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KR20100009811A - Pink pigment using crcl3 and process for producing the same - Google Patents

Pink pigment using crcl3 and process for producing the same Download PDF

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KR20100009811A
KR20100009811A KR1020080070613A KR20080070613A KR20100009811A KR 20100009811 A KR20100009811 A KR 20100009811A KR 1020080070613 A KR1020080070613 A KR 1020080070613A KR 20080070613 A KR20080070613 A KR 20080070613A KR 20100009811 A KR20100009811 A KR 20100009811A
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pink
crcl
pigment
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이현수
이병하
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명지대학교 산학협력단
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28Compounds of silicon
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/34Compounds of chromium
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06Treatment with inorganic compounds

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  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Silicon Compounds (AREA)

Abstract

본 발명은 말라야이트(Malayaite, CaSnSiO5)에 Cr이 고용된 안료로서, 발색제로 CrCl3를 사용한 것을 특징으로 하는 핑크계열의 세라믹안료에 관한 것이다.The present invention relates to a pink-based ceramic pigment, characterized in that CrCl 3 is used as a colorant as Cr is a solid solution of Cr in Malayaite (CaSnSiO 5 ).

본 발명에 따른 핑크계열의 세라믹안료는, (a)CrCl3, SnO2, CaO, SiO2를 0.001~0.04:0.99925~0.97:1:1의 몰비로 조성하여 혼합하는 단계; (b)상기 (a)단계의 혼합 조성물을 산화분위기에서 소성하는 단계; 그리고, (c)상기 (b)단계의 소성물을 분쇄하는 단계;를 포함하여 이루어지는 과정으로 제조된다.Pink-based ceramic pigments according to the present invention, (a) CrCl 3 , SnO 2 , CaO, SiO 2 composition and mixing in a molar ratio of 0.001 ~ 0.04: 0.99925 ~ 0.97: 1: 1; (b) firing the mixed composition of step (a) in an oxidizing atmosphere; And, (c) the step of pulverizing the fired product of step (b); is prepared by a process comprising a.

Description

CrCl₃를 발색제로 사용한 핑크계열의 세라믹안료 및 이의 제조방법{Pink pigment using CrCl3 and process for producing the same}Pink pigment using CrC3₃ as a coloring agent and its manufacturing method {Pink pigment using CrCl3 and process for producing the same}

본 발명은 발색제로 CrCl3를 사용하여 말라야이트(Malayaite, CaSnSiO5)에 Cr을 고용시킨 핑크계열의 세라믹안료와, 그러한 세라믹안료의 제조방법에 관한 것이다.The present invention relates to a pink-based ceramic pigment in which Cr is dissolved in malayaite (CaSnSiO 5 ) using CrCl 3 as a coloring agent, and a method for producing such a ceramic pigment.

세라믹안료는 도자기·유리·법랑 등에 쓰이는 착색제로서 높은 온도로 소성해서 색을 나타내는 것인데, 주로 금속산화물이 쓰이지만 이를 융제, 유약, 소지 등과 섞어서 쓰기도 한다. 세라믹안료의 색은 첨가되는 착색물질에 따라 변하기도 하고 또는 소성온도나 소성분위기(산화, 환원, 중성)에 따라서도 변하며, 색깔에 따라 흑색, 회색, 황색, 다갈색, 녹색, 청색, 핑크로 구별된다.Ceramic pigment is a colorant used in ceramics, glass, enamel, etc. It is colored by firing at high temperature. It is mainly used for metal oxides, but it can also be mixed with flux, glaze and base material. The color of ceramic pigments may change depending on the colorant added, or also depending on the firing temperature or minor component (oxidation, reduction, neutral), depending on the color, black, gray, yellow, dark brown, green, blue, pink do.

세라믹안료로서 금속산화물은 소성온도나 소성분위기에 따라서도 쉽게 변하는 등 불안정하기 때문에, 산화물 또는 탄산염을 고온에서 소성하여 안정적인 결정 으로 합성한 세라믹안료가 선호된다. 다양한 색깔의 세라믹안료 중에서 현재 핑크계열의 안료로서 주목받으며 많이 사용되는 것으로 말라야이트(Malayaite)결정과 Cr2O3를 사용한 스펜(Sphene)결정의 안료가 있다.As metal pigments, metal oxides are unstable, such as easily changing depending on firing temperature or minor component risk. Ceramic pigments synthesized by stable crystals by firing oxides or carbonates at high temperatures are preferred. Among the pigments of various colors, the pigments of pink series are now attracting attention and are widely used. There are malayaite crystals and pigments of Sphene crystals using Cr 2 O 3 .

