KR20020058117A - Near-infrared absorber, method for preparing same and ink including same - Google Patents

Near-infrared absorber, method for preparing same and ink including same Download PDF

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KR20020058117A
KR20020058117A KR1020000084956A KR20000084956A KR20020058117A KR 20020058117 A KR20020058117 A KR 20020058117A KR 1020000084956 A KR1020000084956 A KR 1020000084956A KR 20000084956 A KR20000084956 A KR 20000084956A KR 20020058117 A KR20020058117 A KR 20020058117A
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oxide
less
group
phosphoric acid
infrared
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KR1020000084956A
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KR100407254B1 (en
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서구원
이상근
조동제
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민태영
한국조폐공사
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14—Security printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks

Abstract

PURPOSE: Provided are a near infrared ray absorbing agent, a preparation thereof, and ink containing the near infrared ray absorbing agent, which can be applied to security documents for preventing forgery and alteration. CONSTITUTION: The near infrared ray absorbing agent is produced by a process comprising the steps of: mixing 20-70wt% of copper tetrafluoroborate, 80-30wt% of a phosphoric acid compound selected from the group consisting of orthophosphate, poly phosphoric acid, and phosphorus pentoxide, and less than 1wt% of a metal oxide selected from the group consisting of magnesium oxide, strontium oxide, zinc oxide, aluminum oxide, and arsenic oxide; wet-stirring the mixture and drying and sintering at 300deg.C or higher; making fine particles with less than 10 micrometer by using a zirconium oxide- or aluminum oxide-based ball mill. Or the near infrared ray absorbing agent is produced by another process comprising the steps of; adding a water solution, containing 20-70wt% of the copper tetrafluoroborate, 80-30wt% of the phosphoric acid compound, and less than 1wt% of the metal oxide, to a water-insoluble solvent; precipitating, filtering, separating, and sintering; making fine-particles with less than 10 micrometer. And the ink contains the near infrared ray absorbing agent.

Description

근적외선 흡수제, 이의 제조방법 및 이를 포함하는 잉크 {Near-infrared absorber, method for preparing same and ink including same}Near-infrared absorber, preparation method thereof and ink including same {Near-infrared absorber, method for preparing same and ink including same}

본 발명은 근적외선 흡수제, 이의 제조방법 및 이를 포함하는 잉크에 관한 것으로, 좀 더 상세하게는 사불화붕산구리(copper tetrafluoroborate), 인산화합물 및 금속산화물로 구성된 근적외선 흡수제, 이의 제조방법 및 이를 포함하는 잉크에 관한 것이다.The present invention relates to a near-infrared absorbent, a method for manufacturing the same, and an ink including the same, and more particularly, a near-infrared absorber composed of copper tetrafluoroborate, a phosphate compound, and a metal oxide, a method for preparing the same, and an ink including the same. It is about.

종래의 안료나 염료 등의 색 재료는 도료나 잉크에 사용되어 고유의 색깔을 나타냄으로써 시각적 효과를 주고 있었다. 이러한 시각적 효과는 안료 및 염료가 가시광선 영역에서 태양광을 흡수 또는 반사함으로써 나타난다.Conventional color materials such as pigments and dyes have been used in paints and inks to give an inherent color to give a visual effect. This visual effect is caused by the pigments and dyes absorbing or reflecting sunlight in the visible region.

그러나 최근에는 염료나 안료의 흡수, 반사 특성을 가시선, 적외선 영역까지 측정하여 이를 물체나 화상의 인식요소로 이용하는 자동화 인식기술이 급진적으로 개발되고 있다.Recently, an automated recognition technology has been developed radically by measuring absorption and reflection characteristics of dyes and pigments in the visible and infrared regions and using them as recognition elements of objects or images.

예를 들어, 형광물질을 잉크 또는 페인트에 혼합하여 이용한 경우 자외선을 조사하여 나타난 여기상태의 형광을 특정 검지기로 측정하여 자동화 식별요소로 쓰며, 자성물질은 테이프, 바코드, MICR 숫자에 이용되어 자성의 유무, 자성의 강도,자성의 패턴 등을 읽어 자동화 분류 또는 식별요소로 이용된다.For example, in the case of using a fluorescent material mixed with ink or paint, the fluorescence of the excited state generated by irradiation of ultraviolet rays is measured by a specific detector and used as an automatic identification element. The magnetic material is used for a tape, a barcode, and a MICR number. It is used as an automated classification or identification element by reading the presence, the strength of the magnetic and the pattern of the magnetic.

