JP2004168842A - Composition for ink to prevent forgery, ink to prevent forgery, and printed matter prevented from forgery - Google Patents

Composition for ink to prevent forgery, ink to prevent forgery, and printed matter prevented from forgery Download PDF

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JP2004168842A
JP2004168842A JP2002334487A JP2002334487A JP2004168842A JP 2004168842 A JP2004168842 A JP 2004168842A JP 2002334487 A JP2002334487 A JP 2002334487A JP 2002334487 A JP2002334487 A JP 2002334487A JP 2004168842 A JP2004168842 A JP 2004168842A
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ink
fine particles
printed
counterfeit
pigment
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JP2002334487A
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JP4314811B2 (en
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Hiromitsu Takeda
広充 武田
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition which is used for ink to prevent forgery, makes reproduction, by e.g. copying, impossible, makes it possible to ascertain the genuineness of a printed matter by using near infrared rays, and is excellent in weatherbility, ink to prevent forgery, and a printed matter prevented from forgery. <P>SOLUTION: The composition and the ink to prevent forgery contain a near infrared absorptive material comprising at least one kind of fine particles selected from fine particles of the hexaboride of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr or Ca, fine particles of ruthenium oxide, and fine particles of rhenium oxide. A more sophisticated printed matter having a higher effect of preventing forgery can be obtained by printing with the composition or the ink which also contains a color pigment, or with the composition or the ink together with an ink comprising only a color pigment. <P>COPYRIGHT: (C)2004,JPO

Description

【0001】
【発明の属する技術分野】
本発明は、近赤外線領域の吸収を利用した偽造防止インク用組成物及び偽造防止インク、並びにこれを用いた偽造防止印刷物に関するものである。
【0002】
【従来の技術】
従来から、預貯金の通帳や身分証明書、クレジットカード、キャッシュカード、小切手、航空券、道路通行券、乗車券、プリペードカード、商品券、証券等の有価印刷物については、偽造を防止するための方法として、その基材や印刷方法に特殊な工夫を施すことが行われてきた。
【0003】
例えば、基材に透かしを入れた特殊印刷(特許文献1)、微細な絵柄の印刷(特許文献2)、バーコードに代表される幾何学形状印刷を用いたデジタル処理化等が行われている。しかし、透かしを入れた特殊印刷の用紙はコストが高く、バーコード印刷はコピー等で簡単に偽造が可能である。また、微細な絵柄の印刷は、現在のカラーコピー機やコンピュータの画像処理技術の向上と、更に人の目による確認という曖昧な要素が加わるため、偽造防止効果が低く汎用的ではない。
【0004】
上記以外の偽造防止方法として、300〜780nmの可視光領域の吸収が少なく且つ600〜1800nmの近赤外線を吸収する印刷インクを利用して、印刷物の真贋情報を検出する方法が提案されている。例えば、可視光領域に吸収の少ない近赤外線吸収材料と樹脂を混合したインクで印刷したものは、その印刷面に赤外線レーザーを照射すると特定波長のみ吸収されるため、反射若しくは透過光を読み取ることで真贋の判定が可能となる。
【0005】
このような近赤外線を吸収する印刷インクとして、フタロシアニン化合物を用いた偽造防止インクが提案されている(特許文献3)。しかしながら、近赤外線吸収材料であるフタロシアニン化合物は、その吸収特性が温度や紫外線等の影響によって低減するため、耐候性に劣るという欠点があった。
【0006】
一方、YやLa等の6ホウ化物微粒子、酸化ルテニウム微粒子等を含む分散膜が、太陽光線の近赤外線を断熱する日射遮蔽膜として提案されている(特許文献4、特許文献5)。しかし、この日射遮蔽膜は窓等からの日射を遮って、室内の温度上昇を防ぐためのものであり、6ホウ化物微粒子や酸化ルテニウム微粒子等の無機微粒子を偽造防止インクに応用することについては全く検討されていなかった。
【0007】
【特許文献1】
特開平09−261418号公報
【特許文献2】
特開平05−338388号公報
【特許文献3】
特開平04−320466号公報
【特許文献4】
特開平11−181336号公報
【特許文献5】
特開2000−096034号公報
【0008】
【発明が解決しようとする課題】
本発明は、このような従来の事情に鑑みてなされたものであり、可視光領域を透過し且つ近赤外線領域に吸収をもつ近赤外線吸収材料を利用して、印刷物の真贋を判定でき、しかも耐候性に優れた偽造防止インク用組成物及び偽造防止インクを提供することを目的とする。
【0009】
また、本発明は、この偽造防止インク用組成物及び偽造防止インクを用いることによって、コピー等では複製が不可能であり、目視判定によらず機械的に確実に真贋の判定ができ、しかも耐侯性に優れていて安価な偽造防止印刷物を提供することを目的とする。
