JP5227733B2 - Bismuth oxide additive for laser marking and method for producing the same - Google Patents
Bismuth oxide additive for laser marking and method for producing the same Download PDFInfo
- Publication number
- JP5227733B2 JP5227733B2 JP2008265823A JP2008265823A JP5227733B2 JP 5227733 B2 JP5227733 B2 JP 5227733B2 JP 2008265823 A JP2008265823 A JP 2008265823A JP 2008265823 A JP2008265823 A JP 2008265823A JP 5227733 B2 JP5227733 B2 JP 5227733B2
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- Prior art keywords
- laser marking
- additive
- oxide
- laser
- marking
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- 238000010330 laser marking Methods 0.000 title claims description 58
- 239000000654 additive Substances 0.000 title claims description 56
- 230000000996 additive effect Effects 0.000 title claims description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910000416 bismuth oxide Inorganic materials 0.000 title description 5
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title description 5
- 239000002994 raw material Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010303 mechanochemical reaction Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 4
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 238000010298 pulverizing process Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 14
- 238000004040 coloring Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 9
- 229910052797 bismuth Inorganic materials 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- -1 ethylene glycol Chemical compound 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005280 amorphization Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
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- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229940049676 bismuth hydroxide Drugs 0.000 description 2
- 229940073609 bismuth oxychloride Drugs 0.000 description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
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- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 description 1
- 229940104825 bismuth aluminate Drugs 0.000 description 1
- 229910002115 bismuth titanate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Laser Beam Processing (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明はレーザー光を利用して樹脂成形物等に管理情報等をマーキングする、即ちレーザーマーキングに使用することのできる添加剤とその製造方法に関し、より詳細には、樹脂成形物の種類や形状に関わらず好適なマーキングを施すことを可能にし、且つ樹脂成形物への添加による同成形物の着色等といった望ましくない作用を極小化しうるレーザーマーキング用添加剤とその製造方法に関する。 The present invention relates to an additive that can be used for laser marking to mark management information etc. on a resin molded article using laser light, that is, a manufacturing method thereof, and more specifically, the type and shape of the resin molded article Regardless of the present invention, the present invention relates to an additive for laser marking and a method for producing the same, which can make a suitable marking regardless of the above and can minimize undesirable effects such as coloring of the molded product by addition to the resin molded product.
レーザーマーキングは、レーザー光を利用して基材に直接、文字、数字、商標、バーコード等の印字や、或いは画像を施すマーキング方法である。 Laser marking is a marking method in which letters, numbers, trademarks, barcodes, etc. are printed or images are directly applied to a substrate using laser light.
レーザー光によるマーキングシステムには、
(1)非接触のマーキング方法であるため、任意の形状の基材に高速でマーキングを行うことができる、
(2)インクを使用しないため、マーキングが耐摩耗性に優れ、改ざんが困難であり、また有機溶剤等の揮発がないため低環境負荷である、
という大きな特徴がある。
For marking system with laser light,
(1) Because it is a non-contact marking method, marking can be performed at high speed on a substrate of any shape,
(2) Since no ink is used, the marking is excellent in abrasion resistance, difficult to tamper with, and since there is no volatilization of organic solvents, etc., it has a low environmental impact.
There is a big feature.
そのため、現在多くの産業において、従来のインクシステムがレーザーマーキングシステムに移行している。 As a result, in many industries, conventional ink systems are now moving to laser marking systems.
レーザーマーキングにはＣＯ２レーザー、Ｎｄ：ＹＡＧレーザー等が使用されるが、精細な印字を可能にするため、主にはＮｄ：ＹＡＧレーザーが好適に使用される。 For laser marking, a CO 2 laser, an Nd: YAG laser, or the like is used. In order to enable fine printing, an Nd: YAG laser is mainly preferably used.
しかしながら、Ｎｄ：ＹＡＧレーザーにより樹脂成形材料へレーザーマーキングを施した場合、ほとんど全ての主要な樹脂成形材料において、視認性や精細度において十分な品質のマーキングが得られない場合が多く、全く印字できない樹脂も少なくない。 However, when laser marking is applied to a resin molding material with an Nd: YAG laser, in most of the main resin molding materials, marking with sufficient quality in terms of visibility and definition is often not obtained, and printing cannot be performed at all. Not a few resins.
そのため、樹脂成形材料にレーザーマーキングの視認性を改善させることのできる添加剤が求められ、幾つかのレーザーマーキング用添加剤が提案されている。 Therefore, an additive capable of improving the visibility of the laser marking is required for the resin molding material, and several additives for laser marking have been proposed.
例えば、特許文献１には、粒径１０〜７０ｎｍの錫およびアンチモンの混合酸化物の粒子をレーザーマーキング用添加剤として成形材料（基材）に添加することが開示されている。 For example, Patent Document 1 discloses that particles of a mixed oxide of tin and antimony having a particle size of 10 to 70 nm are added to a molding material (base material) as an additive for laser marking.
特許文献２には、雲母薄片やＳｉＯ２フレーク等の薄片状基質に、アンチモン、砒素、ビスマス、銅、ガリウム、ゲルマニウまたはそれらの酸化物をドープした酸化錫を被覆した顔料をレーザーマーキング用の添加剤として含む熱可塑性プラスチックが、レーザーマーキング可能であると記載されている。 Patent Document 2 discloses that a pigment coated with tin oxide doped with antimony, arsenic, bismuth, copper, gallium, germanium or their oxide is added to a flaky substrate such as mica flakes or SiO 2 flakes for laser marking. Thermoplastics included as agents are described as being laser-markable.