또한, 최근에는 화상을 인식하고 감지하기 위한 광원으로서 근적외선 부근에서의 반도체 레이저가 개발되어서 700∼1600㎚의 파장 범위에서 흡수 및 반사를 기기적으로 측정할 수 있게 되었으며, 이 파장은 근적외선 영역이기 때문에 사람의 시각으로는 인식이 불가능하다.In addition, recently, a semiconductor laser near the near infrared has been developed as a light source for recognizing and detecting an image, so that absorption and reflection can be measured mechanically in the wavelength range of 700 to 1600 nm. Since the wavelength is a near infrared region, It is impossible to recognize from the human perspective.

일반적인 염료나 안료는 가시광선의 특정파장을 부분적으로 흡수 또는 반사하지만, 적외선 영역에서의 흡수 또는 반사 특성이 가시광선과 일치하지 않으며, 대부분의 염료나 안료들은 근적외선에서 강한 흡수를 하지 않는다.Typical dyes or pigments partially absorb or reflect certain wavelengths of visible light, but their absorption or reflection properties in the infrared region do not coincide with visible light, and most dyes or pigments do not have strong absorption in the near infrared.

종래의 염료나 안료 중에 근적외선을 흡수하는 것은 카본블랙, 프탈로시아닌블루, 니트로소계 염료, 시아닌계 염료, 니그로신계 염료, 트리페닐메탄계 염료와 금속의 착화합물인 니켈디티올렌계 등이 있으나 외관적으로 색깔을 띠고 있다.Conventional dyes and pigments absorb near infrared rays include carbon black, phthalocyanine blue, nitroso-based dyes, cyanine-based dyes, nigrosine-based dyes, triphenylmethane-based dyes, and nickeldithiene-based complexes of metals. Is wearing.

그러나 가시광선을 모두 반사하는 물질, 즉 외관색이 무색인 상태에서 근적외선을 흡수하는 물질이 효과적으로 이용될 수 있지만, 분자 에너지 준위 때문에 이론적으로 불가능하다. 그렇지만 외관색이 옅은 상태에서의 근적외선 흡수제는 개발이 지속되고 있으며, 흡수능이 강한 물질을 여러 나라에서 중점적으로 연구하고 있다.However, a material that reflects all visible light, i.e., a material that absorbs near infrared light in a colorless appearance, may be effectively used, but is theoretically impossible due to molecular energy levels. However, the development of near-infrared absorbers in the state of pale appearance is continuing, and many countries are researching strong absorbent materials.

일본국 특개평 5-279078호에는 무색에 가까운 미청색의 물질로서 CuCl2, CuSO4, CuOH, CuO의 구리화합물과 인화합물이 근적외선을 흡수하는 효과가 있는 것이 기재되어 있으나, 구리와 불화붕소와의 착화합물에 대해서는 언급된 바 없다.또한 한국 공개특허공보 제98-42794호에는 산성물질 흡착제, 농업용 필름의 적외선 흡수제, 잉크제트용 기록매체 등에 적합한 화합물이 기재되어 있다.Japanese Patent Application Laid-open No. Hei 5-279078 discloses that copper compounds and phosphorus compounds of CuCl 2 , CuSO 4 , CuOH, and CuO absorb near-infrared rays as a colorless, almost blue-colored substance. There is no mention of complexing compounds. Korean Patent Publication No. 98-42794 discloses compounds suitable for acid adsorbents, infrared absorbers for agricultural films, inkjet recording media and the like.