【0010】
【課題を解決するための手段】
上記の目的を達成するため、本発明が提供する偽造防止インク用組成物は、近赤外線吸収材料として、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sr、Caのいずれかの6ホウ化物微粒子、酸化ルテニウム微粒子、及び酸化レニウム微粒子から選ばれた少なくとも1種の微粒子を含むことを特徴とする。また、前記微粒子の表面は、Si、Ti、Al、Zrから選ばれた少なくとも1種の化合物で被覆されていても良い。
【0011】
上記本発明の偽造防止インク用組成物は、前記微粒子と共に、近赤外線を透過する着色顔料を含有することができる。その場合、前記着色顔料は、Cu−Fe−Mn、Cu−Cr、Cu−Cr−Mn、Cu−Cr−Mn−Ni、Cu−Cr−Fe、Co−Cr−Feのいずれかの複合酸化物、チタンブラック、窒化チタン、酸窒化チタン、暗色アゾ顔料、ペリレンブラック顔料、アニリンブラック顔料、カーボンブラックから選ばれた少なくとも1種の近赤外線を透過する黒色顔料であることが好ましい。
【0012】
また、本発明が提供する偽造防止インクは、上記したいずれかの偽造防止インク用組成物、即ち前記微粒子を含むか又は前記微粒子と共に着色顔料を含有する偽造防止インク用組成物を、溶媒中に分散させたことを特徴とするものである。この偽造防止インクの前記溶媒中には、有機バインダーを含むことができる。
【0013】
更に、本発明が提供する偽造防止印刷物は、上記したいずれかの偽造防止インクを、被印刷基材の片面又は両面に印刷したことを特徴とするものである。
【0014】
上記本発明の偽造防止印刷物においては、前記被印刷基材の片面又は両面の少なくとも偽造防止インクの印刷膜上に、更に近赤外線を透過する着色顔料を含有した着色インクを印刷塗布することができる。この場合、前記着色インクは、着色顔料として、Cu−Fe−Mn、Cu−Cr、Cu−Cr−Mn、Cu−Cr−Mn−Ni、Cu−Cr−Fe、Co−Cr−Feのいずれかの複合酸化物、チタンブラック、窒化チタン、酸窒化チタン、暗色アゾ顔料、ペリレンブラック顔料、アニリンブラック顔料、カーボンブラックから選ばれた少なくとも1種の近赤外線を透過する黒色顔料含有することが好ましい。
【0015】
【発明の実施の形態】
本発明において、偽造防止インク用組成物及び偽造防止インクに用いる近赤外線吸収材料は、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sr、Caの6ホウ化物微粒子、あるいは酸化ルテニウム微粒子又は酸化レニウム微粒子である。これらの無機微粒子は、暗色系の材料であるが、微細な微粒子状では、可視光領域(380〜780nm)に透過率のピークを持ち、近赤外線領域(600〜1800nm)に透過率のボトムを持つ透過特性を示す。
【0016】
これらの無機微粒子を含む本発明の偽造防止インクは、可視光領域の吸収が少なく且つ近赤外線領域に吸収をもつため、その印刷面に赤外線レーザーを照射したとき特定の波長を吸収する。従って、この偽造防止インクを被印刷基材の片面又は両面に印刷した印刷物は、特定波長の近赤外線を照射してその反射若しくは透過を読み取ることによって、反射量又は透過量の違いから、印刷物の真贋を判定することができる。
【0017】
例えば、後述する実施例1のLaB微粒子を含有する偽造防止インクは、図1に示すような透過プロファイルを有している。図1から分るように、この偽造防止インクは、可視光領域に透過率のピークを持つため着色が少なく、同時に近赤外線領域に透過率のボトム(吸収ピーク)があるため、その情報を赤外線センサーで読み取ることにより、その情報を用いて印刷物の真贋を判定することが可能である。
【0018】
本発明で近赤外線吸収材料として用いる上記6ホウ化物微粒子、酸化ルテニウム微粒子又は酸化レニウム微粒子は、いずれも無機微粒子であるため、耐侯性に優れている。耐候性を更に向上させるために、その微粒子表面をSi、Ti、Al、Zrの1種又は2種以上の化合物で被覆することができる。これらの化合物は基本的に透明であり、添加したことによって可視光透過率を低下させることはない。
【0019】
また、上記近赤外線吸収材料の透過特性は、6ホウ化物微粒子等の無機微粒子の大きさによっても変化する。即ち、無機微粒子の粒子径が小さいほど、可視光領域の透過率のピークと近赤外線領域の吸収のボトムとの透過率差は大きくなる。逆に粒子径が大きいと、その透過率差が小さくなり、可視光透過率のピークに対する近赤外線の吸収が低下する。そのため、近赤外線吸収材料である6ホウ化物微粒子、酸化ルテニウム微粒子、及び酸化レニウム微粒子の大きさは、目的とする使用方法等に応じて適宜設定することが望ましい。
【0020】
本発明による偽造防止インクの場合、その近赤外線吸収材料として用いる無機微粒子、即ち6ホウ化物微粒子、酸化ルテニウム微粒子、及び酸化レニウム微粒子の粒子径は2μm以下が好ましい。粒子径が2μmを超えると、上記透過率のピークと近赤外線領域の吸収とのボトムの差が小さくなり、可視光領域の透明性を有する近赤外線吸収材料としての効果が低減するからである。
【0021】
また、被印刷基材として用いる透明基材の透明性を維持したり、又は下地印刷の透視可能な透明性を維持したい場合など、実質的に透明な偽造防止コードやバーコードを印刷するためには、無機微粒子の粒子径は更に小さい方が好ましい。即ち、実質的に透明性を保持したまま近赤外線を効率良く吸収する印刷膜を必要とする場合には、偽造防止インク中の無機微粒子の粒子径は800nm以下とすることが好ましい。800nmを超える粒子径の無機微粒子は光を大きく散乱するため、優れた透明性を保持した偽造防止印刷が難しいからである。
【0022】
特に、可視光領域の透明性を重視する偽造防止印刷の場合には、無機粒子による光の散乱をより考慮する必要がある。無機微粒子の粒子径が200nmよりも大きいと、幾何学散乱若しくはミー散乱によって400〜780nmの可視光線領域の光を散乱し、半曇りガラスのようになり、鮮明な透明性が得られないからである。
【0023】
従って、偽造防止印刷に澄んだ透明性を必要とする場合は、無機微粒子の粒子径は200nm以下が好ましく、100nm以下が更に好ましい。粒子径が200nm以下になると、光散乱が低減してレイリー散乱領域になり、散乱光は粒子径の6乗に反比例して低減するため、粒子径の減少に伴って透明性が向上する。また、粒子径が100nm以下になると、散乱光は非常に少なくなり更に好ましい。また、近赤外光線においても、粒子径を小さくすることで散乱が減少し、吸収効率が上昇するため好ましい。
【0024】
本発明の偽造防止インク用組成物は、上記6ホウ化物微粒子、酸化ルテニウム微粒子、又は酸化レニウム微粒子を含むが、これらの無機微粒子と共に、近赤外線と透過する着色顔料を含むことができる。このような着色顔料を含むことによって、人の目に感じる可視光領域では着色顔料と同等の色を呈するが、近赤外線領域では特徴的な吸収を持つ着色した偽造防止インク及びその偽造防止印刷物を得ることができる。尚、この着色した偽造防止インクインクは、可視光領域における吸収が少ないため、着色顔料の色調は保持される。
【0025】