特許文献３には、酸化ビスマスを含有する樹脂組成物がレーザー光の照射により黒色にマーキング可能であると記載されている。 Patent Document 3 describes that a resin composition containing bismuth oxide can be marked black by irradiation with laser light.
特許文献４には、ビスマスと、Ｚｎ，Ｔｉ，Ｆｅ，Ｃｕ，Ａｌ，Ｚｒ，Ｐ，Ｓｎ，Ｓｒ，Ｓｉ，Ｙ，Ｎｂ．Ｌａ，Ｔａ，Ｐｒ，Ｃａ，Ｍｇ，Ｍｏ，Ｗ，Ｓｂ，Ｃｒ，ＢａおよびＣｅから選択される少なくとも１つの付加的な金属との酸化物を含有するレーザーマーキング可能な化合物が開示されている。 Patent Document 4 includes bismuth, Zn, Ti, Fe, Cu, Al, Zr, P, Sn, Sr, Si, Y, Nb. Laser markable compounds containing oxides with at least one additional metal selected from La, Ta, Pr, Ca, Mg, Mo, W, Sb, Cr, Ba and Ce are disclosed.
しかしながら、これら特許文献に記載の添加剤を含む樹脂成形物にレーザーマーキングを適用した場合、視認性改善の効果はある程度認められるものの、マーキングの黒さやコントラストといったマーキング性は、なお満足されるものではない。 However, when laser marking is applied to resin moldings containing the additives described in these patent documents, the effect of improving visibility is recognized to some extent, but marking properties such as marking blackness and contrast are still not satisfactory. Absent.
一方、発明者らは、特許文献５において、銅とモリブデンからなる複合酸化物がレーザー光の照射により黒度の高い色調に変色することを見出した。該複合酸化物はほとんど全ての樹脂成形物に、優れたレーザーマーキング性を与える。しかしながら該複合酸化物は酸化物自体が黄色に着色しているため、樹脂成形物そのものを若干着色してしまうという、望ましくない問題点を抱える。
本発明の目的は、上記問題点に鑑み、樹脂成形物の望ましくない着色を起こさず、且つ黒さとコントラストに優れたマーキングを可能にするレーザーマーキング用添加剤を提供することにある。 In view of the above problems, an object of the present invention is to provide an additive for laser marking that does not cause undesirable coloring of a resin molded product and enables marking with excellent blackness and contrast.
本発明の別の目的は、樹脂成形物の望ましくない着色を起こさず、且つ黒さとコントラストに優れたマーキングを可能にするレーザーマーキング用添加剤の製造方法を提供することにある。 Another object of the present invention is to provide a method for producing an additive for laser marking that does not cause undesirable coloring of a resin molded product and enables marking with excellent blackness and contrast.
本発明のさらに別の目的は、樹脂成形物の望ましくない着色を起こさず、且つ黒さとコントラストに優れたマーキングを可能にするレーザーマーキング用添加剤を含む樹脂成形物を提供することである。 Still another object of the present invention is to provide a resin molding containing an additive for laser marking that does not cause undesirable coloring of the resin molding and enables marking with excellent blackness and contrast.
本発明によるレーザーマーキング用添加剤は、下記一般式で表される金属酸化物を含有することを特徴とするものである。 The additive for laser marking according to the present invention contains a metal oxide represented by the following general formula .
Ｂｉ（１−ｘ）ＭｘＯｙ
（式中、Ｍはガドリウムおよびネオジムから選択される少なくとも１つの金属、ｘおよびｙはそれぞれ０．００１＜ｘ＜０．５、１＜ｙ＜２．５の関係を有する値である。）
本発明によるレーザーマーキング用添加剤は、上記添加剤を構成する元素の酸化物、あるいは熱を加えることにより酸化物となる化合物を、所定の割合で配合した原料配合物を粉砕機で乾式処理することにより、メカノケミカル反応を起こすに充分なエネルギーをその原料配合物に与える工程と、それを３００℃以上の温度で焼成すること工程を含む方法により好適に製造することができる。
Bi (1-x) M x O y
(In the formula, M is at least one metal selected from gadolinium and neodymium, and x and y are values having a relationship of 0.001 <x <0.5 and 1 <y <2.5, respectively.)
The additive for laser marking according to the present invention is a dry processing of a raw material blend in which a compound that becomes an oxide by applying heat or an oxide that forms an oxide by adding heat in a predetermined ratio is processed by a pulverizer. Thus, it can be suitably produced by a method including a step of giving energy sufficient to cause a mechanochemical reaction to the raw material blend and a step of firing it at a temperature of 300 ° C. or higher.
本発明はまた、上記レーザーマーキング用添加剤を含むレーザーマーキング可能な成形物を提供する。 The present invention also provides a laser markable molded article containing the laser marking additive.
この成形物にレーザーマーキングを施すのに用いるレーザーとしては、たとえば固体パルス・レーザー、エキシマ・レーザー、ＹＡＧ：Ｎｄレーザー、およびＣＯ２レーザー等が挙げられ、ＹＡＧ：Ｎｄレーザーが好ましく使用できる。 Examples of the laser used for laser marking on the molded product include a solid pulse laser, an excimer laser, a YAG: Nd laser, and a CO 2 laser, and a YAG: Nd laser can be preferably used.
以下、本発明をさらに詳しく説明する。 Hereinafter, the present invention will be described in more detail.