또한, 근적외선 흡습성 수지조성물로서, 구리염과 인산기를 함유한 아민의 화합물이 일본국 특개평 11-52127호와 미국특허 제5,800,861호에 기재되어 있고, 카메라 등의 촬영장치에 내장된 광학소자용 인산염유리 제조방법이 일본국 특개평 11-268927호에 기재되어 있다. CuO와 오산화인(P2O5) 및 미량의 금속산화물을 혼합하여 소성한 근적외선 흡수물질에 대한 제조방법이 일본국 특개평 6-207161호에, 철염과 인산을 혼합하고 소성하여 근적외선 흡수제를 제조하는 방법이 일본국 특개평 6-346044호에 기재되어 있다.In addition, as a near-infrared hygroscopic resin composition, a compound of an amine containing a copper salt and a phosphate group is described in Japanese Patent Laid-Open Nos. 11-52127 and 5,800,861, and includes a phosphate for an optical element embedded in a photographing apparatus such as a camera. Glass manufacturing methods are described in Japanese Patent Laid-Open No. 11-268927. A method for preparing near-infrared absorbing materials obtained by mixing CuO with phosphorus pentoxide (P 2 O 5 ) and trace amounts of metal oxides is disclosed in Japanese Patent Application Laid-Open No. 6-207161, which is prepared by mixing and firing iron salts with phosphoric acid. How to do this is described in Japanese Patent Laid-Open No. 6-346044.

이러한 폴리인산 및 인산과, 황산구리, 수산화구리, 탄산구리, 염화구리, 초산구리 및 철염 등으로 구성되는 종래기술의 방법들은 근적외선의 흡수 특성으로서 외관색이 무색이거나 입자특성 및 몰 흡광계수가 우수하다.The prior art methods composed of such polyphosphoric acid and phosphoric acid, copper sulfate, copper hydroxide, copper carbonate, copper chloride, copper acetate, iron salt, and the like have colorless appearance or excellent particle characteristics and molar extinction coefficient as absorption characteristics of near infrared rays. .

따라서 본 발명의 목적은 상기 종래기술보다도 더욱 무색에 가까운 미청색을 나타내면서 몰 흡광계수와 입자화 특성이 더욱 우수한 구리, 붕소 및 불소의 착화합물과 인산화합물을 포함하는 근적외선 흡수제를 제공하는데 있다.It is therefore an object of the present invention to provide a near-infrared absorber comprising a complex of phosphorus and phosphorus compounds of copper, boron and fluorine, which exhibits a more off-white color than the prior art and is more excellent in molar extinction coefficient and granulation properties.

또 다른 본 발명의 목적은 상기 근적외선 흡수제를 제조하는 방법 및 상기 근적외선 흡수제를 잉크에 적용하는 방법을 제공하는데 있다.Another object of the present invention is to provide a method for producing the near infrared absorber and a method for applying the near infrared absorber to an ink.

상기 목적을 달성하기 위한 본 발명의 근적외선 흡수제는, 사불화붕산구리20 내지 70중량%, 정인산, 폴리인산 및 오산화인으로 이루어진 군으로부터 선택된 인산화합물 80 내지 30중량% 및 산화마그네슘, 산화스트론튬, 산화아연, 산화알루미늄 및 산화비소로 이루어진 군으로부터 선택된 금속산화물 1중량% 이하로 이루어진다.The near-infrared absorbent of the present invention for achieving the above object, 20 to 70% by weight copper tetrafluoroborate, 80 to 30% by weight phosphate compound selected from the group consisting of phosphoric acid, polyphosphoric acid and phosphorus pentoxide and magnesium oxide, strontium oxide, oxidation 1 wt% or less of a metal oxide selected from the group consisting of zinc, aluminum oxide and arsenic oxide.