例えば、近赤外線を透過する着色顔料として黒色顔料を混合した偽造防止インクは、黒色顔料のみを含む黒色インクと比較すると、人の目には同等の黒色として認識されるが、赤外線を照射して比較すると異なる透過プロファイルを有することが読み取れる。従って、この黒色の偽造防止インクを用いた印刷物、例えばバーコード印刷した印刷物は、近赤外線吸収材料を含まない通常の黒色インクをダミーとして印刷することで、更に複雑で高度な偽造防止が可能となる。
【0026】
また、本発明の偽造防止インクを被印刷基材の片面又は両面に印刷した印刷物の印刷膜上に、黒色顔料その他の近赤外線と透過する着色顔料を用いた着色インクを塗布又は印刷して偽造防止印刷物とすることもできる。この偽造防止印刷物は、人の目には黒又はその他に着色されて認識されるが、その同じ領域に赤外線でのみ読み取れる文字や記号等が隠れて印刷されているため、赤外線を照射することによって印刷物の真贋を判定することができる。
【0027】
このような着色顔料としては、近赤外線を透過する黒色顔料が好ましい。また、黒色顔料の好ましい具体例としては、Cu−Fe−Mn、Cu−Cr、Cu−Cr−Mn、Cu−Cr−Mn−Ni、Cu−Cr−Fe、Co−Cr−Fe等の複合酸化物、あるいはチタンブラック、窒化チタン、酸窒化チタン、暗色アゾ顔料、ペリレンブラック顔料、アニリンブラック顔料、カーボンブラックを挙げることができる。
【0028】
偽造防止インク中における黒色顔料の粒子径は、近赤外線吸収材料である上記6ホウ化物微粒子、酸化ルテニウム微粒子及び酸化レニウム微粒子と同様に、2μm以下が好ましい。
【0029】
また、透明な被印刷基材の透明性を維持し、又は下地印刷の透視可能な透明性を維持したい場合には、黒色顔料の粒子径も小さい方が好ましい。この場合、黒色の偽造防止インクや、偽造防止印刷膜上に印刷する黒色インクについて、そのインク中の黒色顔料の粒子径は800nm以下が好ましい。
【0030】
特に可視光領域の透明性を重視する場合には、黒色粒子の粒子径は200nm以下、好ましくは100nm以下が良い。その理由は、上述した近赤外線吸収材料である6ホウ化物微粒子、酸化ルテニウム微粒子及び酸化レニウム微粒子の場合と同様である。
【0031】
また、黒色顔料の粒子径を小さくすることで色調に深みが現れ、意匠的に好まれやすい。更にまた、微細な印刷を必要とする場合は、粒子径を小さくすることで光の散乱が少なくなるため、印刷パターンの輪郭が明瞭になり好ましい。
【0032】
本発明の偽造防止インクは、近赤外線吸収材料である上記6ホウ化物微粒子、酸化ルテニウム微粒子、又は酸化レニウム微粒子、及び必要に応じて着色顔料を溶媒中に分散させることで作製する。溶媒としては、エタノール等のアルコール類、メチルエチルケトン等のケトン類、トルエンやキシレン等、使用目的に応じて選択することが可能である。その際、上記微粒子や着色顔料を分散させる方法としては、特に限定されないが、超音波や媒体撹拌ミル等を使用すれば、粒子をほぐして微細化することができるので好ましい。
【0033】
また、上記偽造防止用インクは、溶媒中に有機バインダーを含むことができる。有機樹脂バインダーとしては、特に限定されず、例えば、アクリル系、ウレタン系、エポキシ系、フッ素系、ビニル系、ロジン系等何れでも良く、用途に適したものが選択可能である。
【0034】
また、上記偽造防止インクは、必要に応じて、グラビヤインク、スクリーンインク、オフセットインク、溶融熱転写インクなど、印刷方法に応じた一般的な配合が可能であり、また、可塑剤、酸化剤防止剤、増粘剤、ワックス等の添加剤を含むことができる。
【0035】
上記偽造防止インクを被印刷基材の表面に通常の方法により塗布又は印刷することにより、偽造防止印刷物を得ることができる。その場合、一般的には有機バインダーを含むため、溶媒を蒸発させて有機バインダーを硬化させることで、被印刷基材との結着性が優れ、良好な表面強度を有する印刷膜を得ることができる。尚、有機バインダーの硬化方法としては、紫外線硬化、熱硬化、常温硬化等が挙げられる。
【0036】
また、偽造防止インクが有機バインダーを含まない場合には、被印刷基材に塗布又は印刷し、溶媒を蒸発させることで印刷膜が得られる。ただし、この場合には、印刷膜の剥離や微粒子の脱落を防止するため、その上に透明樹脂からなるカバー層を設けることが好ましい。
【0037】
偽造防止印刷物中における近赤外線吸収材料の含有量は、目的とする用途に応じて変更可能であるが、通常は0.01g/m以上が好ましい。0.01g/m未満の使用量では、近赤外線領域の吸収が顕著に表れないため、偽造防止インクとして機能させることが難しい。また、含有量の上限は特に限定されないが、5g/m以上になると可視光領域の光を大幅に吸収してしまうため、透明性を維持する必要がある場合には5g/mより少ない含有量が好ましい。尚、上記含有量は、全てのフィラーが印刷面に入射する光線に対して同等に作用するため、1m当たりの量で評価することができる。
【0038】
偽造防止インクを印刷するための被印刷基材は、目的とする用途にあったものを使用すればよく、紙の他に、樹脂とパルプの混合物、樹脂フィルム等を用いることができる。また、シール上に偽造防止インクで印刷し、このシールを被印刷基材に貼付してもかまわない。
【0039】
このようにして作製した本発明の偽造防止印刷物は、コピー等では複製が不可能であって、目視判定によらず、赤外線を照射し且つその反射又は透過を検出することによって機械的に確実に、真贋の判定を行うことができる。しかも、赤外線吸収材料としてホウ化物微粒子、酸化ルテニウム微粒子又は酸化レニウム微粒子の無機微粒子を用い、これを印刷法により被印刷基材に適用するため、耐候性に優れ、安価な偽造防止印刷物を提供することができる。
【0040】
【実施例】
次に、実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるわけではない。尚、膜の光学特性は、分光光度計U−4000(日立製作所(株)製)を用いて測定した。実施例中の可視光透過率は、JIS R3106に従って測定を行った。また、平均分散粒子径は、動的光散乱法を用いた測定装置ELS−8000(大塚電子(株)製)により測定した平均値をもって示した。
【0041】
実施例1
20gのLaB微粒子をシランカップリング剤と共にエタノール78gに撹拌混合し、これを分散処理して、平均分散粒子径が100nmの分散液Aを作製した。この分散液Aの100gを、紫外線硬化樹脂UV3701(東亞合成(株)製)20gと混合して、偽造防止インクとした。
【0042】
被印刷基材として厚さ50μmの透明PETフィルムを使用し、その表面に上記偽造防止インクをバーコーターにより成膜した。この膜を70℃で1分間乾燥して溶媒を蒸発させた後、高圧水銀ランプを用いて紫外線を照射し、紫外線硬化樹脂を硬化させた。
【0043】
得られた印刷膜の可視光透過率は76%であった。また、可視光領域の550nmの透過率は78%であり、近赤外線領域の800nmの透過率は44%、900nmの透過率は35%、1000nmの透過率は33%であった。この印刷膜の透過プロファイルを図1に示す。
【0044】
このように、赤外線吸収材料としてLaB微粒子を含む印刷膜は、可視光領域では高い透過率を示し、近赤外線領域では透過率が顕著に低くなっている。従って、実施例1の印刷膜は、近赤外線領域の光線を用いてデータ処理することにより真贋を判定でき、偽造防止印刷物として有効であることが分る。
【0045】
