KR950011223B1 - Pink emitting luminescent material - Google Patents

Pink emitting luminescent material Download PDF

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KR950011223B1
KR950011223B1 KR1019920020740A KR920020740A KR950011223B1 KR 950011223 B1 KR950011223 B1 KR 950011223B1 KR 1019920020740 A KR1019920020740 A KR 1019920020740A KR 920020740 A KR920020740 A KR 920020740A KR 950011223 B1 KR950011223 B1 KR 950011223B1
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reactant
samarium
minutes
matrix
cdmoo
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KR940011603A (en
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안승덕
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한국조폐공사
황원오
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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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten

Abstract

m+3 is mfd. by (a) reacting 0.2-0.5 mol cadmium chloride (CdCl2) with 0.2-0.5 mol sodium molybdate (Na2MoO4) in the water to make a reactant matrix (CdMoO4), (b) mixing the reactant matrix with 0.001-0.009 mol sodium chloride (SmCl3), (c) heating the reactant in the alundum crucible under the oxidation atmosphere at 600-800 deg.C. for 60-90 min, and then crushing it to 10 micrometer size, (d) firing the reactant at 1100-1200 deg.C. for 60-90 min, and then crushing it to 3 micrometer size, and (e) heating the reactant at 500-600 deg.C. for 60 min, and then slowly cooling it. The fluorescent material for a forgery prevention printing ink has a good acid alkali, chemical and light resistance.

Description

분홍색 형광물질 및 그 제조방법Pink fluorescent substance and its manufacturing method

본 발명은 위조방지 인쇄잉크용 분홍색 형광물질 및 그 제조방법에 관한 것이다.The present invention relates to a pink fluorescent substance for anti-counterfeiting printing ink and a manufacturing method thereof.

현재 무기계 황색 형광물질의 대표적인 것으로 ZnS : Mn과 (Zn, Cd)S : Cu가, 무기계 적색 형광물질로서는 Y2O2S : Eu가 알려져 있으나 특히 무기계 적색 형광물질인 Y2O2S : Eu는 그 후단에 유황(S)이 결합되어 있어 비교적 안정성이 부족하며 인쇄잉크 안료용으로 사용하기에는 가격이 고가인 결점이 있다.Current as a representative example of the inorganic yellow phosphor material ZnS: Mn and (Zn, Cd) S: Cu is, as the inorganic red phosphor Y 2 O 2 S: Eu is known, but the particular inorganic red phosphor Y 2 O 2 S: Eu Sulfur (S) is coupled to the rear end thereof is relatively lacking in stability and has the disadvantage that the price is expensive to use for printing ink pigments.

그리하여 본 발명자는 가격면에서 훨씬 경제적이고 상기 Y2O2S : Eu와 동일한 발광 강도(Intensity)를 가지며, 전색제(Vehicle)와 혼합하여 인쇄잉크용 안료로 사용하더라도 변색, 변질되지 아니하며 형광효과도 감소하지 않고 내성이 강한 적색 형광물질인 CdMoO4: Eu3+를 개발한 바 있다. (본 출원인의 1991년 특허출원 제91-24925호) 그러나 이는 자외선에 의하여 여기(勵起 : Excitation)되었다가 적색광만을 발하게 될뿐 다른색의 광(光)을 발하지는 못하였던 것이다. 그리하여 본 발명자는 선발명인 상기 CdMoO4: Eu3+의 제조방법에 있어서의 구성물질인 활성화제(Activator)를 바꾸어가며 다른색의 광(光)이 발하여지는 형광물질을 찾아던바, 드디어 596mm의 발광스펙트럼을 가지는 사마리움(Sm : Samarium)을 활성화제(Activator)로 사용하므로서 UV(Ultra-Violet) 영역인 340mm 주파장 범위의 광에 의해 여기에는 본 발명의 분홍색 형광물질을 발명하기에 이르렀다.Thus, the present inventors are much more economical in terms of cost and have the same luminescence intensity as the Y 2 O 2 S: Eu, and do not discolor or deteriorate even when used as a pigment for printing ink by mixing with a vehicle. We have developed CdMoO 4 : Eu 3+ , a red phosphor that is not resistant and is resistant. (Applicant's 1991 Patent Application No. 91-24925) However, it was excitated by ultraviolet rays and only emitted red light, but did not emit light of another color. Thus, the present inventors changed the activator, which is a constituent in the manufacturing method of CdMoO 4 : Eu 3+ , which is the first invention, and found a fluorescent material emitting light of a different color. By using the spectrum (Sm: Samarium) as an activator (Activator) by the light of the 340mm dominant wavelength range of the UV (ultra-violet) region has led to the invention of the pink fluorescent material of the present invention.