또 다른 목적을 달성하기 위한 본 발명의 근적외선 흡수제의 제조방법은, 사불화붕산구리 20 내지 70중량%, 정인산, 폴리인산 및 오산화인으로 이루어진 군으로부터 선택된 인산화합물 80 내지 30중량% 및 산화마그네슘, 산화스트론튬, 산화아연, 산화알루미늄 및 산화비소로 이루어진 군으로부터 선택된 금속산화물 1중량% 이하를 혼합하여 습식상태로 교반시킨 다음 충분히 건조시키고 300℃ 이상의 온도에서 소성시켜서 산화지르코니움계 또는 산화알루미늄계 볼밀 분쇄기로 10㎛ 이하로 미세입자화시켜서 달성되거나, 사불화붕산구리 20 내지 70중량%, 정인산, 폴리인산 및 오산화인으로 이루어진 군으로부터 선택된 인산화합물 80 내지 30중량% 및 산화마그네슘, 산화스트론튬, 산화아연, 산화알루미늄 및 산화비소로 이루어진 군으로부터 선택된 금속산화물 1중량% 이하를 포함하는 수용액을 비수용성 용제(메탄올, 에탄올, 프로판올 등의 알콜류)에 첨가하여 침전시킨 다음 여과하고 분리하여 소성시켜서 산화지르코니움계 또는 산화알루미늄계 볼밀 분쇄기로 10㎛ 이하로 미세입자화시킨다.Method for producing a near-infrared absorber of the present invention for achieving another object, 20 to 70% by weight copper tetrafluoroborate, 80 to 30% by weight phosphoric acid compound selected from the group consisting of phosphoric acid, polyphosphoric acid and phosphorus pentoxide and magnesium oxide, Zirconium oxide or aluminum oxide ball mills are mixed with 1% by weight or less of a metal oxide selected from the group consisting of strontium oxide, zinc oxide, aluminum oxide and arsenic oxide, stirred in a wet state, dried sufficiently and calcined at a temperature of 300 ° C. or higher. 80 to 30% by weight of phosphate compounds selected from the group consisting of 20 to 70% by weight of copper tetrafluoroborate, regular phosphoric acid, polyphosphoric acid and phosphorus pentoxide, and magnesium oxide, strontium oxide, and oxidation Metal oxide selected from the group consisting of zinc, aluminum oxide and arsenic oxide An aqueous solution containing 1% by weight or less of water is added to a non-aqueous solvent (alcohols such as methanol, ethanol, propanol, etc.), precipitated, filtered, separated, and calcined to 10 μm or less with a zirconium oxide or aluminum oxide ball mill. Microparticles.

또 다른 목적을 달성하기 위한 상기 적용방법은, 전술한 근적외선 흡수제를 위·변조 방지기능을 갖는 잉크에 적용하는 것이다.The above application method for achieving another object is to apply the above-mentioned near-infrared absorbent to an ink having a forgery / modulation prevention function.

이하, 본 발명을 좀 더 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.

전술한 바와 같이, 본 발명은 구리와 붕소, 불소의 착화합물과 인산 화합물의 조성물로부터 완성된다.As mentioned above, this invention is completed from the composition of the complex compound of copper, boron, fluorine, and a phosphoric acid compound.

구리, 붕소 및 불소의 착화합물로서, 사불화붕산구리(Cu(BF4)2)를 들 수 있는데, 이러한 사불화붕산구리는 종래에는 유기물과 무기물의 이온성 부여 및 착화합물 제조에 주로 이용되어 오고 있지만, 본 발명에서와 같이 근적외선 흡수제로서 탁월한 효과가 있음이 밝혀진 바 없다.As a complex compound of copper, boron and fluorine, copper tetrafluoroborate (Cu (BF 4 ) 2 ) may be mentioned. Such copper tetrafluoroborate has conventionally been mainly used for providing ionic and organic compounds with organic and inorganic compounds. As in the present invention, it has not been found that there is an excellent effect as a near infrared absorber.

종래부터 구리를 함유하는 화합물은 2가의 구리 이온이 근적외선을 강하게 흡수하기 때문에 일반적으로 황산 제2구리의 복합 황산염이 이용되었으며 그 외에도 금속을 소량 첨가하여 색을 옅게 하거나 흡수율과 화학적 특성을 개선하였고, 특히 구리 화합물과 함께 인산화합물이 존재할 경우에는 일반적으로 흑색, 갈색 또는 청색을 띠며 대략적으로 700∼1500nm의 근적외선 부근의 파장대를 흡수하였다.Conventionally, copper-containing compounds have generally used complex sulphate of cupric sulfate because divalent copper ions strongly absorb near infrared rays. In addition, a small amount of metal was added to make the color lighter or to improve absorption and chemical properties. In particular, when a phosphoric acid compound is present together with a copper compound, it is generally black, brown, or blue and absorbs a wavelength band near near infrared rays of about 700 to 1500 nm.