本発明による、ａ）ビスマスの酸化物と、ｂ）ガドリウムおよびネオジムから選択される少なくとも１つの金属の酸化物とを含有するレーザーマーキング用添加剤は、後述の実施例によって実証されているように、酸化ビスマス単独、ないしは、ビスマスと、Ｚｎ，Ｔｉ，Ｆｅ，Ｃｕ，Ａｌ，Ｚｒ，Ｐ，Ｓｎ，Ｓｒ，Ｓｉ，Ｙ，Ｎｂ，Ｌａ，Ｔａ，Ｐｒ，Ｃａ，Ｍｇ，Ｍｏ，Ｗ，Ｓｂ，Ｃｒ，ＢａおよびＣｅから選択される少なくとも１つの付加的な金属の酸化物を含有するものに比べ、明らかに黒度に優れたマーキングを可能にする。更にこの化合物の色はいずれも白色か、非常に淡い黄色であり、従って成形物をほとんど着色することなく添加可能である。 The laser marking additive according to the present invention comprising a) an oxide of bismuth and b) an oxide of at least one metal selected from gadolinium and neodymium, as demonstrated by the examples below. Bismuth oxide alone or bismuth and Zn, Ti, Fe, Cu, Al, Zr, P, Sn, Sn, Si, Y, Nb, La, Ta, Pr, Ca, Mg, Mo, W, Sb, Marking with a clearly superior blackness is possible compared to those containing at least one additional metal oxide selected from Cr, Ba and Ce. Furthermore, the color of this compound is either white or very pale yellow, so that it can be added with little coloring of the molding.
一般式、Ｂｉ（１−ｘ）ＭｘＯｙ（式中、Ｍはガドリウムおよびネオジムから選択される少なくとも１つの金属、ｘおよびｙはそれぞれ０．００１＜ｘ＜０．５、１＜ｙ＜２．５の関係を有する値である。）で表される好ましい金属酸化物において、式中のｘおよびｙが上記範囲を下回っても上回ってもマーキング性は低下する。 General formula, Bi (1-x) M x O y (wherein M is at least one metal selected from gadolinium and neodymium, x and y are 0.001 <x <0.5, 1 <y <, respectively) In the preferable metal oxide represented by the formula (2), the marking property is deteriorated even when x and y in the formula are below or above the above range.
本発明によるレーザーマーキング用添加剤は、その粒子径が小さい程、より高精細なマーキングを可能にする。該添加剤の粒子径は、平均粒子径Ｄ５０が好ましくは１０μｍ以下、より好ましくはＤ５０が１μｍ以下である。 The additive for laser marking according to the present invention enables higher-definition marking as the particle diameter is smaller. As for the particle diameter of the additive, the average particle diameter D50 is preferably 10 μm or less, and more preferably D50 is 1 μm or less.
次に、本発明によるレーザーマーキング用添加剤の製造法について、説明をする。 Next, the manufacturing method of the additive for laser marking by this invention is demonstrated.
この添加剤を製造する好ましい製造方法は、上記添加剤を構成する元素の酸化物、あるいは熱を加えることにより酸化物となる化合物を、所定の割合で配合した原料配合物を粉砕機で乾式粉砕することにより、メカノケミカル反応を起こすに充分なエネルギーをその原料配合物に与える工程と、それを３００℃以上の温度で焼成すること工程を含むことである。ここで、「所定の割合」とは、例えば一般式、Ｂｉ（１−ｘ）ＭｘＯｙ（式中、Ｍはガドリウムおよびネオジムから選択される少なくとも１つの金属、ｘおよびｙはそれぞれ０．００１＜ｘ＜０．５、１＜ｙ＜２．５の関係を有する値である。）で表される金属酸化物を得るのに必要な原料化合物の割合である。 A preferable production method for producing this additive is a dry pulverization of a raw material blend in which a compound which becomes an oxide by adding heat, or a compound which becomes an oxide by applying heat in a predetermined ratio, is pulverized by a pulverizer. By doing so, it includes a step of giving the raw material formulation sufficient energy to cause a mechanochemical reaction, and a step of firing it at a temperature of 300 ° C. or higher. Here, the “predetermined ratio” is, for example, a general formula, Bi (1-x) M x O y (wherein M is at least one metal selected from gadolinium and neodymium, and x and y are each 0. 001 <x <0.5 and 1 <y <2.5.) The ratio of the raw material compounds necessary to obtain the metal oxide represented by:
原料化合物は、上記添加剤を構成する元素の酸化物、あるいは熱を加えることにより酸化物となる化合物であれば特に限定されない。例えば、ビスマス源として、酸化ビスマス、オキシ塩化ビスマス、硝酸ビスマス、水酸化ビスマス等が挙げられる。後の焼成工程において有害なガスが発生しない酸化ビスマスや水酸化ビスマス等が好ましい。ガドリウム源およびネオジム源もこれらの酸化物か、あるいは熱を加えることにより酸化物となる化合物を使用可能である。例えばこれら金属の酸化物、水酸化物、硝酸塩、塩化物、硫酸塩等が使用でき、焼成工程における排ガス発生の観点から酸化物、水酸化物の使用が好ましい。 The raw material compound is not particularly limited as long as it is an oxide of an element constituting the additive, or a compound that becomes an oxide when heated. Examples of the bismuth source include bismuth oxide, bismuth oxychloride, bismuth nitrate, and bismuth hydroxide. Bismuth oxide, bismuth hydroxide and the like that do not generate harmful gas in the subsequent firing step are preferable. As the gadolinium source and the neodymium source, either of these oxides or a compound that becomes an oxide when heated can be used. For example, oxides, hydroxides, nitrates, chlorides, sulfates and the like of these metals can be used, and oxides and hydroxides are preferably used from the viewpoint of exhaust gas generation in the firing process.