즉, 본 발명은 선발명인 CdMoO4: Eu3+의 제조방법중 매트릭스에 가하는 활성화제를 염화사마리움(Samarium Chloride : SmDl3)으로 대체하므로서 본 발명의 새로운 형광물질인 CdMoO4: Eu3+를 얻을 수 있었는바, 이와 같은 본 발명을 상세히 설명하면 다음과 같다.That is, the present invention replaces the new fluorescent material CdMoO 4 : Eu 3+ of the present invention by replacing the activator added to the matrix in the process for the preparation of CdMoO 4 : Eu 3+ , which is the first invention, with Samarium Chloride (SmDl 3 ) The present invention was described in detail as follows.

제조방법Manufacturing method

제 1 공정 : 염화카드뮴(Cadmium Chloride : CdCl2) 0.20 내지 0.50mol 바람직하게는 0.37mol과 소디움 몰리브데이트(Sodium Molybdate : Ma2MoO4) 0.20 내지 0.50mol 바람직하게는 0.37mol을 각각 물에 녹여서 수용액으로 한다음 침전물을 형성시키므로서 반응물 A인 매트릭스(Matrix)를 제조한다. 이때 그 반응식은 다음과 같다.First step: 0.20 to 0.50 mol of cadmium chloride (CdCl 2 ), preferably 0.37 mol and sodium molybdate (Ma 2 MoO 4 ) 0.20 to 0.50 mol, preferably 0.37 mol, respectively, The aqueous solution was then prepared to form a precipitate, thereby preparing a matrix as reactant A. The reaction formula is as follows.

CdCl2+Na2MoO4+H2O → CdMoO4+2NaCl+H2OCdCl 2 + Na 2 MoO 4 + H 2 O → CdMoO 4 + 2NaCl + H 2 O

제 2 공정 : 매트릭스 반응물 A에 활성화제로 염화사마리움(Samarium Chloride : SmCl3)을 매트릭스량에 0.001-0.009mol 바람직하게는 0.002mol이 되게 투입하고 균일 혼합하여 반응물 B를 형성시킨다.Second Step: Saturated chloride (Samarium Chloride: SmCl 3 ) is added to the matrix reactant A in an amount of 0.001-0.009 mol, preferably 0.002 mol, and uniformly mixed to form reactant B.

제 3 공정 : 반응물 B를 아란담 도가니(Alundum crudible)에 장입하고 산화성 분위기중의 전기로에서 600-800℃ 바람직하게는 600℃로 60-90분간 바람직하게는 60분간 가열하면서 활성화제를 매트릭스에 확산시키는 반응을 실시한후 10㎛정도로 분쇄하여 반응물 C를 얻는다.Step 3: Charge reactant B into an Alundum crudible and diffuse the activator into the matrix while heating at 600-800 ° C., preferably 600 ° C. for 60-90 minutes, preferably 60 minutes, in an electric furnace in an oxidizing atmosphere. After the reaction was carried out to grind to about 10㎛ to obtain the reactant C.

제 4 공정 : 반응물 C를 1100-1200℃ 바람직하게는 1100℃에서 60-90분간 바람직하게는 60분간 결정화를 위한 고온반응을 실시한후 약 3㎛정도로 분쇄하여 반응물 D를 얻는다.Fourth step: The reactant C is subjected to a high temperature reaction for crystallization at 1100-1200 ° C., preferably at 1100 ° C. for 60-90 minutes, preferably 60 minutes, and then ground to about 3 μm to obtain reactant D.

제 5 공정 : 반응물 D를 500-600℃ 바람직하게는 500℃에서 약 60분간 가열후 서냉(爐內冷却)하여 스트레스(Stress)를 제거하고 발광강도 증진등을 위한 안정화 반응을 종결하므로서 본 발명의 형광물질인 CdMoO4: Sm3+를 얻을 수 있었다.Fifth step: The reactant D is heated at 500-600 ° C., preferably at 500 ° C. for about 60 minutes, and then cooled slowly to remove stress and to terminate the stabilization reaction for enhancing luminous intensity. A fluorescent substance CdMoO 4 : Sm 3+ was obtained.