본 발명에서는, 근적외선을 흡수하는 물질의 주성분으로 인산화합물과 사불화붕산구리를 선택하며, 이 물질의 최종 형태는 오산화인(P2O5)과 구리염(Cu(BF4)2)이 구리와 산소, 인과 산소, 구리와 불화붕소의 폴리머적인 형태의 교차결합 구조로 되어 있고 소량의 금속산화물이 첨가되어 구리이온에 의한 청색의 색상을 감소시키고 있다.In the present invention, the phosphorus compound and copper tetrafluoroborate are selected as main components of the material absorbing near infrared rays, and the final forms of the material are phosphorus pentoxide (P 2 O 5 ) and copper salt (Cu (BF 4 ) 2 ). It has a crosslinked structure in the form of polymers of oxygen, phosphorus and oxygen, copper and boron fluoride, and a small amount of metal oxide is added to reduce the blue color caused by copper ions.

본 발명에서 사용되는 인산화합물에는 정인산(P2O5·nH2O),폴리인산(PnO3n+1)(n+2)-및 오산화인으로 이루어진 군으로부터 선택되고, 구리이온에 의해 나타나는 청색 색상을 감소시키기 위하여 사용되는 금속산화물은 산화마그네슘, 산화스트론튬, 산화아연, 산화알루미늄 및 산화비소로 이루어진 군으로부터 선택된다.The phosphoric acid compound used in the present invention is selected from the group consisting of phosphorous acid (P 2 O 5 · nH 2 O), polyphosphoric acid (PnO 3n + 1 ) (n + 2) -and phosphorus pentoxide, which is represented by copper ions. The metal oxide used to reduce the color is selected from the group consisting of magnesium oxide, strontium oxide, zinc oxide, aluminum oxide and arsenic oxide.

본 발명에 있어서, 근적외선 흡수제는 사불화붕산구리 20 내지 70중량%, 인산화합물 80 내지 30중량% 및 금속산화물 1중량% 이하로 이루어지는데, 상기 사불화붕산구리가 20중량% 미만 함유되면 근적외선의 흡수가 약하고 흡습성이 강하여 잉크제조용 안료로 이용하기 나쁘며, 70중량%를 초과하여 사용하면 근적외선 흡수는 강해지지만, 색상이 짙은 청색으로 변하고 입자화가 어려운 문제가 있다. 또한 인산화합물이 80중량%를 초과하여 함유되면 근적외선의 흡수가 약하고 흡습성이 강하여 잉크제조용 안료로 이용하기 나쁘며, 30중량% 미만이면 근적외선 흡수는 강해지지만, 색상이 짙은 청색으로 변하고 입자화가 어려운 문제가 있다. 한편, 상기 금속산화물의 함량이 1중량% 이하이어야 무색상태로 제조되며 1중량%를 초과하면 첨가한 금속산화물에 의한 색상이 나타나게 된다.In the present invention, the near-infrared absorbing agent is composed of 20 to 70% by weight of copper tetrafluoroborate, 80 to 30% by weight of phosphate compound and 1% by weight of metal oxide, when the copper tetrafluoride is contained in less than 20% by weight of near infrared ray The absorption is weak and the hygroscopicity is bad to use as a pigment for ink production, when used in excess of 70% by weight, the near infrared absorption is strong, but the color becomes dark blue and difficult to granulate. In addition, when the phosphoric acid compound is contained in excess of 80% by weight, the absorption of near-infrared light is weak and strong hygroscopicity, so it is bad to use as a pigment for ink production.When it is less than 30% by weight, the absorption of near-infrared light becomes strong, but the color becomes dark blue and difficult to form particles. have. On the other hand, when the content of the metal oxide is 1% by weight or less to be prepared in a colorless state, when the content exceeds 1% by weight will appear the color by the added metal oxide.