これらの原料化合物を所定の割合で混合し、この混合物を粉砕機で乾式粉砕に付す。乾式による粉砕処理を続けることで原料粉体に、粉砕に必要なエネルギー以上のエネルギーが付加される。それによりメカノケミカル反応として知られる、原料粒子表面からの非晶質化（無定形化）や原料粒子同士の強固な接合、複合化を原料粉体に付加せしめることが、本発明の製造方法の大きな特徴である。該粉砕工程におけるメカノケミカル反応の進行は、粉砕工程前後のＸ線回折パターンによる非晶質化の進行、ＴＧ−ＤＴＡ、ＤＳＣなどの熱分析での発熱、吸熱ピークの消滅やシフト、走査電子顕微鏡とそれに付随するエネルギー分散型Ｘ線分析装置による元素マッピング等の手法により観察、管理することが可能である。従って該粉砕工程においてメカノケミカル反応を起こすに充分なエネルギーをその原料配合物に与える為に必要な粉砕時間は、用いる粉砕機によって大きく異なる為に一概には規定できないが、上述の手法のいずれか、ないしは複数の手法の組み合わせを用いて決定することが出来る。該粉砕工程と後述の焼成工程を経ることにより、レーザーマーキング性能が顕著に優れた添加剤を得ることができる。 These raw material compounds are mixed at a predetermined ratio, and this mixture is subjected to dry pulverization with a pulverizer. By continuing the dry pulverization process, energy more than that required for pulverization is added to the raw material powder. As a result, it is known as mechanochemical reaction that amorphization (amorphization) from the surface of the raw material particles, strong bonding between the raw material particles, and addition of the composite are added to the raw material powder. It is a big feature. Progress of the mechanochemical reaction in the pulverization process is progress of amorphization by X-ray diffraction patterns before and after the pulverization process, exotherm in thermal analysis such as TG-DTA, DSC, disappearance and shift of endothermic peak, scanning electron microscope It is possible to observe and manage by means of element mapping using an energy dispersive X-ray analyzer associated therewith. Therefore, the pulverization time required to give the raw material mixture sufficient energy to cause a mechanochemical reaction in the pulverization step varies greatly depending on the pulverizer to be used. It can be determined using a combination of a plurality of methods. By going through the pulverization step and the firing step described later, an additive with remarkably excellent laser marking performance can be obtained.
用いる粉砕機は汎用のものでよく、例えば転動ボールミル、振動ミル、石臼型ミル、ジスクミル、ピンミル、媒体攪拌型ミル、遊星ボールミルなどが使用可能である。これらの粉砕機による乾式粉砕の際に、エタノール、プロパノール等のアルコール、エチレングリコール等の多価アルコール類、およびジエタノールアミン等のアルコール系アミン類等の液体を粉砕助剤として少量添加しても良い。 The grinder to be used may be a general-purpose one, and for example, a rolling ball mill, a vibration mill, a stone mill type mill, a disc mill, a pin mill, a medium stirring mill, a planetary ball mill, or the like can be used. In dry pulverization using these pulverizers, a small amount of liquid such as alcohol such as ethanol and propanol, polyhydric alcohols such as ethylene glycol, and alcoholic amines such as diethanolamine may be added as a pulverization aid.
このようにして調製した粉砕物を３００℃以上、好ましくは６００℃〜８２０℃の温度で焼成することでレーザーマーキング添加剤としての性能を顕著に向上させることができる。焼成の雰囲気は大気中であって良い。３００℃以下では得られる添加剤の性能は十分でなく、８２０℃以上ではビスマス原料が溶解してしまうため、好ましくない。即ち、３００℃〜８２０℃の温度範囲は、レーザーマーキング用添加剤として十分な性能が得られ、且つ下記する焼成後の粉砕により微粉化が可能な焼成温度範囲である。 The performance as a laser marking additive can be remarkably improved by baking the pulverized material thus prepared at a temperature of 300 ° C. or higher, preferably 600 ° C. to 820 ° C. The firing atmosphere may be in the air. The performance of the additive obtained is not sufficient at 300 ° C. or lower, and the bismuth raw material is dissolved at 820 ° C. or higher. That is, the temperature range of 300 ° C. to 820 ° C. is a firing temperature range in which sufficient performance can be obtained as an additive for laser marking and can be pulverized by pulverization after firing described below.
焼成後、焼成物は汎用の粉砕機により粉砕される。粉砕方法は特に限定をされないが、添加剤の粒子径を小さくするためには湿式粉砕が好適に適用される。粉砕後、乾燥、解砕工程を経ることで、本発明のレーザーマーキング用添加剤が得られる。 After firing, the fired product is pulverized by a general-purpose pulverizer. The pulverization method is not particularly limited, but wet pulverization is suitably applied to reduce the particle size of the additive. After the pulverization, the laser marking additive of the present invention is obtained by passing through drying and crushing steps.
次に、本発明によるレーザーマーキング用添加剤を含むレーザーマーキング可能な成形物について、説明をする。 Next, a laser markable molded article containing the laser marking additive according to the present invention will be described.
