladium (II), tetrakis (triphenylphosphine) palladium (O) or methyltrioxorhenium (VI
I). Specific examples of compounds having at least one NC = S group are thiourea, 1,3-dimethylthiourea, 1,3-diethyl-2-thiourea or zinc dimethyldithiocarbamate. As the inorganic oxide, alumina is preferable, and particularly, the average particle diameter is 0.04 μm to 0.8.
0 μm alumina is preferred.

Other marking components that can be used in the present invention include transition metal halides and alkali metal halides. Specific examples of the transition metal halide include silver (I) chloride, and specific examples of the alkali metal halide include potassium iodide. Further, other marking components that can be used in the present invention include calcium carbonate or carbon black.

The content of these marking components is preferably 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the resin composition.

In the resin composition of the present invention, the above components are uniformly mixed (for example, melt-kneaded) by using a kneader such as an extruder, a kneader, a mixer or a roll.
Then, various moldings can be formed using a conventional molding machine such as an extrusion molding machine, an injection molding machine, or a compression molding machine. Then, marking can be performed by irradiating these molded products with active energy rays.

The film or sheet molded from the marking resin composition of the present invention may be laminated or sandwiched with a transparent resin or glass to form a laminate. By using such a laminate, the application of the present resin composition can be expanded, and further improvement in weather resistance and mechanical properties can be expected.

BEST MODE FOR CARRYING OUT THE INVENTION A best mode for carrying out a method and apparatus for easily and quickly marking clear, high-speed and high-accuracy patterns such as letters and illustrations on a resin molded product made of the resin composition of the present invention will be described with reference to the drawings. The details will be described below.

In the marking method of the present invention, a resin composition containing a marking component sensitive to active energy rays and a transparent resin is molded, and the dose of active energy rays is adjusted at the marking portion of the resin molded body. While irradiating, the marking and movement are repeated to mark various characters and illustrations on the resin molded body. A mercury lamp or Nd: YA is used as a means for irradiating active energy rays for marking.
Solid-state lasers such as G, YVO4, and YLF, semiconductor lasers, carbon dioxide lasers, and the like can be used, but it is preferable to use laser light because it is non-contact, has a high marking speed, and is easy to automate and manage processes. Among them, various markings can be applied to the resin molded product by adjusting the irradiation amount using laser light in the near infrared wavelength region. Depending on the type and amount of resin, marking components, additives, etc., for example, when an Nd: YAG laser (wavelength 1064 nm) is used, by setting the irradiation amount to 7.0 to 9.0 kW / cm ² , Color marking can be applied to the inside of the resin molded body. By making the irradiation amount of the laser light about 1.5 times (10.0 to 14.0 kW / cm ² ) as compared with the internal color marking, it is possible to make white marking inside the resin molded body. Also, the irradiation amount of the laser light is about three times as large as that at the time of white marking inside (20.0 to 27.0 kW / c
m ² ) makes it possible to provide white convex markings on the surface of the resin composition. It is also possible to perform Braille processing on the surface of the resin molded body by utilizing the raised height of the white convex marking portion.

In the marking device of the present invention, the active energy ray generating section, the driving section for moving the active energy ray irradiating section, and the active energy ray generating section and the driving section are controlled to irradiate the active energy ray. A computer control unit for adjusting the amount and irradiating it to a proper position is provided, and various characters and illustrations are marked on the resin molded body.

(1) The active energy ray generator generates an active energy ray having strong emission in the infrared wavelength region or the ultraviolet wavelength region, and is selected from those which are inexpensive and capable of pulse operation. As the active energy ray, for example, N
Examples thereof include solid lasers such as d: YAG (wavelength 1064 nm), Nd: YAG third harmonic (wavelength 355 nm), YVO4 and YLF, semiconductor lasers, carbon dioxide lasers, and the like, but are not limited thereto. Among these,
A solid-state laser typified by Nd: YAG can obtain a high peak in the Q-switch mode, and is therefore suitable for the marking method and apparatus of the present invention. When marking is performed by irradiating the above laser light, the laser is operated in the Q-switch mode at a repetition frequency of 1 to 100 KHz, preferably 1.0 to 3.0 KHz, and an average output of 20 W or less to form a resin molded body. Concentrated irradiation is performed, and the focus of laser light is moved at a scanning speed of 100 to 300 mm / sec for marking.

(2) The drive unit for moving the active energy ray irradiation unit may be one that moves a plurality of mirrors by a galvanometer to move the active energy ray irradiation unit, or a resin molding which is a marking object. The active energy ray irradiation unit may be moved by driving a stage having a fixed position.

(3) By controlling the above (1) and (2),
The computer control unit for adjusting the irradiation amount of the active energy ray and irradiating it to the proper position of the resin molding is a PCI controller.
A personal computer NC equipped with a bus can be used.