実施例2
近赤外線を透過する黒色顔料Paliotol Black L0080(BASF製)20gを、高分子系分散剤と共にエタノール78gに撹拌混合し、これを分散処理して、平均分散粒子径120nmの分散液Bを作製した。この分散液Bを、上記実施例1における分散液A及び紫外線硬化樹脂UV3701(東亞合成(株)製)と混合して、黒色の偽造防止インクを作製した。
【0046】
被印刷基材として厚さ50μmの透明PETフィルムを使用し、その表面に上記黒色の偽造防止インクをバーコーターにより成膜した。この膜を70℃で1分間乾燥して溶媒を蒸発させた後、高圧水銀ランプを用いて紫外線を照射し、紫外線硬化樹脂を硬化させた。
【0047】
得られた印刷膜の可視光透過率は1%であった。また、可視光領域の550nmの透過率は1%であり、近赤外線領域の800nmの透過率は24%、900nmの透過率は20%、1000nmの透過率は19%であった。この印刷膜の透過プロファイルを図2に示す。
【0048】
比較例1
上記実施例2における分散液Bを、紫外線硬化樹脂UV3701(東亞合成(株)製)と混合し、近赤外線吸収材料を含まない黒色インクとした。この黒色インクを用い、上記実施例2と同様にして、厚さ50μmの透明PETフィルム上に印刷膜を形成した。
【0049】
得られた印刷膜の可視光透過率は1%であった。また、可視光領域の550nmの透過率は1%であり、近赤外線領域の800nmの透過率は78%、900nmの透過率は82%、1000nmの透過率は85%であった。この印刷膜の透過プロファイルを図2に示す。
【0050】
図2に示した実施例2と比較例1の各印刷膜の透過プロファイから、実施例2の印刷膜は可視光領域では比較例1と同様の黒色を示すが、近赤外線領域では透過率が大きく異なることが分る。従って、実施例2の黒色の印刷膜は、肉眼では同一の黒色印刷として認識されるが、近赤外線領域の光線を用いたデータ処理によって検出可能であり、偽造防止印刷物として有効であることが分る。
【0051】
【発明の効果】
本発明によれば、可視光領域の光を透過し且つ近赤外線領域に吸収をもち、耐候性に優れた偽造防止インク用組成物及び偽造防止インクを提供することができる。また、この偽造防止インク用組成物及び偽造防止インクを用いることによって、コピー等では複製が不可能であり、目視判定によらず機械的に簡単且つ確実に真贋の判定ができ、しかも耐侯性に優れた安価な偽造防止印刷物を提供することができる。
【0052】
更に、近赤外線を透過する着色顔料と併用することにより、可視光領域の光を透過し且つ近赤外線領域に吸収をもち、耐候性に優れ、黒色等に着色した偽造防止インク用組成物及び偽造防止インクを提供することができる。この着色した偽造防止インクは、着色顔料のみのインクと組合わせて印刷することにより、一層複雑で、偽造防止効果の高い偽造防止印刷物を得ることができる。
【図面の簡単な説明】
【図1】本発明のLaB微粒子を含む偽造防止インクによる実施例1の印刷膜の透過プロファイルを示すグラフである。
【図2】本発明のLaB微粒子と黒色顔料を含む偽造防止インクによる実施例2の印刷膜の透過プロファイルと、黒色インクによる比較例1の印刷膜の透過プロファイルを示すグラフである。
[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an anti-counterfeit ink composition and anti-counterfeit ink utilizing absorption in the near infrared region, and an anti-counterfeit print using the same.
[0002]
[Prior art]
Methods for preventing counterfeiting of valuable printed materials such as bankbooks and ID cards for deposits and savings, credit cards, cash cards, checks, air tickets, road tickets, tickets, prepaid cards, gift certificates, securities, etc. In particular, special measures have been taken for the base material and the printing method.
[0003]
For example, special printing with a watermark on a base material (Patent Literature 1), printing of a fine pattern (Patent Literature 2), digital processing using geometric shape printing represented by a bar code, and the like are performed. . However, special printing paper with a watermark is expensive, and bar code printing can be easily forged by copying or the like. In addition, printing of a fine pattern is not general-purpose because it has a low anti-counterfeiting effect because it has an improved image processing technology of current color copiers and computers and furthermore has an obscure element of confirmation by human eyes.
[0004]
As a forgery prevention method other than the above, there has been proposed a method of detecting authenticity information of a printed material by using a printing ink that has a small absorption in a visible light region of 300 to 780 nm and absorbs a near infrared light of 600 to 1800 nm. For example, when printing with an ink that is a mixture of a near-infrared absorbing material and resin with low absorption in the visible light region, only a specific wavelength is absorbed when the printed surface is irradiated with an infrared laser. The authenticity can be determined.