成形物の基材の代表的な例は合成樹脂製のものであるが、基材は劣化を生じるほどの高い加工温度を必要としないガラスやセラミックからなるものでもよい。 A typical example of the base material of the molded product is made of a synthetic resin, but the base material may be made of glass or ceramic that does not require a high processing temperature to cause deterioration.
合成樹脂の種類は特に限定されず、熱可塑性樹脂でも熱硬化性樹脂でもよい。 The kind of the synthetic resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin.
熱可塑性樹脂の例としては、ポリオレフィン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、ポリ酢酸ビニル、ポリテトラフルオロエチレン、アクリロニトリルブタジエンスチレン、ポリアクリルメタクリレート、ポリアミド、ナイロン、ポリアセタール、ポリカーボネート、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリフェニレンスルファイド、ポリスルホン、ポリイミド、ポリアミド、およびこれらの混合物およびこれらをベースとした共重合体等が挙げられる。 Examples of thermoplastic resins include polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene, polyacryl methacrylate, polyamide, nylon, polyacetal, polycarbonate, polybutylene terephthalate, polyethylene Examples thereof include terephthalate, polyphenylene sulfide, polysulfone, polyimide, polyamide, a mixture thereof, and a copolymer based on these.
熱硬化性樹脂の例としては、フェノール樹脂、エポキシ樹脂、メラミン樹脂、尿素樹脂、不飽和ポリエステル樹脂、アルキド樹脂、ポリウレタン、熱硬化性ポリイミドおよびこれらの混合物等が挙げられる。 Examples of thermosetting resins include phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethanes, thermosetting polyimides, and mixtures thereof.
本発明によるレーザーマーキング用添加剤は、シリコーン等の珪素骨格ポリマーにも適用することが可能である。 The additive for laser marking according to the present invention can be applied to a silicon skeleton polymer such as silicone.
基材の形状および大きさは、任意であってよい。例えば部材や容器、包装品、電子部品、カードおよびコーティング組成物等が一例として挙げられる。 The shape and size of the substrate may be arbitrary. Examples thereof include members, containers, packages, electronic parts, cards, and coating compositions.
成形物中のレーザーマーキング用添加剤の最適な量は、樹脂の種類や基材の形状により異なる。その為、最適な添加量は使用条件によりその都度決定されるが、本発明のレーザーマーキング用添加剤の場合、最小で０．０１重量％程度の添加量から十分なレーザーマーキング性能が得られる。よりマーキングの黒度を向上させたい場合、ないしは基材の形状がフィルムや塗料のような薄膜の形状である場合、十分なレーザーマーキング性能を付与する為には、本発明のレーザーマーキング用添加剤の添加量を増やすことで必要なレーザーマーキング性能を確保することができる。目安としては、添加量は最大でも３０重量％程度まで添加すれば良く、成形性等のその他の諸物性に影響がでない範囲で添加量を増やしても良い。 The optimum amount of the laser marking additive in the molded product varies depending on the type of resin and the shape of the substrate. Therefore, the optimum addition amount is determined each time depending on the use conditions, but in the case of the additive for laser marking of the present invention, sufficient laser marking performance can be obtained from the addition amount of about 0.01% by weight at the minimum. When it is desired to further improve the blackness of the marking, or when the shape of the base material is a thin film such as a film or paint, the additive for laser marking of the present invention is used to impart sufficient laser marking performance. The necessary laser marking performance can be ensured by increasing the amount of addition. As a guide, the addition amount may be up to about 30% by weight at the maximum, and the addition amount may be increased within a range that does not affect other physical properties such as moldability.
本発明によるレーザーマーキング用添加剤は、基材への着色を目的として、無機ないしは有機顔料および染料との併用の形態で基材に添加することができる。 The additive for laser marking according to the present invention can be added to a substrate in the form of a combination with an inorganic or organic pigment and a dye for the purpose of coloring the substrate.
無機顔料の例としては、酸化チタン、酸化亜鉛、酸化アンチモン、硫化亜鉛等の白色顔料；酸化マグネシウム、酸化カルシウム等の体質顔料；酸化鉄、群青、紺青、カーボンブラック；チタンイエローやコバルトブルー等の複合酸化物顔料等の着色顔料；オキシ塩化ビスマス、酸化チタン等で被覆された雲母顔料のような高輝性顔料が挙げられる。 Examples of inorganic pigments include white pigments such as titanium oxide, zinc oxide, antimony oxide, and zinc sulfide; extender pigments such as magnesium oxide and calcium oxide; iron oxide, ultramarine blue, bitumen, carbon black; titanium yellow, cobalt blue, etc. Color pigments such as complex oxide pigments; high luster pigments such as mica pigments coated with bismuth oxychloride, titanium oxide and the like.
有機顔料の例としては、アゾ、アゾメチン、メチン、アントラキノン、フタロシアニン、ペリレン、チオインジゴ、キナクリドン、およびキノフタロン顔料等が挙げられる。 Examples of organic pigments include azo, azomethine, methine, anthraquinone, phthalocyanine, perylene, thioindigo, quinacridone, and quinophthalone pigments.
染料の例としては、アントラキノン系、アゾ染料の金属錯体、更にクマリン、ナフタルイミド、キサンテン、チアジン等の蛍光染料が挙げられる。 Examples of the dye include anthraquinone series, metal complexes of azo dyes, and fluorescent dyes such as coumarin, naphthalimide, xanthene, and thiazine.
