JPH111065A - Laser marking material developing black-based color upon irradiation with laser light and resin composition containing it - Google Patents
Laser marking material developing black-based color upon irradiation with laser light and resin composition containing itInfo
- Publication number
- JPH111065A JPH111065A JP9171048A JP17104897A JPH111065A JP H111065 A JPH111065 A JP H111065A JP 9171048 A JP9171048 A JP 9171048A JP 17104897 A JP17104897 A JP 17104897A JP H111065 A JPH111065 A JP H111065A
- Authority
- JP
- Japan
- Prior art keywords
- marking material
- laser marking
- titanium dioxide
- resin composition
- laser
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/267—Marking of plastic artifacts, e.g. with laser
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、レーザー光の照射
により黒色系に発色するレーザーマーキング材料及びそ
れを含む樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laser marking material which develops a black color upon irradiation with a laser beam and a resin composition containing the same.
【０００２】[0002]
【従来の技術】従来、電子部品等の物品表面に文字や記
号を表示するために、熱硬化型や紫外線硬化型のインク
を用いた転写印刷法が行なわれていた。しかしながら、
この方法は、物品表面へのゴミの付着防止、物品表面へ
のインクのなじみの調整等に困難を伴い、印刷後にイン
クの硬化を必要とする等の問題があった。また、前記印
刷法に代わる方法として、あらかじめ、レーザーマーキ
ング材料を配合した樹脂組成物を成形等した表面に、レ
ーザー光を照射し、画像を形成させる方法が提案されて
いる。レーザー光の照射により黒色系に発色するレーザ
ーマーキング材料としては、例えば、鉛化合物（特開平
２−４８９８４号公報、特開平３−５２９４４号公報参
照）、シュウ酸銅（特開平３−５２９４５号公報参照）
等が提案されている。鉛化合物をレーザーマーキング材
料に用いると、鮮明な黒色系の発色が得られるが、鉛等
の重金属には、人体に対する毒性や環境汚染の問題があ
る。電子部品等のレーザーマーキング材料として、シュ
ウ酸銅を用いた場合、レーザー光の照射により黒色系の
画像を形成した電子部品等を、アルカリ洗浄液で洗浄す
ると、黒色系の発色が退色し、画像が不鮮明になるとい
う問題がある。2. Description of the Related Art Heretofore, in order to display characters and symbols on the surface of an article such as an electronic component, a transfer printing method using a thermosetting type or an ultraviolet curing type ink has been performed. However,
This method involves difficulties in preventing dust from adhering to the surface of the article, adjusting the familiarity of the ink to the surface of the article, and has a problem that the ink needs to be cured after printing. In addition, as an alternative to the printing method, there has been proposed a method in which an image is formed by irradiating a surface of a resin composition containing a laser marking material with a laser beam beforehand, for example. Examples of a laser marking material which develops a black color upon irradiation with a laser beam include lead compounds (see JP-A-2-48984 and JP-A-3-52944) and copper oxalate (see JP-A-3-52945). reference)
Etc. have been proposed. When a lead compound is used for a laser marking material, a clear black color can be obtained. However, heavy metals such as lead have problems of toxicity to the human body and environmental pollution. When copper oxalate is used as a laser marking material for electronic components and the like, when an electronic component or the like on which a black image is formed by irradiating a laser beam is washed with an alkaline cleaning solution, the black color is faded and the image is discolored. There is a problem of blurring.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、レーザー光
の照射により黒色系に発色し、その発色がアルカリによ
り退色することがなくかつ人体に対する毒性や環境汚染
の問題のないレーザーマーキング材料及びそれを含む樹
脂組成物を提供することを課題とする。DISCLOSURE OF THE INVENTION The present invention relates to a laser marking material which develops a black color upon irradiation with a laser beam, does not lose its color due to alkali, and has no problem of toxicity to the human body and environmental pollution. It is an object to provide a resin composition containing:
【０００４】[0004]
【課題を解決するための手段】本発明者は、前記課題を
解決すべく鋭意研究を重ねた結果、本発明を完成するに
至った。即ち、本発明によれば、レーザー光の照射によ
り黒色系に発色する二酸化チタンと還元剤とからなるレ
ーザーマーキング材料が提供される。また、本発明によ
れば、レーザー光の照射により黒色系に発色する二酸化
チタンと還元剤とからなるレーザーマーキング材料を含
む樹脂組成物が提供される。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, there is provided a laser marking material comprising titanium dioxide which develops a black color upon irradiation with a laser beam and a reducing agent. Further, according to the present invention, there is provided a resin composition containing a laser marking material composed of titanium dioxide and a reducing agent which develops a black color when irradiated with laser light.