[0005]
As a printing ink absorbing such near infrared rays, a forgery prevention ink using a phthalocyanine compound has been proposed (Patent Document 3). However, the phthalocyanine compound, which is a near-infrared absorbing material, has a disadvantage that it has poor weather resistance because its absorption characteristics are reduced by the influence of temperature, ultraviolet rays and the like.
[0006]
On the other hand, a dispersion film containing hexaboride fine particles such as Y and La, ruthenium oxide fine particles, and the like has been proposed as a solar shading film that insulates near infrared rays of sunlight (Patent Documents 4 and 5). However, this solar shading film is for blocking the sunshine from windows and the like to prevent the temperature from rising in the room. Regarding the application of inorganic fine particles such as hexaboride fine particles and ruthenium oxide fine particles to the forgery prevention ink, Not considered at all.
[0007]
[Patent Document 1]
JP 09-261418 A [Patent Document 2]
JP 05-338388 A [Patent Document 3]
JP-A-04-320466 [Patent Document 4]
JP-A-11-181336 [Patent Document 5]
Japanese Patent Application Laid-Open No. 2000-096034
[Problems to be solved by the invention]
The present invention has been made in view of such conventional circumstances, and can determine the authenticity of a printed matter by using a near-infrared absorbing material that transmits a visible light region and absorbs in a near-infrared region, and An object of the present invention is to provide a composition for anti-counterfeit ink and an anti-counterfeit ink excellent in weather resistance.
[0009]
In addition, the present invention uses the anti-counterfeit ink and the anti-counterfeit ink to make it impossible to copy by copying or the like, and to reliably and mechanically judge authenticity without visual judgment. An object of the present invention is to provide an inexpensive anti-counterfeit printed matter having excellent properties.
[0010]
[Means for Solving the Problems]
In order to achieve the above object, the anti-counterfeit ink composition provided by the present invention includes, as near-infrared absorbing materials, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, and Er. , Tm, Yb, Lu, Sr, and Ca, at least one type of fine particles selected from hexaboride fine particles, ruthenium oxide fine particles, and rhenium oxide fine particles. Further, the surface of the fine particles may be coated with at least one compound selected from Si, Ti, Al, and Zr.
[0011]
The anti-counterfeit ink composition of the present invention may contain a coloring pigment that transmits near infrared rays together with the fine particles. In that case, the coloring pigment is a composite oxide of any of Cu-Fe-Mn, Cu-Cr, Cu-Cr-Mn, Cu-Cr-Mn-Ni, Cu-Cr-Fe, and Co-Cr-Fe. And at least one black pigment that transmits near-infrared rays selected from titanium black, titanium nitride, titanium oxynitride, dark azo pigments, perylene black pigments, aniline black pigments, and carbon black.
[0012]
Further, the anti-counterfeit ink provided by the present invention is any one of the anti-counterfeit ink compositions described above, that is, the anti-counterfeit ink composition containing the fine particles or a color pigment together with the fine particles, in a solvent. It is characterized by being dispersed. An organic binder can be contained in the solvent of the anti-counterfeit ink.
[0013]
Further, the anti-counterfeit printed matter provided by the present invention is characterized in that one of the anti-counterfeit inks described above is printed on one side or both sides of a substrate to be printed.
[0014]
In the anti-counterfeit printed matter of the present invention, at least on one side or both sides of the substrate to be printed, at least on the anti-counterfeit ink printing film, a colored ink containing a color pigment that transmits near-infrared rays can be applied by printing. . In this case, the coloring ink may be any one of Cu-Fe-Mn, Cu-Cr, Cu-Cr-Mn, Cu-Cr-Mn-Ni, Cu-Cr-Fe, and Co-Cr-Fe as a coloring pigment. , A black pigment that transmits at least one kind of near-infrared ray selected from the group consisting of: titanium black, titanium nitride, titanium oxynitride, dark azo pigment, perylene black pigment, aniline black pigment, and carbon black.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, the near infrared absorbing material used for the anti-counterfeit ink and the anti-counterfeit ink is Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Hexaboride particles of Lu, Sr, and Ca, or ruthenium oxide particles or rhenium oxide particles. These inorganic fine particles are dark-colored materials, but in the case of fine fine particles, have a transmittance peak in the visible light region (380 to 780 nm), and have a transmittance bottom in the near infrared region (600 to 1800 nm). It shows the transmission characteristics it has.
[0016]
Since the anti-counterfeit ink of the present invention containing these inorganic fine particles has little absorption in the visible light region and has absorption in the near infrared region, it absorbs a specific wavelength when its printed surface is irradiated with an infrared laser. Therefore, the printed matter printed on one or both sides of the substrate to be printed with the forgery prevention ink is irradiated with near-infrared light of a specific wavelength and its reflection or transmission is read. The authenticity can be determined.
[0017]
For example, the anti-counterfeit ink containing LaB 6 fine particles of Example 1 described later has a transmission profile as shown in FIG. As can be seen from FIG. 1, the anti-counterfeit ink has a transmittance peak in the visible light region and therefore has little coloring, and at the same time, has a transmittance bottom (absorption peak) in the near-infrared region. By reading with a sensor, it is possible to determine the authenticity of the printed matter using the information.
[0018]
The hexaboride fine particles, ruthenium oxide fine particles or rhenium oxide fine particles used as the near-infrared absorbing material in the present invention are all inorganic fine particles, and thus have excellent weather resistance. In order to further improve the weather resistance, the surface of the fine particles can be coated with one or more compounds of Si, Ti, Al, and Zr. These compounds are basically transparent, and do not reduce the visible light transmittance when added.
[0019]
In addition, the transmission characteristics of the near-infrared absorbing material vary depending on the size of inorganic fine particles such as hexaboride fine particles. That is, as the particle diameter of the inorganic fine particles is smaller, the transmittance difference between the transmittance peak in the visible light region and the absorption bottom in the near infrared region becomes larger. Conversely, if the particle size is large, the difference in transmittance becomes small, and the absorption of near infrared rays with respect to the peak of visible light transmittance decreases. Therefore, it is desirable that the size of the hexaboride fine particles, the ruthenium oxide fine particles, and the rhenium oxide fine particles, which are the near-infrared absorbing materials, be appropriately set according to the intended use.