말라야이트결정의 핑크안료는 말라야이트(Malayaite, CaSnSiO5) 결정에 Cr이 고용된 것이다. 이러한 핑크안료를 제조하는 방법으로는 (1)CaCO3, SnO2, SiO2를 배합하고 발색제로 K2Cr2O7를 첨가하고 광화제로 Na2B4O7, B2O3 등을 첨가해서 1200℃ 전후에서 소성하여 제조하는 방법과, (2)SnO2, CaO, SiO2를 배합하고 발색제로 Cr2O3를 첨가하고 광화제로 H3BO3 등을 첨가하여 1200℃ 전후에서 소성하여 제조하는 방법이 있다. 이렇게 제조된 핑크안료들은 일정의 발색도를 나타내기는 하지만, 한편으로는 이보다도 더욱 우수한 발색도를 나타내는 핑크안료에 대한 요구 또한 있는 상황이다.The pink pigment of the malayaite crystal is obtained by dissolving Cr in the malayaite (CaSnSiO 5 ) crystal. As a method of preparing such a pink pigment (1) CaCO 3 , SnO 2 , SiO 2 is blended, K 2 Cr 2 O 7 is added as a color developer, and Na 2 B 4 O 7 , B 2 O 3, etc. are added as a mineralizer. And (2) SnO 2 , CaO and SiO 2 are mixed, Cr 2 O 3 is added as a coloring agent, H 3 BO 3, etc. is added as a mineralizer and calcined at around 1200 ° C. There is a method of manufacturing. Although the pink pigments thus produced show a certain degree of color development, on the other hand, there is also a demand for pink pigments that exhibit even better color development.

본 발명은 상기한 기술적 요구에 따라 개발된 것으로서, 말라야이트 결정에 Cr이 고용된 핑크안료로서 종래의 핑크안료보다 우수한 발색도를 가지는 핑크계열의 세라믹안료를 제공하는데 기술적 과제가 있다.The present invention has been developed in accordance with the technical requirements described above, and has a technical problem in providing a pink pigment-based ceramic pigment having a color development superior to that of a conventional pink pigment as a pink pigment in which Cr is dissolved in a malayaite crystal.

본 발명은 말라야이트 결정을 최적으로 생성함과 동시에 최상의 발색도를 나 타내는 핑크계열의 세라믹안료를 제조하는 방법을 제공하는데 다른 기술적 과제가 있다.The present invention has another technical problem to provide a method for producing a pink-based ceramic pigments that produce the malayaite crystals at the same time and exhibits the best color development.

상기한 기술적 과제를 해결하기 위해, 본 발명은 말라야이트(Malayaite, CaSnSiO5)에 Cr이 고용된 안료로서, 발색제로 CrCl3를 사용한 것을 특징으로 하는 핑크계열의 세라믹안료를 제공한다.In order to solve the above technical problem, the present invention provides a pink-based ceramic pigment, characterized in that CrCl 3 is used as a colorant as a solid solution of Cr in Malayaite (CaSnSiO 5 ).

또한, 본 발명은 (a)CrCl3, SnO2, CaO, SiO2를 0.001~0.04:0.99925~0.97:1:1의 몰비로 조성하여 혼합하는 단계; (b)상기 (a)단계의 혼합 조성물을 산화분위기에서 소성하는 단계; 그리고, (c)상기 (b)단계의 소성물을 분쇄하는 단계;를 포함하여 이루어지는 것을 특징으로 하는 세라믹안료 제조방법을 제공한다.In addition, the present invention comprises the steps of (a) CrCl 3 , SnO 2 , CaO, SiO 2 composition and mixing in a molar ratio of 0.001 ~ 0.04: 0.99925 ~ 0.97: 1: 1; (b) firing the mixed composition of step (a) in an oxidizing atmosphere; And, (c) the step of pulverizing the fired product of the step (b); provides a ceramic pigment manufacturing method comprising a.

본 발명에 따르면 다음과 같은 효과가 기대된다.According to the present invention, the following effects are expected.