また、光安定剤や酸化防止剤、難燃化剤、ガラス繊維など樹脂の加工に汎用されている添加剤を用途に応じ併用しても良い。さらに紫外線吸収剤、帯電防止剤、電磁波遮断用添加剤等の既知の添加剤との併用も可能である。 Moreover, you may use together the additive generally used for processing of resin, such as a light stabilizer, antioxidant, a flame retardant, glass fiber, according to a use. Furthermore, it can be used in combination with known additives such as an ultraviolet absorber, an antistatic agent, and an electromagnetic wave shielding additive.
発明のレーザーマーキング用添加剤を用いることで、樹脂成形物の望ましくない着色を起こさず、且つ黒さとコントラストに優れたマーキングを可能にする樹脂成形物を提供することができる。 By using the additive for laser marking of the invention, it is possible to provide a resin molded product that does not cause undesirable coloring of the resin molded product and enables marking with excellent blackness and contrast.
つぎに、本発明を具体的に説明するために、本発明の実施例およびこれとの比較を示すための比較例をいくつか挙げる。 Next, in order to specifically explain the present invention, some examples of the present invention and comparative examples for showing comparison with the examples will be given.
実施例１
三酸化ビスマス１９８．６ｇと三酸化ガドリウム１．４ｇを、直径１５ｍｍのアルミナボール２ｋｇの入った内容積２リットルの転動ボールミルに入れ、１２時間粉砕混合を行った。この混合物をるつぼに詰め、電気炉に入れて８００℃で３時間焼成した。得られた焼成物を転動ボールミルで平均粒子径が２〜３μｍになるまで湿式粉砕し、乾燥して淡黄色のレーザーマーキング用添加剤を得た。
Example 1
Bismuth trioxide (198.6 g) and gadolinium trioxide (1.4 g) were placed in a rolling ball mill having an internal volume of 2 liters containing 2 kg of alumina balls having a diameter of 15 mm, and pulverized and mixed for 12 hours. The mixture was packed in a crucible and placed in an electric furnace and baked at 800 ° C. for 3 hours. The obtained fired product was wet pulverized with a rolling ball mill until the average particle size became 2 to 3 μm and dried to obtain a light yellow laser marking additive.
実施例２
原料を、三酸化ビスマス１９９．３ｇと三酸化ネオジム０．７ｇに変えた以外、実施例１と同様の操作を行い、淡黄色のレーザーマーキング用添加剤を得た。
Example 2
A light yellow laser marking additive was obtained in the same manner as in Example 1 except that the raw materials were changed to 199.3 g of bismuth trioxide and 0.7 g of neodymium trioxide.
比較例１
市販の三酸化ビスマス（平均粒径２．９μｍ）を用意した。
Comparative Example 1
Commercially available bismuth trioxide (average particle size 2.9 μm) was prepared.
比較例２
特許文献４に記載の方法に従ってジルコン酸ビスマス化合物２６７−０２４ａを製造した。すなわち、三酸化ビスマス９５．７ｇと酸化ジルコニウム４．３ｇを混合し、且つ１０００℃で１０分間るつぼ中で溶融させ、得られた溶融物をついで水浴中に注いだ。その後、乾燥、粉砕を経て黄色のレーザーマーキング用添加剤を得た。
Comparative Example 2
According to the method described in Patent Document 4, bismuth zirconate compound 267-024a was produced. That is, 95.7 g of bismuth trioxide and 4.3 g of zirconium oxide were mixed and melted in a crucible at 1000 ° C. for 10 minutes, and the obtained melt was then poured into a water bath. Then, the yellow laser marking additive was obtained through drying and pulverization.
比較例３
特許文献４に記載の方法に従ってニオブ酸ビスマス化合物２６７−０５９ａを製造した。すなわち、三酸化ビスマス９８．８ｇと五酸化ニオブ１．２ｇを混合し、且つ１０００℃で１０分間、１０９３℃で１０分間、るつぼ中で加熱し、ついでこの混合物を水浴中に注いだ。その後、乾燥、粉砕を経て淡黄色のレーザーマーキング用添加剤を得た。
Comparative Example 3
According to the method described in Patent Document 4, bismuth niobate compound 267-059a was produced. That is, 98.8 g of bismuth trioxide and 1.2 g of niobium pentoxide were mixed and heated in a crucible at 1000 ° C. for 10 minutes and 1093 ° C. for 10 minutes, and then the mixture was poured into a water bath. Then, after drying and grinding, a light yellow laser marking additive was obtained.
比較例４
特許文献４に記載の方法に従ってビスマス亜鉛酸化物化合物１７４−１１５ｅを製造した。すなわち、三酸化ビスマス９７．７ｇと酸化亜鉛２．３ｇを混合し、且つ７４９℃で６５時間、コージエライト・サガー中で加熱した。その後、この混合物を粉砕することにより淡黄色のレーザーマーキング用添加剤を得た。
Comparative Example 4
According to the method described in Patent Document 4, bismuth zinc oxide compound 174-115e was produced. That is, 97.7 g of bismuth trioxide and 2.3 g of zinc oxide were mixed and heated in cordierite sagar at 749 ° C. for 65 hours. Thereafter, this mixture was pulverized to obtain a light yellow laser marking additive.