[0020]
In the case of the anti-counterfeit ink according to the present invention, the inorganic fine particles used as the near-infrared absorbing material, that is, the hexaboride fine particles, ruthenium oxide fine particles and rhenium oxide fine particles preferably have a particle diameter of 2 μm or less. If the particle diameter exceeds 2 μm, the difference between the peak of the transmittance and the bottom between the absorption in the near infrared region becomes smaller, and the effect as a near infrared absorbing material having transparency in the visible light region is reduced.
[0021]
In addition, to maintain the transparency of the transparent substrate used as the substrate to be printed, or to maintain the see-through transparency of the underlying printing, such as to print a substantially transparent forgery prevention code or bar code It is preferable that the particle diameter of the inorganic fine particles be smaller. That is, when a printing film that efficiently absorbs near infrared rays while maintaining transparency is required, the particle diameter of the inorganic fine particles in the forgery prevention ink is preferably 800 nm or less. This is because inorganic fine particles having a particle diameter of more than 800 nm scatter light greatly, so that it is difficult to perform forgery prevention printing while maintaining excellent transparency.
[0022]
In particular, in the case of anti-counterfeit printing in which transparency in the visible light region is emphasized, it is necessary to further consider light scattering by inorganic particles. When the particle diameter of the inorganic fine particles is larger than 200 nm, light in the visible light region of 400 to 780 nm is scattered by geometric scattering or Mie scattering, and the glass becomes semi-frosted glass, and clear transparency cannot be obtained. is there.
[0023]
Therefore, when clear transparency is required for anti-counterfeit printing, the particle diameter of the inorganic fine particles is preferably 200 nm or less, more preferably 100 nm or less. When the particle diameter is 200 nm or less, light scattering is reduced to form a Rayleigh scattering region, and the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the transparency is improved as the particle diameter decreases. Further, when the particle diameter is 100 nm or less, scattered light is extremely reduced, which is more preferable. Also, in the case of near-infrared rays, it is preferable to reduce the particle diameter to reduce scattering and increase absorption efficiency.
[0024]
The anti-counterfeit ink composition of the present invention contains the above-mentioned hexaboride fine particles, ruthenium oxide fine particles or rhenium oxide fine particles, and may contain a coloring pigment that transmits near infrared rays together with these inorganic fine particles. By containing such a coloring pigment, a colored anti-counterfeit ink having a characteristic absorption in the near-infrared region, while exhibiting the same color as the colored pigment in the visible light region perceived by human eyes, and its anti-counterfeit printed matter. Obtainable. In addition, since the colored anti-counterfeit ink has little absorption in the visible light region, the color tone of the colored pigment is maintained.
[0025]
For example, anti-counterfeit ink mixed with a black pigment as a color pigment that transmits near-infrared light, when compared to a black ink containing only a black pigment, is recognized as equivalent black to human eyes, In comparison it can be seen that they have different transmission profiles. Therefore, printed matter using this black anti-counterfeit ink, for example, a bar code-printed printed matter, can be further complicated and advanced forgery prevention by printing a normal black ink containing no near infrared absorbing material as a dummy. Become.
[0026]
Further, on a printed film of a printed material in which the anti-counterfeiting ink of the present invention is printed on one side or both sides of a substrate to be printed, a coloring ink using a black pigment or another coloring pigment that transmits near infrared rays is applied or printed by printing or printing. Prevention prints can also be made. This anti-counterfeit printed matter is recognized by the human eye as being colored black or otherwise, but characters and symbols that can only be read with infrared are hidden and printed in the same area, so by irradiating infrared rays The authenticity of the printed matter can be determined.
[0027]
As such a coloring pigment, a black pigment transmitting near infrared rays is preferable. Preferred specific examples of the black pigment include composite oxides such as Cu-Fe-Mn, Cu-Cr, Cu-Cr-Mn, Cu-Cr-Mn-Ni, Cu-Cr-Fe, and Co-Cr-Fe. Products, or titanium black, titanium nitride, titanium oxynitride, dark azo pigments, perylene black pigments, aniline black pigments, and carbon black.
[0028]
The particle size of the black pigment in the anti-counterfeit ink is preferably 2 μm or less as in the case of the above-mentioned hexaboride fine particles, ruthenium oxide fine particles and rhenium oxide fine particles, which are near-infrared absorbing materials.
[0029]
Further, when it is desired to maintain the transparency of the transparent substrate to be printed or to maintain the see-through transparency of the underlying printing, the smaller the particle size of the black pigment, the better. In this case, for the black forgery prevention ink or the black ink to be printed on the forgery prevention printing film, the particle diameter of the black pigment in the ink is preferably 800 nm or less.
[0030]
In particular, when importance is placed on transparency in the visible light region, the particle size of the black particles is preferably 200 nm or less, and more preferably 100 nm or less. The reason is the same as in the case of the hexaboride fine particles, ruthenium oxide fine particles and rhenium oxide fine particles which are the above-mentioned near infrared absorbing materials.
[0031]
Further, when the particle size of the black pigment is reduced, the color tone becomes deeper, and the design is easily liked. Furthermore, when fine printing is required, the scattering of light is reduced by reducing the particle diameter, so that the contour of the printed pattern is clear, which is preferable.
[0032]
The anti-counterfeit ink of the present invention is prepared by dispersing the above-mentioned hexaboride fine particles, ruthenium oxide fine particles, or rhenium oxide fine particles, which are near-infrared absorbing materials, and, if necessary, a coloring pigment in a solvent. As the solvent, alcohols such as ethanol, ketones such as methyl ethyl ketone, and toluene and xylene can be selected according to the purpose of use. At this time, the method for dispersing the fine particles and the color pigment is not particularly limited. However, it is preferable to use an ultrasonic wave or a medium stirring mill because the particles can be loosened and made fine.