본 발명에 있어서의 근적외선 흡수제의 제조방법을 살펴보면, 전술한 사불화붕산구리 20 내지 70중량%, 인산화합물 80 내지 30중량% 및 금속산화물 1중량% 이하를 혼합하여 습식상태로 교반시킨 다음, 105℃ 이상에서 충분히 건조시키고 300℃ 이상의 온도에서 소성시켜서 산화지르코니움계 또는 산화알루미늄계 볼밀 분쇄기로 10㎛ 이하로 미세입자화시켜서 달성되거나, 사불화붕산구리 20 내지 70중량%,인산화합물 80 내지 30중량% 및 금속산화물 1중량% 이하를 함유하는 수용액을 메탄올, 에탄올, 프로판올 등의 알콜류로부터 선택된 비수용성 용제에 첨가하여 침전시킨 다음 여과하고 분리하여 소성시켜서 산화지르코니움계 또는 산화알루미늄계 볼밀 분쇄기로 10㎛ 이하로 미세입자화시켜 제조될 수 있다.Looking at the manufacturing method of the near-infrared absorbent in the present invention, after mixing 20 to 70% by weight of the copper tetrafluoroborate, 80 to 30% by weight phosphate compound and 1% by weight or less of the metal oxide and stirred in a wet state, 105 Dried sufficiently at or above ℃ and calcined at a temperature of 300 ℃ or more to achieve a fine particle 10μm or less with a zirconium oxide-based or aluminum oxide-based ball mill grinder, or 20 to 70% by weight of copper tetrafluoroborate, 80 to 30 phosphoric acid compound Aqueous solutions containing up to 1% by weight and up to 1% by weight of metal oxides are added to a non-aqueous solvent selected from alcohols such as methanol, ethanol and propanol, precipitated, filtered, separated and calcined, and then sintered into a zirconium oxide or aluminum oxide ball mill grinder. It can be prepared by microparticles up to 10㎛.

상기 소성온도가 300℃ 이상이어야 흡습성 없어지고 내구성이 좋아진다. 또한, 근적외선 흡수물질의 입자화는 분쇄시 분쇄기의 재질에 의한 착색 또는 오염을 막기 위하여 금속재질의 분쇄기보다는 금속산화물 재질인 산화지르코니움계 또는 산화알루미늄계 볼밀 등의 분쇄기가 효과적이며 용융 고속분사 방식도 이용 가능하다. 또한, 입자의 크기는 요판, 그라비아, 평판잉크 등에 이용하기 위해서 10미크론 이하가 적당하다.When the firing temperature is 300 ° C. or higher, the hygroscopicity is lost and durability is improved. In addition, the granulation of near-infrared absorbing materials is more effective in pulverizing a metal oxide material such as a zirconium oxide-based or aluminum oxide-based ball mill than a metal pulverizer in order to prevent coloration or contamination by the material of the pulverizer. Also available. The particle size is preferably 10 microns or less for use in intaglio, gravure, flat plate ink and the like.

본 발명에 따른 근적외선 흡수제를 미세입자화한 다음 잉크 제조용 바니시와 혼합하고 연육하여 잉크로 제조할 수 있고, 특정 패턴으로 인쇄를 하면 무색에 가까운 인쇄물이 얻어진다. 이 패턴은 무색상태이기 때문에 시각적으로는 확인이 어렵지만 적외선 파장이 780㎚인 갈륨 반도체레이저 또는 830㎚의 알루미늄·비소 반도체 레이저를 이용하면 인식이 용이하여 기기감지용 특수잉크로 사용될 수 있다.The near-infrared absorber according to the present invention can be finely granulated, mixed with the varnish for ink production, and then softened to produce an ink, and printed with a specific pattern yields a colorless print. Although the pattern is colorless, it is difficult to visually confirm, but it is easy to recognize using a gallium semiconductor laser with an infrared wavelength of 780 nm or an aluminum and arsenic semiconductor laser with a 830 nm, and can be used as a special ink for device detection.

이하의 실시예를 통해 본 발명을 좀 더 구체적으로 살펴보지만, 이에 본 발명이 한정되는 것이 아니다.The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

실시예 1Example 1

건조된 사불화붕산구리 160g, 정인산 120g 및 산화알루미늄 5g을 혼합하고 교반하여 150℃에서 충분히 건조한 다음 600℃에서 2시간 소성한다. 이 소성물을50미크론 정도가 되도록 스틸밀로 전처리하고 산화지르코니움 재질의 볼밀기를 이용하여 입자가 8미크론이 되도록 분쇄하였다.160 g of dried copper tetrafluoroborate, 120 g of phosphoric acid, and 5 g of aluminum oxide are mixed, stirred, dried sufficiently at 150 ° C., and calcined at 600 ° C. for 2 hours. The calcined product was pretreated with a steel mill so as to be about 50 microns and ground to a particle size of 8 microns using a ball mill made of zirconium oxide.