FIG. 1 is a device diagram showing a marking device according to an embodiment of the present invention. The main configuration of this marking device is an active energy ray generator 1 including a laser oscillator,
A Y-axis mirror 2 held by a galvanometer spindle, a galvanometer 3 for driving the Y-axis mirror 2,
An X-axis mirror 4, a galvanometer 5 for driving the X-axis mirror 4, a drive unit for moving an active energy ray irradiation unit including an bender mirror 6 of 45 ° and an f-θ lens 7, and 8 is a marking object. A resin molding, which is 9
Is a computer control unit connected by a cable (not shown) for adjusting the amount of active energy ray irradiation and irradiating it at a proper position. 10 is the optical path of the active energy rays, 11 is the direction of rotation of the Y-axis galvanometer 3, and 12 is X.
The rotation direction of the axial galvanometer 5 is shown.

FIG. 2 is an enlarged view of an active energy ray irradiation portion of an embodiment of the present invention. 10-1 and 10
Reference numeral -2 indicates the outer shape of the active energy ray incident along the optical path 10 of the active energy ray, and the active energy ray incident in parallel to the f-θ lens 7 is condensed and further inside the resin molded body. Refracted and focused. Reference numeral 13 is a marking area formed by the condensed active energy rays. The converging diameter b is determined by the focal length of the f-θ lens, the diameter of the laser light, the spread angle thereof, and the like. The depth a from the center of the internal marking portion 13 to the surface of the resin molding can be set to a desired value by adjusting the distance c between the f-θ lens and the resin molding. Further, when a fixed optical lens having a short focus is used, the active energy ray can be condensed more rapidly, and three-dimensional marking can be performed in combination with the XYZ moving table.

[0024]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The marking devices used in all of the examples have an active energy ray generating part including a laser oscillator, a driving part by a galvano scanner, and a focus control mechanism by an f-θ optical system. Example 1 Polymethylmethacrylate (light transmittance 92
%) 100 parts by weight, thiourea (H ₂ NCSNH ₂ ) 0.
10 parts by weight and 0.05 part of bis (triphenylphosphine) nickel (II) bromide (C ₃₆ H ₃₀ Br ₂ NiP ₂ ) were melt-kneaded with a kneader at 220 to 240 ° C. to give thiourea in the resin. And bis (triphenylphosphine) bromide
Nickel (II) was sufficiently dispersed to prepare a pellet-shaped resin composition. Further, this resin composition was molded into a keytop shape with an injection molding machine equipped with a keytop-shaped mold to obtain a resin molded body. A Nd: YAG laser having a wavelength of 1064 nm was used for the resin molded body thus obtained, and the pseudo multi-beam mode, Q-SW repetition frequency 1.0 kHz, average output 2.5 W, scan speed 100
mm / s, distance between f-θ lens and resin molding 15
9.0mm, irradiation amount to the marking area about 8.0kW /
By irradiating with a laser beam under the condition of cm ² , FIG.
It was possible to make a clear yellow color marking such as in the inside of the resin molded body. This marking portion had a vertical range inside the resin molded body, and no protrusion to the surface of the molded body was observed. Furthermore, Q-SW repetition frequency 3.
0 kHz, average output 3.4 W, scan speed 100 mm
/ S, f-? Distance between lens and resin molding 159.
0 mm, irradiation amount to the marking area about 12.0 kW / c
By irradiating with a laser beam under the condition of m ² , white marking could be made on the inside of the resin molded body.

Example 2 100 parts by weight of polymethylmethacrylate (light transmittance 92%), 0.10 parts by weight of 1,3-dimethylthiourea ((CH ₃ NH) ₂ CS) and bis (triphenyl bromide) Phosphine) nickel (II) (C ₃₆ H
0.05 part of ₃₀ Br ₂ NiP ₂ ) was mixed with a kneading machine to obtain 22 parts.
Melt kneading at 0 to 240 ° C. to sufficiently disperse 1,3-dimethylthiourea and bis (triphenylphosphine) nickel (II) bromide in the resin to prepare a pellet-shaped resin composition. Further, this resin composition was molded into a shape of 75 mm × 50 mm × 2 mm with an injection molding machine equipped with a lithographic mold to obtain a resin molded body. A Nd: YAG laser having a wavelength of 1064 nm was used for the resin molded body thus obtained, and the pseudo multi-beam mode, Q-SW repetition frequency 1.0 kHz, average output 2.5 W, scan speed 100
mm / s, distance between f-θ lens and resin molding 15
9.0mm, irradiation amount to the marking area about 8.0kW /
By irradiating with a laser beam under the condition of cm ² , FIG.
It was possible to impart a clear yellow color marking such as the above to the inside of the resin molded body. Furthermore, Q-SW repetition frequency 3.0 kHz, average output 9.3 W, scan speed 10
0 mm / s, distance between f-θ lens and resin molding 1
59.0 mm, irradiation amount to the marking area is about 24.0 k
By irradiating with laser light under the condition of W / cm ² ,
White convex markings could also be applied to the surface of the resin molding as shown in FIG.