이와 같이하여 제조된 본 발명의 형광물질은 우수한 발광강도를 가지며, 인쇄용 안료로 사용되기에 적합한 미세 입자크기를 가지며, 전색제(Vehicle)와 혼합하여 인쇄 잉크용 안료로 사용할 경우 변색 또는 변질되지 아니하며 형광효과도 감소되지 아니한다. 또한 본 발명의 형광물질은 내산성, 내알카리성, 내약품성 내광성을 가지며 고온과 저온등 급격한 온도변화에도 우수한 내성을 갖고 잇으므로 이러한 내성이 요구되는 산업분야에의 이용시 효과의 극대화를 기할 수 있을 것으로 기대되는 신규의 분홍색 형광물질인 것이다.The fluorescent material of the present invention prepared as described above has excellent luminous intensity, has a fine particle size suitable for use as a pigment for printing, and does not discolor or deteriorate when used as a pigment for printing ink by mixing with a vehicle. The effect is not diminished. In addition, since the fluorescent material of the present invention has acid resistance, alkali resistance, chemical resistance light resistance, and excellent resistance to rapid temperature changes such as high temperature and low temperature, the fluorescent material of the present invention can be expected to maximize the effect when used in an industrial field requiring such resistance. It is a new pink fluorescent substance.

이와 같은 본 발명의 형광물질을 인쇄 잉크용 안료로 사용하여 인쇄한 인쇄효과 및 발광강도는 다음과 같다. 본 발명의 효과 측정을 위해 사용한 전색제는 쿠마론인딘레진(Coumarone Indene Resin)인 메탈릭 잉크바니쉬(Metallic Ink Varnish : 대한잉크 주식회사 제품)이었으며 그 효과는 다음과 같이 바람직한 것으로 나타났다.The printing effect and luminous intensity printed using the fluorescent material of the present invention as a pigment for printing ink are as follows. The colorant used for measuring the effects of the present invention was a metallic ink varnish (Coumarone Indene Resin) (Metallic Ink Varnish: manufactured by Daehan Ink Co., Ltd.), and the effects were as follows.

실험 1 : 투입율에 따른 발광 강도실험Experiment 1: Luminous Intensity Test According to Input Rate

전색제에 대한 본 발명의 형광물질 투입률은 10, 20, 30, 40Wt%로 하여 잉크를 제조한 후 동일 인쇄패턴(Pattern)을 갖는 인쇄물로 인쇄하여 발광강도를 측정한 결과 다음의 표(1)과 같이 투입률에 비례하는 발광강도(Emission Intensity)를 얻을 수 있었다.Fluorescent substance input rate of the present invention to the colorant was 10, 20, 30, 40 Wt%, and after the ink was prepared, printed with a printed material having the same pattern (Pattern), and the emission intensity was measured. The following table (1) As shown in FIG. 2, emission intensity was proportional to the input rate.

[표 1]TABLE 1

실험 2 : 잉크 두께와 발광 강도실험Experiment 2: Ink Thickness and Luminous Intensity Test

본 발명의 형광물질은 상기 전색제에 대하여 15Wt% 투입한 잉크로 10, 20, 30, 40, 50㎛ 잉크필름의 두께를 갖는 인쇄물을 제작하여 발광강도를 측정한 결과 다음의 표(2)와 같이 잉크필름의 두께에 비례하는 발광강도를 얻을 수 있었다.The fluorescent material of the present invention is a 15 Wt% ink with respect to the colorant to prepare a printed material having a thickness of 10, 20, 30, 40, 50㎛ ink film to measure the emission intensity as shown in the following Table (2) Luminescent intensity in proportion to the thickness of the ink film was obtained.

[표 2]TABLE 2

실험 3 : 평판 인쇄실험Experiment 3: Flat Printing Experiment

평판인쇄물의 다량 제조를 위해 평판인쇄물성을 테크(Tack)(3min, 32℃, 50m/min) 162, Flow(3min, 20℃) 870dyne/cm2로 제조하여 아이테크(Itek) 평판인쇄시험기(Itek Graphix 3985 : U.S.A)상에서 평판인쇄실험을 실시한 결과 전이성등 제반 인쇄적성과 내약품성, 내광성등 제반내성과 발광효과등 형광인쇄물로서의 효과가 양호하였다.In order to manufacture a large amount of flatbed, the flatbed printability is manufactured by Tack (3min, 32 ℃, 50m / min) 162, Flow (3min, 20 ℃) 870dyne / cm 2 Itek Graphix 3985: USA) showed the results of plate printing experiments such as transferability and chemical resistance, resistance to light and resistance to light and effects of fluorescence printing.