페놀변성수지 100g을 톨루엔 200ml에 녹인 다음 여기에 미세화된 근적외선 분말을 30g 가하여 충분히 교반하여 그라비어 잉크를 제조한다. 제조된 잉크를 이용하여 특정패턴으로 인쇄하면 인쇄부분이 거의 무색에 가깝게 보인다. 이 인쇄된 부위의 근적외선 흡수정도를 측정한 결과 적외선 영역의 700∼1500㎚에서 흡수가 있었으며, 900㎚ 부근에서 가장 강한 흡수대를 형성하였다. 카본블랙의 흡수강도를 100으로 기준할 경우 이 근적외선 흡수물질의 흡수강도는 87로 나타났다.100 g of a phenol-modified resin was dissolved in 200 ml of toluene, and 30 g of fine-infrared near-infrared powder was added thereto, followed by sufficiently stirring to prepare a gravure ink. When printed in a specific pattern using the prepared ink, the printed part is almost colorless. As a result of measuring the near-infrared absorption degree of this printed site, there was absorption in 700-1500 nm of an infrared region, and the strongest absorption band was formed in the vicinity of 900 nm. Based on the absorption strength of carbon black as 100, the absorption intensity of this near-infrared absorber was 87.

실시예 2Example 2

사불화붕산구리 160g을 100㎖의 물에 녹인 용액과 폴리인산 120g을 100㎖의 물에 녹인 용액과 산화스트론튬 5g을 1ℓ의 에탄올 용액에 고속으로 교반하면서 첨가하여 침전물이 형성되도록 하며, 이 침전물을 여과하여 건조한다. 소성 단계부터는 실시예 1과 동일하게 실시하였다. 그 결과, 실시예 1과 동일한 적외선 흡수강도를 나타내었으며, 입자화가 더욱 용이하였다.160 g of copper tetrafluoroborate was dissolved in 100 ml of water, 120 g of polyphosphoric acid was dissolved in 100 ml of water, and 5 g of strontium oxide was added to 1 liter of ethanol with high speed to form a precipitate. Filtered and dried. The firing step was carried out in the same manner as in Example 1. As a result, it showed the same infrared absorption strength as in Example 1, it was easier to granulate.

상기 실시예를 통해 알 수 있는 바와 같이, 본 발명에 따른 근적외선 흡수제를 이용한 잉크는 종래의 근적외선 흡수제를 포함한 잉크보다 근적외선의 흡수강도가 높았으며, 색상은 아주 옅은 미청색으로 바니시와 혼합하여 잉크화하였기 때문에 인쇄시 시각적으로 확인이 어렵고, 가시영역에서는 가시선을 반사하면서 적외선 영역에서는 근적외선 부분을 흡수함으로써, 보안문서 등에 적용할 경우에 진위를용이하게 식별하고 복사로는 재현할 수 없으므로, 위·변조를 방지할 수 있다.As can be seen through the above embodiment, the ink using the near-infrared absorber according to the present invention had a higher absorption intensity of near-infrared than the ink containing the conventional near-infrared absorber, the color is very pale blue-blue mixed with varnish ink Because of this, it is difficult to visually check when printing, and by reflecting the visible line in the visible region and absorbing the near-infrared portion in the infrared region, it is easy to identify the authenticity when applied to security documents and cannot reproduce by copying. Can be prevented.