첫째, 본 발명에 따른 세라믹안료는 저온에서의 반응성이 좋으면서 용융점이 낮은 CrCl3를 발색제로 사용하기 때문에, 효과적으로 말라야이트(Malayaite, CaSnSiO5) 결정에 많은 양의 Cr(Ⅳ)이온을 고용시킬 수 있어 채도와 발색도에서 우수한 효과를 발휘한다.First, since the ceramic pigment according to the present invention uses CrCl 3 having good reactivity at low temperature and low melting point as a coloring agent, it is possible to effectively employ a large amount of Cr (IV) ions in malayaite (CaSnSiO 5 ) crystals. It can exert an excellent effect in saturation and color development.

둘째, 본 발명에 따른 세라믹안료는 발색제로 CrCl3를 사용한 결과 Cr2O3을 사용할 때보다 같은 양을 사용하여도 발색도와 채도가 좋으며, 결국 적은 양의 Cr을 갖고서도 효과를 극대화할 수 있다.Secondly, the ceramic pigment according to the present invention has good color and saturation even when the same amount of Cr 2 O 3 is used as a result of using CrCl 3 as a color developing agent, and thus, the effect can be maximized even with a small amount of Cr. .

셋째, 본 발명에 따른 세라믹안료 제조방법은 소성단계를 저온단계와 고온단계로 구분하여 진행하기 때문에 고온에서의 소성시간을 줄임으로써 에너지를 절감하고 아울러 제조비용을 절감할 수 있다.Third, the ceramic pigment manufacturing method according to the present invention can proceed by dividing the firing step into a low temperature step and a high temperature step, thereby reducing energy and reducing manufacturing costs by reducing the firing time at a high temperature.

본 발명에 따른 핑크계열의 세라믹안료는 말라야이트(Malayaite, CaSnSiO5)에 Cr이 고용된 안료로서, 발색제로 CrCl3를 사용한 것을 특징으로 한다. 말라야이트 결정의 핑크안료에서 고용되는 Cr은 산화상태가 Cr(Ⅲ)보다는 Cr(Ⅳ)일 때 발색에 미치는 영향이 더 큰데, 본 발명에 따른 연구결과 말라야이트 결정이 저온 800℃ 부근에서 생성되기 시작하는 것으로 나타났는 바, 이를 감안하여 본 발명에서는 발색제로 CrCl3를 채택하고 있다. CrCl3는 Cr2O3보다 저온에서 반응성이 좋은 것은 물론 용융점이 낮으므로 소성 중에 Cr이온의 산화상태가 Cr(Ⅳ) 상태로 빨리 전환되며, 그 결과 낮은 온도에서도 효과적으로 많은 양의 Cr(Ⅳ)이온을 고용시킬 수 있을 것으로 기대된다. 이와 같은 Cr(Ⅳ)이온의 고용효과 개선은 발색제의 함량을 최소화하면서도 세라믹안료의 발색도를 극대화시키는데 기여할 것이다.Pink-based ceramic pigments according to the present invention is a pigment in which Cr is dissolved in Malayaite (Malayaite, CaSnSiO 5 ), characterized in that CrCl 3 is used as a coloring agent. Cr, which is dissolved in the pink pigment of malayaite crystals, has a greater effect on the color development when the oxidation state is Cr (IV) than Cr (III). In view of this, the present invention employs CrCl 3 as a colorant. CrCl 3 is more responsive at lower temperatures than Cr 2 O 3 and has a lower melting point, so that the oxidation state of Cr ions is quickly converted into Cr (IV) state during firing, and as a result, a large amount of Cr (IV) is effectively applied even at low temperatures. It is expected that ions can be dissolved. Improving the solid solution effect of Cr (IV) ions will contribute to maximize the color development of ceramic pigments while minimizing the content of colorants.