【０００５】[0005]
【発明の実施の形態】本発明に用いる二酸化チタンは、
ルチル型、アナタース型又はブルッカイト型のどの結晶
構造を有するものでもよいが、好ましくは、表面未処理
のものである。二酸化チタンの平均粒径は、１〜１００
０ｎｍ、好ましくは、５０〜５００ｎｍである。二酸化
チタンの平均粒径が１０００ｎｍより大きいと、レーザ
ー光を照射したときに十分な反応が得られなくなり、画
像も不均一になる。本発明に用いる還元剤は、レーザー
光の照射により二酸化チタンを低次酸化チタンに還元す
るものであればよく、特に限定されないが、好ましく
は、蓚酸第一錫等の有機酸金属塩、特に、蓚酸金属塩で
ある。この場合の金属は、低次価数と高次価数の両方を
示すことのできる遷移金属あり、低次価数の金属の有機
酸塩が用いられる。金属塩としては、第１錫塩が好まし
く用いられる。本発明に用いる二酸化チタンと還元剤と
の配合割合は、好ましくは、二酸化チタン１ｍｏｌに対
し、還元剤０．１〜１０ｍｏｌである。還元剤の配合割
合が０．１ｍｏｌより少なくないと、レーザー光を照射
したときの二酸化チタンの低次酸化チタンへの還元が不
十分になり、十分な黒色系の発色が得られなくなり、１
０ｍｏｌ以上配合しても発色性の大きな向上は見られな
い。DETAILED DESCRIPTION OF THE INVENTION The titanium dioxide used in the present invention is:
It may have any crystal structure of rutile type, anatase type or brookite type, but preferably has an untreated surface. The average particle size of titanium dioxide is 1 to 100.
0 nm, preferably 50 to 500 nm. If the average particle size of titanium dioxide is larger than 1000 nm, a sufficient reaction cannot be obtained when irradiating laser light, and the image becomes non-uniform. The reducing agent used in the present invention is not particularly limited as long as it reduces titanium dioxide to lower titanium oxide by irradiation with laser light, but is not particularly limited, but is preferably an organic acid metal salt such as stannous oxalate, particularly, It is a metal salt of oxalic acid. The metal in this case is a transition metal capable of exhibiting both a low valence and a high valence, and an organic acid salt of a low valence metal is used. As a metal salt, stannous salt is preferably used. The mixing ratio of the titanium dioxide and the reducing agent used in the present invention is preferably 0.1 to 10 mol of the reducing agent per 1 mol of titanium dioxide. If the compounding ratio of the reducing agent is not less than 0.1 mol, the reduction of titanium dioxide to lower titanium oxide upon irradiation with laser light becomes insufficient, so that a sufficient black color cannot be obtained.
Even if it is added in an amount of 0 mol or more, no significant improvement in coloring properties is observed.