比較例５
特許文献４に記載の方法に従ってチタン酸ビスマス化合物１７４−０１３ａを製造した。すなわち、三酸化ビスマス９７．２ｇと酸化チタン２．８ｇを混合し、且つ１０００℃で１０分間、るつぼ中で溶融させ、得られた溶融物をついで水浴中に注いだ。その後、乾燥、粉砕を経て淡黄色のレーザーマーキング用添加剤を得た。
Comparative Example 5
According to the method described in Patent Document 4, bismuth titanate compound 174-013a was produced. That is, 97.2 g of bismuth trioxide and 2.8 g of titanium oxide were mixed and melted in a crucible at 1000 ° C. for 10 minutes, and the obtained melt was then poured into a water bath. Then, after drying and grinding, a light yellow laser marking additive was obtained.
比較例６
特許文献４に記載の方法に従ってストロンチウムビスマス酸化物化合物２６７−０４７ａを製造した。すなわち、三酸化ビスマス８７．１ｇと炭酸ストロンチウム１２．９ｇを混合し、且つ１０００℃で１０分間、１０９３℃で１０分間、１１４９℃で１分間、るつぼ中で溶融させ、得られた溶融物をついで水浴中に注いだ。その後、乾燥、粉砕を経て黄色のレーザーマーキング用添加剤を得た。
Comparative Example 6
Strontium bismuth oxide compound 267-047a was produced according to the method described in Patent Document 4. That is, 87.1 g of bismuth trioxide and 12.9 g of strontium carbonate were mixed and melted in a crucible at 1000 ° C. for 10 minutes, 1093 ° C. for 10 minutes, and 1149 ° C. for 1 minute, and the resulting melt was then added. It was poured into a water bath. Then, the yellow laser marking additive was obtained through drying and pulverization.
比較例７
特許文献４に記載の方法に従ってアルミン酸ビスマス化合物２６７−０２２ａを製造した。すなわち、三酸化ビスマス９９．１ｇと酸化アルミニウム０．９ｇを混合し、且つ１０００℃で１０分間るつぼ中で溶融させ、得られた溶融物をついで水浴中に注いだ。その後、乾燥、粉砕を経て黄色のレーザーマーキング用添加剤を得た。
Comparative Example 7
According to the method described in Patent Document 4, bismuth aluminate compound 267-022a was produced. That is, 99.1 g of bismuth trioxide and 0.9 g of aluminum oxide were mixed and melted in a crucible at 1000 ° C. for 10 minutes, and the obtained melt was then poured into a water bath. Then, the yellow laser marking additive was obtained through drying and pulverization.
比較例８
原料を、三酸化ビスマス１９８．５ｇと酸化サマリウム１．６ｇに変えた以外、実施例１と同様の操作を行い、淡黄色のレーザーマーキング用添加剤を得た。
Comparative Example 8
A light yellow laser marking additive was obtained in the same manner as in Example 1 except that the raw material was changed to 198.5 g of bismuth trioxide and 1.6 g of samarium oxide.
比較例９
原料を、三酸化ビスマス１９９．２ｇと酸化ユウロピウム０．８ｇに変えた以外、実施例１と同様の操作を行い、淡黄色のレーザーマーキング用添加剤を得た。
Comparative Example 9
A light yellow laser marking additive was obtained in the same manner as in Example 1 except that the raw materials were changed to 199.2 g of bismuth trioxide and 0.8 g of europium oxide.
比較例１０
原料を、三酸化ビスマス１９９．２ｇと酸化ジスプロシウム０．８ｇに変えた以外、実施例１と同様の操作を行い、淡黄色のレーザーマーキング用添加剤を得た。
Comparative Example 10
A light yellow laser marking additive was obtained in the same manner as in Example 1 except that the raw materials were changed to 199.2 g of bismuth trioxide and 0.8 g of dysprosium oxide.
比較例１１
原料を、三酸化ビスマス１９９．２ｇと酸化ホルミウム０．８ｇに変えた以外、実施例１と同様の操作を行い、淡黄色のレーザーマーキング用添加剤を得た。
Comparative Example 11
A light yellow laser marking additive was obtained in the same manner as in Example 1 except that the raw material was changed to 199.2 g of bismuth trioxide and 0.8 g of holmium oxide.
比較例１２
原料を、三酸化ビスマス１９９．２ｇと酸化イッテルビウム０．８ｇに変えた以外、実施例１と同様の操作を行い、淡黄色のレーザーマーキング用添加剤を得た。
Comparative Example 12
A light yellow laser marking additive was obtained in the same manner as in Example 1, except that the raw materials were changed to 199.2 g of bismuth trioxide and 0.8 g of ytterbium oxide.
比較例１３
特許文献５に記載の銅モリブデン系複合酸化物（東罐マテリアル・テクノロジー社製４２−９０３Ａ、平均粒径１．５μｍ）を用意した。
Comparative Example 13
A copper-molybdenum-based composite oxide described in Patent Document 5 (42-903A manufactured by Toago Material Technology Co., Ltd., average particle size of 1.5 μm) was prepared.
評価試験
実施例および比較例で得られたレーザーマーキング用添加剤に対し、下記の方法で、樹脂への初期着色性およびレーザーマーキング特性を評価した。得られた結果を表１にまとめて示す。
Evaluation Test With respect to the additives for laser marking obtained in Examples and Comparative Examples, the initial coloring property to the resin and the laser marking characteristics were evaluated by the following methods. The obtained results are summarized in Table 1.