본 발명에 따른 핑크계열의 세라믹안료는 말라야이트(Malayaite, CaSnSiO5) 결정에서 Cr이 고용된 것으로, CaCrxSnySiO5(x=0.001~0.04, y=1-x=0.99925~0.97)의 화학식으로 표현된다. 특히, 본 발명에서는 CrCl3, SnO2, CaO, SiO2를 기본 원료로 하고 이들을 각각 0.001~0.04:0.99925~0.97:1:1의 몰비로 조성하여 합성할 것을 제안하는데, 상기와 같은 조성비로 조성할 때 상기 화학식으로 합성되어 핑크계열로 발색하게 된다. 또한, 본 발명은 상기 조성물에 광화제를 더 첨가하여 합성할 것을 제안하며, 광화제의 첨가로 말라야이트 결정 생성이 촉진되기 때문에 안료 합성에 유리해진다. 상기 광화제는 반응성이 좋은 H3B03가 바람직하며, H3B03는 전체 조성물(CrCl3 +SnO2 +CaO +SiO2 +H3B03)중량의 2중량%로 첨가하도록 한다. 물론 Borax 등 다른 종류의 광화제를 이용하는 것도 가능하다.Pink-based ceramic pigments according to the present invention is a solid solution of Cr in Malayaite (Malayaite, CaSnSiO 5 ) crystals, CaCr x Sn y SiO 5 (x = 0.001 ~ 0.04, y = 1-x = 0.99925-0.97) It is represented by the chemical formula. Particularly, in the present invention, CrCl 3 , SnO 2 , CaO, and SiO 2 are used as basic raw materials, and they are synthesized in a molar ratio of 0.001 to 0.04: 0.99925 to 0.97: 1: 1, respectively. When synthesized in the above formula will be colored pink. In addition, the present invention proposes to synthesize by further adding a mineralizer to the composition, it is advantageous for pigment synthesis because the addition of the mineralizer promotes the production of malayarite crystals. Preferably, the mineralizer is H 3 B0 3 having high reactivity, and H 3 B0 3 is added at 2% by weight of the total composition (CrCl 3 + SnO 2 + CaO + SiO 2 + H 3 B0 3 ). Of course, it is also possible to use other kinds of mineralizers such as Borax.

본 발명에 따른 세라믹안료는 도자기 유약에 혼합하는 색유약으로, 또는 도자기 장식으로 위한 하회안료로, 또는 도자기 소지에 첨가하는 색소지로, 또는 도자기 전사를 위한 전사안료로 사용가능하다. The ceramic pigment according to the present invention may be used as a color glaze mixed with porcelain glaze, as a lower pigment for porcelain decoration, or as a coloring paper added to porcelain base, or as a transfer pigment for porcelain transfer.

본 발명에 따른 세라믹안료 제조방법은, (a)CrCl3, SnO2, CaO, SiO2를 0.001~0.04:0.99925~0.97:1:1의 몰비로 조성하여 혼합하는 단계; (b)상기 (a)단계의 혼합 조성물을 산화분위기에서 소성하는 단계; 그리고, (c)상기 (b)단계의 소성물을 분쇄하는 단계;를 포함하여 이루어지는 것을 특징으로 한다. 이와 같은 일련 의 과정은 전반적으로 종래의 안료 제조방법과 유사하나, 발색제로 CrCl3 를 채택하는 점에서 큰 차이가 있다. CrCl3는 Cr2O3보다 수용성이기 때문에 다른 원료들과 쉽게 혼합하며, 또한 반응성이 좋기 때문에 Cr의 고용효과를 극대화하며, 나아가 용융점이 낮기 때문에 낮은 온도에서 세라믹안료를 제조할 수 있게 한다.Ceramic pigment manufacturing method according to the present invention, (a) CrCl 3 , SnO 2 , CaO, SiO 2 composition and mixing in a molar ratio of 0.001 ~ 0.04: 0.99925 ~ 0.97: 1: 1; (b) firing the mixed composition of step (a) in an oxidizing atmosphere; And, (c) pulverizing the fired product of the step (b); characterized in that comprises a. This series of processes is generally similar to the conventional pigment production method, but there is a big difference in adopting CrCl 3 as a colorant. Since CrCl 3 is more water-soluble than Cr 2 O 3 , it is easily mixed with other raw materials, and because of its high reactivity, it maximizes the solid solution effect of Cr.

상기 (a)단계는 광화제와 휘발성 알코올 중 하나 이상을 더 첨가하여 혼합한 후 건조하는 과정으로 이루어질 수 있다. 광화제의 첨가로 말라야이트 결정 생성을 촉진시킬 수 있으며, 광화제로는 앞서 살펴본 바와 같이 H3BO3를 전체 조성물 중량의 2중량% 사용할 수 있다. 또한, 휘발성 알코올의 첨가로 기본 재료들을 잘 혼합시킴과 동시에 건조시킬 수 있으며, 휘발성 알코올로는 메탄올, 에탄올 등을 채택할 수 있다.The step (a) may be made by adding one or more of the mineralizer and the volatile alcohol, followed by mixing and drying. The addition of mineralizers may promote malayaite crystal production, and as described above, H 3 BO 3 may be used in an amount of 2% by weight of the total composition. In addition, it is possible to mix the basic materials well with the addition of volatile alcohol and to dry at the same time, methanol, ethanol and the like can be adopted as the volatile alcohol.