[0033]
Further, the anti-counterfeit ink may include an organic binder in a solvent. The organic resin binder is not particularly limited, and may be, for example, any of acrylic, urethane, epoxy, fluorine, vinyl, rosin, and the like, and a material suitable for the use can be selected.
[0034]
In addition, the anti-counterfeit ink can be used as required, such as gravure ink, screen ink, offset ink, and fusion heat transfer ink, in a general formulation according to the printing method. , Thickeners, waxes and other additives.
[0035]
By applying or printing the anti-counterfeit ink on the surface of the substrate to be printed by a usual method, a anti-counterfeit print can be obtained. In this case, since the organic binder is generally contained, by evaporating the solvent and curing the organic binder, it is possible to obtain a printed film having excellent binding properties to the substrate to be printed and having good surface strength. it can. In addition, as a curing method of the organic binder, ultraviolet curing, heat curing, room temperature curing and the like can be mentioned.
[0036]
When the anti-counterfeit ink does not contain an organic binder, it is applied or printed on a substrate to be printed and the solvent is evaporated to obtain a printed film. However, in this case, it is preferable to provide a cover layer made of a transparent resin on the printed film in order to prevent peeling of the printed film and falling off of the fine particles.
[0037]
The content of the near-infrared absorbing material in the anti-counterfeit print can be changed according to the intended use, but is usually preferably 0.01 g / m 2 or more. If the amount is less than 0.01 g / m 2 , absorption in the near-infrared region is not remarkably exhibited, so that it is difficult to function as an anti-counterfeit ink. The upper limit of the content is not particularly limited. However, when the content is 5 g / m 2 or more, light in the visible light region is significantly absorbed. Therefore, when the transparency needs to be maintained, the content is less than 5 g / m 2. Content is preferred. The above content can be evaluated in terms of the amount per 1 m 2 since all the fillers act equally on the light rays incident on the printing surface.
[0038]
The substrate to be printed for printing the anti-counterfeit ink may be one suitable for the intended use, and in addition to paper, a mixture of resin and pulp, a resin film, and the like can be used. Alternatively, the seal may be printed with a forgery prevention ink, and the seal may be attached to the substrate to be printed.
[0039]
The anti-counterfeit printed matter of the present invention produced in this manner cannot be duplicated by copying or the like, and is reliably mechanically irradiated with infrared rays and detecting the reflection or transmission thereof, regardless of visual judgment. , Authenticity can be determined. In addition, boric acid fine particles, ruthenium oxide fine particles or rhenium oxide fine particles are used as the infrared absorbing material, and the fine particles are applied to a substrate to be printed by a printing method. be able to.
[0040]
【Example】
Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. The optical properties of the film were measured using a spectrophotometer U-4000 (manufactured by Hitachi, Ltd.). The visible light transmittance in the examples was measured according to JIS R3106. In addition, the average dispersed particle diameter is represented by an average value measured by a measuring device ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.) using a dynamic light scattering method.
[0041]
Example 1
The 20 g LaB 6 fine particles were stirred and mixed in ethanol 78g with a silane coupling agent, which was distributed processing, average dispersed particle diameter to prepare a dispersion A of 100 nm. 100 g of this dispersion A was mixed with 20 g of an ultraviolet curable resin UV3701 (manufactured by Toagosei Co., Ltd.) to obtain a forgery prevention ink.
[0042]
A transparent PET film having a thickness of 50 μm was used as a substrate to be printed, and the above-described forgery prevention ink was formed into a film on the surface of the transparent PET film using a bar coater. After drying the film at 70 ° C. for 1 minute to evaporate the solvent, the film was irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet-curable resin.
[0043]
The visible light transmittance of the obtained printed film was 76%. The transmittance at 550 nm in the visible light region was 78%, the transmittance at 800 nm in the near-infrared region was 44%, the transmittance at 900 nm was 35%, and the transmittance at 1000 nm was 33%. FIG. 1 shows the transmission profile of the printed film.
[0044]
As described above, the printing film containing the LaB 6 fine particles as the infrared absorbing material has a high transmittance in the visible light region and a significantly low transmittance in the near infrared region. Therefore, the printed film of Example 1 can be authenticated by performing data processing using light rays in the near-infrared region, and it can be seen that the printed film is effective as a forgery prevention printed matter.
[0045]
Example 2
20 g of a black pigment, Paliotol Black L0080 (manufactured by BASF) that transmits near-infrared rays, was stirred and mixed with 78 g of ethanol together with a polymer-based dispersant, and this was subjected to dispersion treatment to prepare a dispersion B having an average dispersed particle diameter of 120 nm. This dispersion B was mixed with the dispersion A in Example 1 and the UV-curable resin UV3701 (manufactured by Toagosei Co., Ltd.) to prepare a black forgery prevention ink.
[0046]
A transparent PET film having a thickness of 50 μm was used as a substrate to be printed, and the above-described black anti-counterfeit ink was formed on the surface of the substrate by a bar coater. After drying the film at 70 ° C. for 1 minute to evaporate the solvent, the film was irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet-curable resin.
[0047]
The visible light transmittance of the obtained printed film was 1%. The transmittance at 550 nm in the visible light region was 1%, the transmittance at 800 nm in the near infrared region was 24%, the transmittance at 900 nm was 20%, and the transmittance at 1000 nm was 19%. FIG. 2 shows the transmission profile of the printed film.
[0048]
Comparative Example 1
The dispersion B in Example 2 was mixed with an ultraviolet curing resin UV3701 (manufactured by Toagosei Co., Ltd.) to obtain a black ink containing no near-infrared absorbing material. Using this black ink, a print film was formed on a transparent PET film having a thickness of 50 μm in the same manner as in Example 2 above.
[0049]
The visible light transmittance of the obtained printed film was 1%. The transmittance at 550 nm in the visible light region was 1%, the transmittance at 800 nm in the near infrared region was 78%, the transmittance at 900 nm was 82%, and the transmittance at 1000 nm was 85%. FIG. 2 shows the transmission profile of the printed film.
[0050]
From the transmission profiles of the printed films of Example 2 and Comparative Example 1 shown in FIG. 2, the printed film of Example 2 shows the same black color in the visible light region as in Comparative Example 1, but has a transmittance in the near infrared region. You can see that it is very different. Therefore, the black print film of Example 2 is recognized by the naked eye as the same black print, but can be detected by data processing using light rays in the near-infrared region, indicating that it is effective as a forgery prevention print. You.