(1)初期着色性
高密度ポリエチレン樹脂に上記添加剤を０．０２５ＰＨＲ（樹脂１００重量部に対する添加剤の重量部数）で分散させた。この組成物を７０℃で３時間乾燥させた後、射出成形機（日本製鋼所社製、ＪＳＷ、Ｊ５０５Ａ１１）を使用し２００℃で板状に成形した。得られた成形板の初期着色性を下記基準で目視にて評価した。
(1) Initial colorability The above additives were dispersed in a high-density polyethylene resin at 0.025 PHR (parts by weight of the additive with respect to 100 parts by weight of the resin). This composition was dried at 70 ° C. for 3 hours, and then molded into a plate at 200 ° C. using an injection molding machine (manufactured by Nippon Steel Works, JSW, J505A11). The initial colorability of the resulting molded plate was visually evaluated according to the following criteria.
初期着色性：成形板作製時の着色度合い
×濃い着色、
○ほとんど着色なし
(2)レーザーマーキング特性
(1)にて作成した成形板に対して、ＹＡＧレーザー（日本電気社製、ＳＬ４７５Ｋ）を照射し、成形板を変色させた。レーザー照射条件は、入力電流２０Ａ、送り速度５００ｍｍ／秒、Ｑ―ｓｗ周波数５ｋＨｚであった。
Initial colorability: Coloring degree when forming plate x dark coloring
○ Almost no coloring
(2) Laser marking characteristics
The molded plate prepared in (1) was irradiated with a YAG laser (manufactured by NEC Corporation, SL475K) to discolor the molded plate. The laser irradiation conditions were an input current of 20 A, a feed rate of 500 mm / second, and a Q-sw frequency of 5 kHz.
変色部分を分光光度計（大日精化工業社製、カラコムＣ）により測色し、その際のＬ＊値より算出した黒度を以下基準で評価した。 The discolored portion was measured with a spectrophotometer (Daiichi Seika Kogyo Co., Ltd., Karakom C), and the blackness calculated from the L * value at that time was evaluated according to the following criteria.
印字黒度：レーザーを照射した際の印字黒度（実施例１の黒度を１００とする指数で表記した）
×ほぼ印字不可（実施例１の黒度１００に対して２０未満）、
△黒度不良（実施例１の黒度１００に対して２０以上８０未満）、
○黒度良（実施例１の黒度１００に対して８０以上９０未満）、
◎黒度非常に良（実施例１の黒度１００に対して９０以上）
印字精細性：レーザーを照射した際の印字繊細性
×ほぼ印字不可、
△印字かすれ、
○印字良、
◎ 繊細な印字
× Almost imprintable (less than 20 for blackness 100 of Example 1),
△ blackness defect (20 or more and less than 80 with respect to blackness 100 of Example 1),
○ Good blackness (80 to less than 90 with respect to 100 blackness in Example 1),
◎ Excellent blackness (90 or more with respect to 100 blackness in Example 1)
Print fineness: Print fineness when irradiated with laser × Almost impossible to print,
△ The print is faint,
○ Good printing,
◎ Delicate printing
表１から明らかなように、実施例によるレーザーマーキング用添加剤を含む成形物は、初期着色性およびレーザーマーキング特性ともに優れている。 As is apparent from Table 1, the molded product containing the additive for laser marking according to the examples is excellent in both initial colorability and laser marking characteristics.
Claims (3)
Ｂｉ（１−ｘ）ＭｘＯｙ
（式中、Ｍはガドリウムおよびネオジムから選択される少なくとも１つの金属、ｘおよびｙはそれぞれ０．００１＜ｘ＜０．５、１＜ｙ＜２．５の関係を有する値である。） An additive for laser marking, comprising a metal oxide represented by the following general formula .
Bi (1-x) M x O y
(In the formula, M is at least one metal selected from gadolinium and neodymium, and x and y are values having a relationship of 0.001 <x <0.5 and 1 <y <2.5, respectively.)
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| JP5991568B2 (en) * | 2010-12-02 | 2016-09-14 | パナソニックＩｐマネジメント株式会社 | Laser marking method and manufacturing method of marked urea resin molding |
| JP6190811B2 (en) | 2012-09-14 | 2017-08-30 | 三菱エンジニアリングプラスチックス株式会社 | Thermoplastic resin composition, resin molded product, and method for producing resin molded product with plating layer |
| JP6421117B2 (en) * | 2013-05-20 | 2018-11-07 | 東罐マテリアル・テクノロジー株式会社 | Additive for bismuth oxide laser marking |
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| JPS61286223A (en) * | 1985-06-11 | 1986-12-16 | Natl Inst For Res In Inorg Mater | Oxide of bismuth-yttrium (bi2-2xy2-xo3) (x=0.215-0.235) having hexagonal laminar structure and its preparation |
| JP2873249B2 (en) * | 1990-11-28 | 1999-03-24 | 日本ペルノックス株式会社 | Resin composition that can be marked black by laser beam irradiation |
| JPH07277735A (en) * | 1994-04-05 | 1995-10-24 | Natl Inst For Res In Inorg Mater | Solid solution of oxides of bismuth and rare earth metals having body-centered cubic lattice structure and production thereof |
| US6503316B1 (en) * | 2000-09-22 | 2003-01-07 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Bismuth-containing laser markable compositions and methods of making and using same |
| JP2004358390A (en) * | 2003-06-05 | 2004-12-24 | Mitsubishi Chemicals Corp | Carbon dioxide absorbing material |
| JP2008117470A (en) * | 2006-11-02 | 2008-05-22 | Sony Corp | Optical information recording medium and method for manufacturing optical information recording medium, bca (burst cutting area) marking method |
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| JP2015232610A (en) * | 2014-06-09 | 2015-12-24 | 株式会社フジシール | Label, heat-shrinkable laminated film, and self-stretchable laminated film |
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