Example 3 100 parts by weight of polymethylmethacrylate (light transmittance 92%), potassium iodide 0.05
Parts and 0.05 parts by weight of silver (I) chloride in a kneader 22
The mixture was melt-kneaded at 0 to 240 ° C. to sufficiently disperse potassium iodide and silver (I) chloride in the resin to prepare a pellet-shaped resin composition. Further, this resin composition was molded into a shape of 70 mm × 50 mm × 2 mm with an injection molding machine equipped with a lithographic mold to obtain a resin molded body. The resin molded body thus obtained was subjected to single beam mode, Q-SW using Nd: YAG third harmonic laser with a wavelength of 355 nm.
Repetition frequency 1.0 kHz, average output 2.5 W, scan speed 100 mm / s, distance between f-θ lens and resin molding 254.0 mm, irradiation amount to marking site about 8.0 kW / cm ² . By irradiating a laser beam with, a clear purple color marking could be provided inside the resin molded body.

Example 4 100 parts by weight of polymethylmethacrylate (light transmittance 92%) and 0.05 parts by weight of molybdenum hexacarbonyl (Mo (CO) ₆ ) were melt-kneaded by a kneader at 220 to 240 ° C. Then, molybdenum hexacarbonyl was sufficiently dispersed in the resin to prepare a pellet-shaped resin composition. Further, this resin composition was molded into a shape of 70 mm × 50 mm × 2 mm with an injection molding machine equipped with a lithographic mold to obtain a resin molded body. A single beam mode, Q-S, was applied to the resin molded body thus obtained using an Nd: YAG third harmonic laser having a wavelength of 355 nm.
W repetition frequency 1.0 kHz, average output 2.5 W, scan speed 100 mm / s, distance between f-θ lens and resin molding 254.0 mm, irradiation amount to marking site about 8.0 kW / cm ² . By irradiating with a laser beam under the conditions, a clear yellow color marking could be provided inside the resin molding. This marking site was completely decolorized after several tens of minutes, and repeated marking was possible.

Example 5 100 parts by weight of polymethylmethacrylate (light transmittance 92%), Rhodamine B Gran
00329 0.05 part by weight of 220-
The mixture was melt-kneaded at 240 ° C. to sufficiently disperse Rhodamine B Gran 00329 in the resin to prepare a pellet-shaped resin composition. Further, this resin composition was molded into a shape of 70 mm × 50 mm × 2 mm with an injection molding machine equipped with a lithographic mold to obtain a resin molded body. The resin molded body thus obtained was subjected to single beam mode, Q-SW using Nd: YAG third harmonic laser with a wavelength of 355 nm.
Repetition frequency 1.0 kHz, average output 2.5 W, scan speed 100 mm / s, distance between f-θ lens and resin molding 254.0 mm, irradiation amount to marking site about 8.0 kW / cm ² . By irradiating a laser beam with, it was possible to give a clear pink color marking to the inside of the resin molded body.

Example 6 100 parts by weight of polymethylmethacrylate (light transmittance 92%), Rhodamine B base
40809 0.05 part by weight of 220-
The mixture was melt-kneaded at 240 ° C. to sufficiently disperse Rhodamine B base 40809 in the resin to prepare a pellet-shaped resin composition. Further, this resin composition was molded into a shape of 70 mm × 50 mm × 2 mm with an injection molding machine equipped with a lithographic mold to obtain a resin molded body. The resin molded body thus obtained was subjected to single beam mode, Q-SW using Nd: YAG third harmonic laser with a wavelength of 355 nm.
Repetition frequency 1.0 kHz, average output 2.5 W, scan speed 100 mm / s, distance between f-θ lens and resin molding 254.0 mm, irradiation amount to marking site about 8.0 kW / cm ² . By irradiating a laser beam with, it was possible to give a clear pink color marking to the inside of the resin molded body.

Example 7 A resin molded product was prepared in the same manner as in Example 4 except that 0.001 part by weight of carbon black was used instead of molybdenum hexacarbonyl. The resin molded body obtained in this way was added with a wavelength of 106
Using a 4 nm Nd: YAG laser, pseudo multi-beam mode, Q-SW repetition frequency 3.0 kHz, average output 3.4 W, scan speed 100 mm / s, distance 159 between f-θ lens and resin molding. By irradiating with a laser beam under the conditions of 0.0 mm and an irradiation amount of about 12.0 kW / cm ² to the marking portion, white marking could be provided inside the resin molded body.

[Examples 8 to 26] Resin components were obtained in the same manner as in Example 2 except that the marking components and the transparent resin were in the proportions shown in Table 1. Irradiation with laser light was also performed according to Example 2.