Claims (4)

사불화붕산구리 20 내지 70중량%, 정인산, 폴리인산 및 오산화인으로 이루어진 군으로부터 선택된 인산화합물 80 내지 30중량% 및 산화마그네슘, 산화스트론튬, 산화아연, 산화알루미늄 및 산화비소로 이루어진 군으로부터 선택된 금속산화물 1중량% 이하로 이루어진 것을 특징으로 하는 근적외선 흡수제.20 to 70 wt% copper tetrafluoroborate, 80 to 30 wt% phosphoric acid compound selected from the group consisting of phosphorous acid, polyphosphoric acid and phosphorus pentoxide and a metal selected from the group consisting of magnesium oxide, strontium oxide, zinc oxide, aluminum oxide and arsenic oxide Near-infrared absorber, characterized by consisting of 1% by weight or less of oxide. 사불화붕산구리 20 내지 70중량%, 정인산, 폴리인산 및 오산화인으로 이루어진 군으로부터 선택된 인산화합물 80 내지 30중량% 및 산화마그네슘, 산화스트론튬, 산화아연, 산화알루미늄 및 산화비소로 이루어진 군으로부터 선택된 금속산화물 1중량% 이하를 혼합하여 습식상태로 교반시킨 다음 건조시키고 300℃ 이상의 온도에서 소성시켜서 산화지르코니움계 또는 산화알루미늄계 볼밀 분쇄기로 10㎛ 이하로 미세입자화시키는 것을 특징으로 하는 근적외선 흡수제의 제조방법.20 to 70 wt% copper tetrafluoroborate, 80 to 30 wt% phosphoric acid compound selected from the group consisting of phosphorous acid, polyphosphoric acid and phosphorus pentoxide and a metal selected from the group consisting of magnesium oxide, strontium oxide, zinc oxide, aluminum oxide and arsenic oxide A method for producing a near-infrared absorber, characterized by mixing 1% by weight or less of an oxide, stirring it in a wet state, drying and baking at a temperature of 300 ° C. or more, and finely granulating the particle to 10 μm or less using a zirconium oxide-based or aluminum oxide-based ball mill. . 사불화붕산구리 20 내지 70중량%, 정인산, 폴리인산 및 오산화인으로 이루어진 군으로부터 선택된 인산화합물 80 내지 30중량% 및 산화마그네슘, 산화스트론튬, 산화아연, 산화알루미늄 및 산화비소로 이루어진 군으로부터 선택된 금속산화물 1중량% 이하를 함유하는 수용액을 비수용성 용제에 첨가하여 침전시킨 다음 여과하고 분리하여 소성시켜서 산화지르코니움계 또는 산화알루미늄계 볼밀 분쇄기로 10㎛ 이하로 미세입자화시키는 것을 특징으로 하는 근적외선 흡수제의 제조방법.20 to 70 wt% copper tetrafluoroborate, 80 to 30 wt% phosphoric acid compound selected from the group consisting of phosphorous acid, polyphosphoric acid and phosphorus pentoxide and a metal selected from the group consisting of magnesium oxide, strontium oxide, zinc oxide, aluminum oxide and arsenic oxide An aqueous solution containing up to 1% by weight of an oxide is added to a non-aqueous solvent, precipitated, filtered, separated and calcined, and finely granulated to 10 μm or less using a zirconium oxide-based or aluminum oxide-based ball mill grinder. Manufacturing method. 제1항 내지 제3항의 어느 한항에 따른 근적외선 흡수제를 포함하는 것을 특징으로 하는 위·변조 방지기능을 갖는 잉크.An ink having a forgery and alteration prevention function, comprising the near-infrared absorbent according to any one of claims 1 to 3.
KR10-2000-0084956A 2000-12-29 2000-12-29 Near-infrared absorber, method for preparing same and ink including same KR100407254B1 (en)

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CN104250470A (en) * 2014-09-03 2014-12-31 安徽雅美油墨有限公司 Antistatic environment-friendly printing ink prepared by reutilizing waste plant oil residue
CN104250470B (en) * 2014-09-03 2016-05-18 安徽雅美油墨有限公司 The antistatic environment-friendly ink of waste vegetable oil pin for a kind of huge profit
WO2017171342A2 (en) 2016-03-29 2017-10-05 부성폴리콤 주식회사 Near-infrared absorbing white material and preparation method thereof
WO2017171342A3 (en) * 2016-03-29 2018-08-02 부성폴리콤 주식회사 Near-infrared absorbing white material and preparation method thereof
US10926354B2 (en) 2016-03-29 2021-02-23 Buseong Polycom Co., Ltd. Near-infrared absorbing white material and preparation method thereof

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