【０００６】本発明のレーザーマーキング材料は、成形
物又は固体表面を形成するための各種の樹脂組成物に配
合して用いることができる。この樹脂組成物の形態は、
特に制約されず、固体状、液体状、懸濁液状等の各種の
形態であることができる。固体状には、粉末状やペレッ
ト状が包含され、液体状には、液体状、粘性液状が包含
され、懸濁液状には、エマルジョンやサスペンジョンが
包含される。また、樹脂組成物の種類も特に制約され
ず、熱や光で硬化する硬化性樹脂組成物、熱可塑性樹脂
組成物、ゴム組成物等が包含される。硬化性樹脂組成物
としては、エポキシ樹脂、フェノキシ樹脂、フェノール
樹脂、不飽和ポリエステル樹脂、アルキド樹脂、ウレタ
ン樹脂、メラミン樹脂、尿素樹脂、グアナミン樹脂、ポ
リイミド樹脂、ビニルエステル樹脂、ジアリルフタレー
ト樹脂、キシレン樹脂、ケイ素樹脂等の硬化性樹脂を樹
脂成分として含む各種の組成物が挙げられる。熱可塑性
樹脂としては、ポリエチレン、ポリプロピレン、ポリス
チレン、合成ゴム（ポリブタジエン、ブタジエン／スチ
レン共重合体、ポリイソプレン、ポリクロロプレン、エ
チエン／プロピレン共重合体）、ポリ酢酸ビニル、ポリ
メタクリル酸エステル、ポリアクリル酸エステル、ポリ
アクリル酸アミド、ポリオキシメチレン、ポリフェニレ
ンオキシド、ポリエステル、ポリアミド、ポリカーボネ
イト、セルロール系樹脂、ポリアクリロニトリル、熱可
塑性ポリイミド、ポリビニルアルコール、ポリビニルピ
ロリドン、ポリ塩化ビニル、フッ素樹脂等の熱可塑性樹
脂を樹脂成分として含む各種の組成物が挙げられる。The laser marking material of the present invention can be used by being blended with various resin compositions for forming a molded product or a solid surface. The form of this resin composition is
There is no particular limitation, and various forms such as a solid state, a liquid state, and a suspension state can be used. The solid form includes a powder form and a pellet form, the liquid form includes a liquid form and a viscous liquid, and the suspension form includes an emulsion and a suspension. The type of the resin composition is not particularly limited, and includes a curable resin composition, a thermoplastic resin composition, a rubber composition, and the like that are cured by heat or light. As the curable resin composition, epoxy resin, phenoxy resin, phenol resin, unsaturated polyester resin, alkyd resin, urethane resin, melamine resin, urea resin, guanamine resin, polyimide resin, vinyl ester resin, diallyl phthalate resin, xylene resin And various compositions containing a curable resin such as a silicon resin as a resin component. Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, synthetic rubber (polybutadiene, butadiene / styrene copolymer, polyisoprene, polychloroprene, ethene / propylene copolymer), polyvinyl acetate, polymethacrylate, polyacrylic acid Thermoplastic resins such as esters, polyacrylamide, polyoxymethylene, polyphenylene oxide, polyester, polyamide, polycarbonate, cellulose resin, polyacrylonitrile, thermoplastic polyimide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl chloride, fluororesin, etc. Various compositions containing as a component are mentioned.
【０００７】本発明のレーザー光の照射により黒色系に
発色する二酸化チタンと還元剤とからなるレーザーマー
キング材料を含む樹脂組成物において、二酸化チタンの
配合割合は、樹脂成分１００重量部に対し、通常、５〜
２００重量部、好ましくは５〜８０重量部、より好まし
くは１０〜５０重量部の割合である。本発明の樹脂組成
物は、二酸化チタンと還元剤とからなるレーザーマーキ
ング材料の他、慣用の補助成分を含むことができる。こ
のような補助成分としては、硬化剤、硬化促進剤、有機
又は無機充填剤、顔料、染料、酸化防止剤、難燃剤、溶
剤等が挙げられる。本発明の樹脂組成物は、例えば、成
形材料や塗装材料として用いられる。成形材料として用
いる場合、その成形方法としては、トランスファー成形
法、射出成形法、圧縮成形法、注型成形法、ディッピン
グ成形法等が挙げられる。一方塗装材料として用いる場
合、その塗装方法としては、流動浸漬法、静電スプレー
法、バーコーター法、ロールコーター法、はけ塗り法等
が挙げられる。本発明の樹脂組成物から得られる成形物
や塗装物の固体表面に対しては、レーザー光の照射によ
り、その表面に、黒色系の文字やマーク等の画像を形成
することができる。レーザーマーキングの対象となる物
品の具体例としては、例えば、表面を樹脂組成物で塗装
されたコンデンサー、抵抗、ダイオード、ＩＣ等の電子
・電気部品等が挙げられる。このような用途では、電気
・電子部品等の識別のために、樹脂組成物を任意の色に
着色することが要求されるが、シュウ酸銅のような青色
系の着色を有するレーザーマーキング材料を用いた場
合、樹脂組成物を任意の色に着色することが困難である
が、本発明に用いる二酸化チタンは、白色であり、樹脂
組成物を顔料や染料で任意の色に着色できる。レーザー
光としては、炭酸ガスレーザー光やＹＡＧレーザー光等
の従来公知のレーザー光を用いることができる。このよ
うなレーザー光発生装置としては、炭酸ガスレーザー発
生装置を始め、ＹＡＧレーザー発生装置等の従来公知の
各種のものを用いることができる。[0007] In the resin composition of the present invention containing a laser marking material comprising titanium dioxide and a reducing agent, which is colored black by irradiation with laser light, the mixing ratio of titanium dioxide is usually 100 parts by weight of the resin component. , 5