[0051]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the composition for anti-counterfeit inks and the anti-counterfeit ink which transmit light in a visible light range and absorb in a near-infrared ray region and have excellent weather resistance can be provided. In addition, by using the anti-counterfeit ink composition and the anti-counterfeit ink, it is impossible to duplicate by copying or the like, and the authenticity can be determined mechanically simply and reliably without visual judgment, and the weather resistance is improved. An excellent and inexpensive anti-counterfeit print can be provided.
[0052]
Furthermore, when used in combination with a coloring pigment that transmits near infrared rays, it transmits light in the visible light range and has absorption in the near infrared range, is excellent in weather resistance, is colored in black, etc. An anti-ink can be provided. By printing this colored anti-counterfeit ink in combination with an ink containing only a color pigment, a more anti-counterfeit print can be obtained which is more complicated and has a high anti-counterfeit effect.
[Brief description of the drawings]
FIG. 1 is a graph showing a transmission profile of a printed film of Example 1 using a forgery prevention ink containing LaB 6 fine particles of the present invention.
FIG. 2 is a graph showing a transmission profile of a printing film of Example 2 using a forgery prevention ink containing LaB 6 fine particles of the present invention and a black pigment, and a transmission profile of a printing film of Comparative Example 1 using black ink.

Claims (10)

近赤外線吸収材料として、Y、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Sr、Caのいずれかの6ホウ化物微粒子、酸化ルテニウム微粒子、及び酸化レニウム微粒子から選ばれた少なくとも1種の微粒子を含むことを特徴とする偽造防止インク用組成物。As near-infrared absorbing materials, hexaboride fine particles of any of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, and Ca, ruthenium oxide A composition for an anti-counterfeit ink comprising fine particles and at least one fine particle selected from rhenium oxide fine particles. 前記微粒子の表面が、Si、Ti、Al、Zrから選ばれた少なくとも1種の化合物で被覆されていることを特徴とする、請求項1に記載の偽造防止インク用組成物。The anti-counterfeit ink composition according to claim 1, wherein the surface of the fine particles is coated with at least one compound selected from Si, Ti, Al, and Zr. 前記微粒子と共に、近赤外線を透過する着色顔料を含有することを特徴とする、請求項1又は2に記載の偽造防止インク用組成物。The anti-counterfeit ink composition according to claim 1, further comprising a coloring pigment that transmits near-infrared rays together with the fine particles. 前記着色顔料が、Cu−Fe−Mn、Cu−Cr、Cu−Cr−Mn、Cu−Cr−Mn−Ni、Cu−Cr−Fe、Co−Cr−Feのいずれかの複合酸化物、チタンブラック、窒化チタン、酸窒化チタン、暗色アゾ顔料、ペリレンブラック顔料、アニリンブラック顔料、カーボンブラックから選ばれた少なくとも1種の近赤外線を透過する黒色顔料であることを特徴とする、請求項3に記載の偽造防止インク用組成物。The color pigment is a composite oxide of any of Cu-Fe-Mn, Cu-Cr, Cu-Cr-Mn, Cu-Cr-Mn-Ni, Cu-Cr-Fe, Co-Cr-Fe, and titanium black. 4. A black pigment transmitting at least one kind of near-infrared ray selected from titanium nitride, titanium oxynitride, dark azo pigment, perylene black pigment, aniline black pigment, and carbon black. Composition for anti-counterfeit ink. 請求項1〜4のいずれかに記載の偽造防止インク用組成物を、溶媒中に分散させたことを特徴とする偽造防止インク。An anti-counterfeit ink comprising the anti-counterfeit ink composition according to any one of claims 1 to 4 dispersed in a solvent. 前記溶媒中に有機バインダーを含むことを特徴とする、請求項5に記載の偽造防止インク。The forgery prevention ink according to claim 5, wherein an organic binder is contained in the solvent. 前記溶媒中に含まれる前記6ホウ化物微粒子、酸化ルテニウム微粒子、及び酸化レニウム微粒子の粒子径が200nm以下であることを特徴とする、請求項5又は6に記載の偽造防止インク。The anti-counterfeit ink according to claim 5, wherein the hexaboride fine particles, ruthenium oxide fine particles, and rhenium oxide fine particles contained in the solvent have a particle diameter of 200 nm or less. 請求項5〜7のいずれかに記載の偽造防止インクを用いて、被印刷基材の片面又は両面に印刷したことを特徴とする偽造防止印刷物。A forgery-prevention printed matter, wherein the forgery-prevention ink according to any one of claims 5 to 7 is printed on one or both sides of a substrate to be printed. 前記被印刷基材の片面又は両面の少なくとも偽造防止インクの印刷膜上に、更に近赤外線を透過する着色顔料を含有した着色インクが印刷塗布されていることを特徴とする、請求項8に記載の偽造防止印刷物。9. A color ink containing a color pigment that transmits near-infrared light is further printed and applied on at least one side or both sides of the substrate to be printed on the print film of the anti-counterfeit ink. Anti-counterfeit printed matter. 前記着色インクは、着色顔料として、Cu−Fe−Mn、Cu−Cr、Cu−Cr−Mn、Cu−Cr−Mn−Ni、Cu−Cr−Fe、Co−Cr−Feのいずれかの複合酸化物、チタンブラック、窒化チタン、酸窒化チタン、暗色アゾ顔料、ペリレンブラック顔料、アニリンブラック顔料、カーボンブラックから選ばれた少なくとも1種の近赤外線を透過する黒色顔料を含有することを特徴とする、請求項9に記載の偽造防止印刷物。The colored ink may be any of composite oxides of Cu-Fe-Mn, Cu-Cr, Cu-Cr-Mn, Cu-Cr-Mn-Ni, Cu-Cr-Fe, and Co-Cr-Fe as color pigments. Product, titanium black, titanium nitride, titanium oxynitride, dark azo pigment, perylene black pigment, aniline black pigment, at least one black pigment that transmits near infrared rays selected from carbon black, A forgery-preventive printed matter according to claim 9.
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