[Table 1] Good marking was able to be applied to any of the resin moldings by irradiation with laser light.

[0032]

According to the present invention, it is possible to provide a highly transparent resin composition that can be marked by irradiation with active energy rays. Further, the resin composition is molded into a resin molded product having a desired shape. By irradiating this with an active energy ray, it is possible to provide a method for marking a clear, high-speed and highly-accurate pattern of characters and illustrations on the resin molded body.

[Brief description of drawings]

FIG. 1 is a device diagram showing a marking device according to an embodiment of the present invention.

FIG. 2 is an enlarged view of a portion irradiated with active energy rays according to an embodiment of the present invention.

FIG. 3 shows a marking formed on the inside of a resin molding having a key top shape according to Example 1 of the present invention.

FIG. 4 shows a flat resin molding according to Example 2 of the present invention in which color marking is provided inside and white convex marking is provided on the surface.

FIG. 5 is a transverse cross-sectional view of a film-shaped molded body made of the resin composition of the present invention, sandwiched between glass plates to form a laminated molded body, and the inside is marked.

[Explanation of symbols]

1 active energy ray generator, 2 Y-axis mirror, 3 Y
Galvanometer for driving the axis mirror, 4 X-axis mirror, 5 Galvanometer for driving the X-axis mirror, 645 ° bender mirror, 7 f-θ lens,
8 resin molding, 9 computer control unit, 10 optical path of active energy rays, 11 rotation direction of galvanometer 3, 12 rotation direction of galvanometer 5, 13 internal marking portion, 14 white convex marking, 15 glass plate

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/36 C08K 5/36 5/56 5/56 // B23K 26/00 B23K 26/00 B (72 ) Inventor Kenichi Inoue 2463 Oshikoshi, Showa-cho, Nakakoma-gun, Yamanashi Prefecture Diaz Kofu 103 F term (reference) 4E068 AB01 CA02 CE02 DB07 DB10 DB11 4F073 AA15 AA31 BA18 BA44 BA52 BB01 BB02 BB08 BB10 CA46 CA53 4J002 BG1271 DD0176 DD076 DD076 EV EZ006

Claims (12)

[Claims] 1. A marking resin composition containing a marking component sensitive to active energy rays and a transparent resin. 2. A marking component which is sensitive to active energy rays comprises an organic transition metal compound, an organic transition metal compound and a compound having at least one NC = S group, or an organic transition metal compound and inorganic oxide fine particles. The marking resin composition according to claim 1, wherein the marking resin composition is selected from the group consisting of: 3. The marking resin composition according to claim 1, wherein the marking component sensitive to active energy rays comprises a transition metal halide and an alkali metal halide. 4. The marking resin composition according to claim 1, wherein the marking component sensitive to active energy rays is calcium carbonate or carbon black. 5. The organic transition metal compound is chromium hexacarbonyl, molybdenum hexacarbonyl, cobalt octacarbonyl, chlorobis (triphenylphosphine).
Nickel (II), bis (triphenylphosphine) nickel (II) bromide, bis (triphenylphosphine) dicarbonyl nickel, cyclopentadienyl (triethylphosphine) copper (I), chlorotriphenylphosphine gold (I),
Rhodamine B Gran 00329, Rhodamine B Base 40809, Copper (II) i-Butyrate, Dichloro (triphenylphosphine) palladium (II), Tetrakis (triphenylphosphine) palladium (O) and Methyltrioxorhenium (VII) A compound having at least one NC = S group selected from thiourea, 1,3-dimethylthiourea, 1,3-diethyl-2
The marking resin composition according to claim 2, wherein the inorganic oxide fine particles are selected from the group consisting of thiourea and zinc dimethyldithiocarbamate, and the inorganic oxide fine particles are alumina. 6. The marking resin composition according to claim 3, wherein the transition metal halide is silver (I) chloride and the alkali metal halide is potassium iodide. 7. The marking resin composition according to claim 1, wherein the marking component sensitive to active energy rays is 0.001 to 10% by weight based on the resin composition. 8. The marking resin composition according to claim 1, wherein the transparent resin is a thermoplastic resin having a light transmittance of at least 50% or more. 9. A marking method, which comprises irradiating an active energy ray to a resin molded product made of the marking resin composition according to claim 1 to perform marking on the resin molded product. 10. The marking method according to claim 9, wherein the active energy ray is laser light in the infrared wavelength region. 11. The marking method according to claim 9, wherein the active energy rays are ultraviolet rays. 12. (1) An active energy ray generator,
(2) The drive unit for moving the irradiation unit of the active energy ray and (3) (1) and (2) are controlled to adjust the irradiation amount of the active energy ray and irradiate it at a proper position. A marking device for use in the method according to claim 9, which comprises a computer control unit.