실험 4 : 활판 인쇄실험Experiment 4: Letterpress Experiment

평판 인쇄실험과는 별도로 인쇄부위를 가급적 작게하고 본 발명의 형광물질의 형광특성을 증대하기 위해 잉크물성을 Teck(3min, 32℃, 50m/min) 116, Flow(3min, 20℃) 633dyne/cm2로 제조하여 활판 인쇄실험을 실시한 결과 잉크제조적성 및 제반 인쇄적성과 발광효과등 형광 인쇄물로서의 효과가 양호하였다.Apart from flat printing experiments, the ink properties are Teck (3min, 32 ℃, 50m / min) 116, Flow (3min, 20 ℃) 633dyne / cm to minimize the printing area as much as possible and increase the fluorescence characteristics of the fluorescent material of the present invention. As a result of performing a letterpress printing experiment with 2 , the effect as a fluorescent printed matter such as ink manufacturing suitability, general printability, and luminous effect was good.

Claims (6)

CdMoO4를 매트릭스로 하고 사마리움(Sm)을 활성화제로 하는 분자식이 CdMoO4: Sm3+인 분홍색 형광물질.A pink fluorescent substance having the molecular formula CdMoO 4 : Sm 3+ having CdMoO 4 as a matrix and samarium (Sm) as an activator. CdMoO4를 매트릭스로 하고 이에 활성화제로 사마리움(Sm)을 가하여 화합시킨후 반응물을 소성시켜 분자식이 CdMoO4: Sm3+인 분홍색 형광물질의 제조방법.CdMoO 4 as a matrix, and after adding samarium (Sm) as an activator to the compound and calcining the reactants to prepare a pink fluorescent substance of the molecular formula CdMoO 4 : Sm 3 + . 제 2 항에 있어서, 사마리움(Sm)은 사마리움 화합물임을 특징으로 하는 분홍색 형광물질의 제조방법.[4] The method of claim 2, wherein samarium (Sm) is a samarium compound. 제 3 항에 있어서, 사마리움 화합물이 염화사마리움(SmCl3)임을 특징으로 하는 분홍색 형광물질의 제조방법.The method of claim 3, wherein the samarium compound is samarium chloride (SmCl 3 ). 제 2 항, 제 3 항 또는 제 4 항에 있어서, 소성방법은 매트릭스와 활성화제의 반응물을 제 1 차로 아란담 도가니(Alundum crucible)에 투입하고 산화성분위기에서 600-800℃로 60-90분간 가열한 후 10㎛정도로 분쇄한후, 다시 제 2 차로 1100-1200℃에서 60-90분간 소성시킨후 약 3㎛정도로 분쇄하며, 다시 제 3 차로 500-600℃에서 60분간 가열한 후 서냉함을 특징으로 하는 분홍색 형광물질의 제조방법.5. The calcination method according to claim 2, 3 or 4, wherein the calcining method firstly introduces the reactant of the matrix and the activator into an Alundum crucible and heats it at 600-800 ° C. for 60-90 minutes in an oxidizing atmosphere. After pulverizing to about 10㎛, and then sintered at 1100-1200 ℃ for 60-90 minutes, pulverized to about 3㎛, and then heated to 500-600 ℃ for 60 minutes and then slowly cooled Method for producing a pink fluorescent substance. 제 5 항에 있어서, 제 1 차의 소성온도와 시간이 각 600℃와 60분간이며, 제 2차의 소성온도와 시간이 1100℃와 60분간이고, 제 3 차의 소성온도가 500℃임을 특징으로 하는 분홍색 형광물질의 제조방법.The method according to claim 5, wherein the first firing temperature and time is 600 ° C and 60 minutes, the second firing temperature and time is 1100 ° C and 60 minutes, and the third firing temperature is 500 ° C. Method for producing a pink fluorescent substance.
KR1019920020740A 1992-11-05 1992-11-05 Pink emitting luminescent material KR950011223B1 (en)

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