The proportion is 200 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 50 parts by weight. The resin composition of the present invention can contain conventional auxiliary components in addition to a laser marking material composed of titanium dioxide and a reducing agent. Such auxiliary components include curing agents, curing accelerators, organic or inorganic fillers, pigments, dyes, antioxidants, flame retardants, solvents and the like. The resin composition of the present invention is used, for example, as a molding material or a coating material. When used as a molding material, examples of the molding method include a transfer molding method, an injection molding method, a compression molding method, a cast molding method, and a dipping molding method. On the other hand, when used as a coating material, examples of the coating method include a fluid immersion method, an electrostatic spray method, a bar coater method, a roll coater method, and a brushing method. An image such as a black character or mark can be formed on the solid surface of a molded product or a coated product obtained from the resin composition of the present invention by irradiating a laser beam. Specific examples of articles to be laser-marked include, for example, electronic and electric parts such as capacitors, resistors, diodes, and ICs, the surfaces of which are coated with a resin composition. In such applications, it is required to color the resin composition to an arbitrary color for identification of electric / electronic parts and the like, but a laser marking material having a blue color such as copper oxalate is used. When used, it is difficult to color the resin composition to any color, but the titanium dioxide used in the present invention is white, and the resin composition can be colored to any color with a pigment or dye. As the laser beam, a conventionally known laser beam such as a carbon dioxide laser beam or a YAG laser beam can be used. As such a laser beam generator, various known devices such as a carbon dioxide laser generator and a YAG laser generator can be used.
【０００８】[0008]
【発明の効果】本発明のレーザーマーキング材料及び樹
脂組成物にレーザー光を照射すると、レーザー光照射箇
所の二酸化チタンが還元剤の作用により低次酸化チタン
に還元され、レーザー照射箇所には、黒色系画像が形成
される。この画像は、アルカリ洗浄液で洗浄しても退色
することがない。さらに、本発明に用いる二酸化チタン
は、白色であり、シュウ酸銅等の有色のレーザーマーキ
ング材料を用いた場合には困難であった、樹脂組成物を
任意の色に着色できるという効果がある。本発明で用い
るレーザーマーキング材料及び樹脂組成物は鉛化合物を
含まないことから、従来の鉛化合物を含有するものに見
られたような人体に対する毒性の問題も殆んどない。When the laser marking material and the resin composition of the present invention are irradiated with a laser beam, the titanium dioxide at the laser beam-irradiated portion is reduced to lower titanium oxide by the action of a reducing agent, and the laser-irradiated portion becomes black. A system image is formed. This image does not fade even when washed with an alkaline washing solution. Furthermore, the titanium dioxide used in the present invention is white, and has an effect that the resin composition can be colored to any color, which was difficult when a colored laser marking material such as copper oxalate was used. Since the laser marking material and the resin composition used in the present invention do not contain a lead compound, there is almost no problem of toxicity to the human body as seen in conventional ones containing a lead compound.
【０００９】[0009]
【実施例】次に、実施例により、本発明をさらに詳細に
説明するが、本発明は、これらの実施例によってなんら
限定されるものではない。なお、樹脂組成物の性能評価
方法は、次のとおりである。 （視認性） ◎：非常に鮮明な画像である。 ○：鮮明な画像である。 △：やや不鮮明な画像である。 ×：画像がほとんど読みとれない。 （画像均一性） ◎：非常に均一な画像である。 ○：均一な画像である。 △：やや不均一な画像である。 ×：部分的な断線等の欠陥がある。Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. The method for evaluating the performance of the resin composition is as follows. (Visibility) ：: Very clear image. ：: A clear image. Δ: Image is slightly unclear. X: Image is hardly readable. (Image uniformity) A: Very uniform image. ：: uniform image. Δ: Image is slightly uneven. ×: There is a defect such as partial disconnection.
【００１０】実施例１〜３、比較例１〜２ 表１に示す樹脂組成物を調製し、８０℃で１時間、更
に、１５０℃で２時間加熱硬化し、０．５ｍｍの厚さの
成形物を作成した。次に、この成形物表面に、波長１
０．６μｍであるレーザー光を１回照射し、画線の太さ
が０．２ｍｍの画像を形成した。このとき使用したレー
ザー光マーキング装置は、ＩＥＡ ＣＯ2レーザー、ユ
ニマーク４００の４Ｊ（ジュール）型（ウシオ電気社
製）である。実施例１〜３、比較例１〜２の樹脂組成物
の成形物表面にレーザー光の照射により形成した画像の
視認性、画像均一性の性能評価結果を表１に示す。な
お、表１に示す成分の具体的内容は、次のとおりであ
る。 エピコート８２８：油化シュルエポキシ社製ビスフェノ
ールＡ型エポキシ樹脂、エポキシ当量１９０ ＴｉＯ2：堺化学工業社製アナタース型二酸化チタン、
平均粒径０．１５μｍ ＣＭＣ−１２Ｓ：龍森社製結晶性シリカ、平均粒径５．
０〜８．０μｍ ＳｎＣ2Ｏ4：日本化学産業社製蓚酸第一錫 ２Ｅ４ＭＺ：四国化成工業社製２−エチル−４−メチル
イミダゾールExamples 1 to 3 and Comparative Examples 1 and 2 The resin compositions shown in Table 1 were prepared and cured by heating at 80 ° C. for 1 hour and further at 150 ° C. for 2 hours to form a mold having a thickness of 0.5 mm. Created things. Next, a wavelength of 1
A laser beam having a thickness of 0.6 μm was irradiated once to form an image having an image thickness of 0.2 mm. The laser beam marking device used at this time was an IEA CO 2 laser, Unimark 400, 4J (Joule) type (manufactured by Ushio Inc.). Table 1 shows the performance evaluation results of the visibility and image uniformity of the images formed by irradiating laser light on the surfaces of the resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2. The specific contents of the components shown in Table 1 are as follows. Epicoat 828: Bisphenol A type epoxy resin manufactured by Yuka Sureppoeki Co., Ltd., epoxy equivalent 190 TiO 2 : Anatas type titanium dioxide manufactured by Sakai Chemical Industry Co., Ltd.
Average particle size 0.15 μm CMC-12S: crystalline silica manufactured by Tatsumori, average particle size 5.
0 to 8.0 μm SnC 2 O 4 : Stannous oxalate manufactured by Nippon Chemical Industry Co., Ltd. 2E4MZ: 2-ethyl-4-methylimidazole manufactured by Shikoku Chemical Industry Co., Ltd.
【００１１】[0011]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｂ４１Ｍ 5/26 Ｓ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI B41M 5/26 S
Claims (3)
ー光の照射により黒色系に発色するレーザーマーキング
材料。1. A laser marking material which develops a black color when irradiated with a laser beam comprising titanium dioxide and a reducing agent.
０．１〜１０ｍｏｌの割合で含む請求項１のレーザーマ
ーキング材料。2. A reducing agent is added to 1 mol of titanium dioxide.
2. The laser marking material according to claim 1, comprising 0.1 to 10 mol.
料を含む樹脂組成物。3. A resin composition comprising the laser marking material according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17104897A JP3713675B2 (en) | 1997-06-12 | 1997-06-12 | LASER MARKING MATERIAL COLORED BLACK BY LASER LIGHT IRRADIATION AND RESIN COMPOSITION CONTAINING THE SAME |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17104897A JP3713675B2 (en) | 1997-06-12 | 1997-06-12 | LASER MARKING MATERIAL COLORED BLACK BY LASER LIGHT IRRADIATION AND RESIN COMPOSITION CONTAINING THE SAME |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH111065A true JPH111065A (en) | 1999-01-06 |
| JP3713675B2 JP3713675B2 (en) | 2005-11-09 |
Family
ID=15916124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17104897A Expired - Fee Related JP3713675B2 (en) | 1997-06-12 | 1997-06-12 | LASER MARKING MATERIAL COLORED BLACK BY LASER LIGHT IRRADIATION AND RESIN COMPOSITION CONTAINING THE SAME |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3713675B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074548A2 (en) | 2001-03-16 | 2002-09-26 | Sherwood Technology Ltd. | Laser-markable compositions |
| US6888095B2 (en) | 2001-02-28 | 2005-05-03 | Sherwood Technology, Inc. | Laser coding |
| DE102004010504A1 (en) * | 2004-03-04 | 2005-09-22 | Degussa Ag | Highly transparent laser-markable and laser-weldable plastic materials |
| WO2006094881A1 (en) * | 2005-03-09 | 2006-09-14 | Degussa Gmbh | Plastic moulding with bidimensional or tridimensional image structures generated by inner laser engraving |
| WO2009024497A1 (en) * | 2007-08-22 | 2009-02-26 | Basf Se | Laser-sensitive coating composition |
| JP2010214666A (en) * | 2009-03-13 | 2010-09-30 | Nissha Printing Co Ltd | Sheet for laser decoration, sheet with laser decorative pattern using the same, and method for manufacturing laser decorative article |
| WO2013049320A1 (en) | 2011-09-27 | 2013-04-04 | Crown Packaging Technology, Inc. | Marking of can ends and/or pull tabs using photonically sensitive ink |
| US9187221B2 (en) | 2011-09-27 | 2015-11-17 | Crown Packaging Technology, Inc. | Can ends having machine readable information |
| JP2020079352A (en) * | 2018-11-13 | 2020-05-28 | 東洋インキＳｃホールディングス株式会社 | Ultraviolet laser marking composition, and printed matter and laminate including the same |
-
1997
- 1997-06-12 JP JP17104897A patent/JP3713675B2/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6888095B2 (en) | 2001-02-28 | 2005-05-03 | Sherwood Technology, Inc. | Laser coding |
| WO2002074548A2 (en) | 2001-03-16 | 2002-09-26 | Sherwood Technology Ltd. | Laser-markable compositions |
| DE102004010504A1 (en) * | 2004-03-04 | 2005-09-22 | Degussa Ag | Highly transparent laser-markable and laser-weldable plastic materials |
| WO2006094881A1 (en) * | 2005-03-09 | 2006-09-14 | Degussa Gmbh | Plastic moulding with bidimensional or tridimensional image structures generated by inner laser engraving |
| WO2009024497A1 (en) * | 2007-08-22 | 2009-02-26 | Basf Se | Laser-sensitive coating composition |
| JP2010536970A (en) * | 2007-08-22 | 2010-12-02 | ビーエーエスエフ ソシエタス・ヨーロピア | Laser sensitive coating composition |
| US9045619B2 (en) | 2007-08-22 | 2015-06-02 | Datalase Ltd. | Laser-sensitive coating composition |
| JP2010214666A (en) * | 2009-03-13 | 2010-09-30 | Nissha Printing Co Ltd | Sheet for laser decoration, sheet with laser decorative pattern using the same, and method for manufacturing laser decorative article |
| WO2013049313A2 (en) | 2011-09-27 | 2013-04-04 | Crown Packaging Technology, Inc. | Can ends having machine readable information |
| WO2013049320A1 (en) | 2011-09-27 | 2013-04-04 | Crown Packaging Technology, Inc. | Marking of can ends and/or pull tabs using photonically sensitive ink |
| US9187221B2 (en) | 2011-09-27 | 2015-11-17 | Crown Packaging Technology, Inc. | Can ends having machine readable information |
| US9637267B2 (en) | 2011-09-27 | 2017-05-02 | Crown Packaging Technology, Inc. | Marking of can ends and/or pull tabs using photonically sensitive ink |
| EP3279104A1 (en) | 2011-09-27 | 2018-02-07 | Crown Packaging Technology, Inc. | Can ends having machine readable information |
| EP3556675A1 (en) | 2011-09-27 | 2019-10-23 | Crown Packaging Technology, Inc. | Can ends having machine readable information |
| EP4173985A1 (en) | 2011-09-27 | 2023-05-03 | Crown Packaging Technology, Inc | Method of decorating can ends |
| JP2020079352A (en) * | 2018-11-13 | 2020-05-28 | 東洋インキＳｃホールディングス株式会社 | Ultraviolet laser marking composition, and printed matter and laminate including the same |
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| Publication number | Publication date |
|---|---|
| JP3713675B2 (en) | 2005-11-09 |
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