한편, 본 발명에서는 상기 (b)단계를 700~1000℃에서 2~6시간 유지한 후 1150~1300℃에서 1~4시간 유지하는 과정으로 구분하여 진행할 것으로 제안한다. 종래에는 소성과정을 1150~1300℃의 고온소성만을 진행하였으나, 본 발명에서는 저온단계를 진행한 후에 고온단계를 진행하고 있다. 저온단계는 말라야이트 결정이 저온 800℃ 부근에서 생성되기 시작한다는 연구결과를 감안한 것으로, 이는 말라야이트 결정의 생성 시작과 동시에 Cr을 고용시켜 Cr의 고용효과를 극대화하고자 함이다.On the other hand, the present invention proposes to proceed to step (b) by maintaining the process for 1 to 4 hours at 1150 ~ 1300 ℃ after maintaining for 2 to 6 hours at 700 ~ 1000 ℃. Conventionally, only the high-temperature firing of 1150 ~ 1300 ℃ the baking process, but the high temperature step is carried out after the low temperature step in the present invention. The low temperature step takes into account the results of the study that malayaite crystals start to form at a low temperature around 800 ° C, which is intended to maximize the solid solution effect of Cr by simultaneously employing Cr in the formation of malayaite crystals.

이하에서 본 발명을 실시예에 의거하여 더욱 상세하게 설명한다. 다만, 하 기의 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위가 이로써 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for illustrating the present invention, but the scope of the present invention is not limited thereto.

[실시예] 발색제의 종류에 따른 세라믹안료의 발색도 EXAMPLES Color Development of Ceramic Pigments According to Types of Coloring Agents

(1)재료 준비(1) material preparation

하기 표 1과 같은 조성의 재료를 준비하였다.To prepare a material of the composition shown in Table 1.

재료 조성Material composition 실시예1,3Example 1,3 실시예2,4Example 2 and 4 비교예1,3Comparative Example 1, 3 비교예2,4Comparative Example 2, 4 CrCl3(mole)CrCl 3 (mole) 0.020.02 0.040.04 -- -- Cr2O3(mole)Cr 2 O 3 (mole) -- -- 0.020.02 0.040.04 SnO2(mole)SnO 2 (mole) 0.9850.985 0.970.97 0.9850.985 0.970.97 CaO(mole)CaO (mole) 1One 1One 1One 1One SiO2(mole)SiO 2 (mole) 1One 1One 1One 1One H3BO3 (전체 조성물의 wt%)H 3 BO 3 (wt% of total composition) 22 22 22 22

(2)세라믹안료 제조(2) ceramic pigment manufacturing

상기 표 1의 각 재료들을 분말상태로 준비하여 고상합성법으로 제조하였다. 즉, 분말상태의 각 재료들을 에탄올을 첨가하여 혼합 건조한 후, 하기 표 2와 같은 조건(저온->고온)으로 소성을 진행하고, 소성물을 분쇄하여 세라믹안료를 제조한 것이다. 최종 제조된 세라믹안료는 도 1과 같이 획득하였다.Each material of Table 1 was prepared in a powder state and prepared by a solid phase synthesis method. In other words, each of the materials in the powder state is mixed with ethanol and dried, and then calcined under the conditions shown in Table 2 (low temperature-> high temperature), and the calcined product is pulverized to prepare a ceramic pigment. The final ceramic pigment was obtained as shown in FIG.

소성 조건Firing conditions 저온Low temperature 고온High temperature 온도(℃)Temperature (℃) 승온속도 (℃/min)Temperature rise rate (℃ / min) 유지시간 (hr)Holding time (hr) 온도(℃)Temperature (℃) 승온속도 (℃/min)Temperature rise rate (℃ / min) 유지시간 (hr)Holding time (hr) 실시예1,2 비교예1,2Example 1, 2 Comparative Example 1, 2 900900 55 33 12001200 33 22 실시예3,4 비교예3,4Examples 3 and 4 Comparative Examples 3 and 4 900900 55 33 13001300 33 22

(3)도자기 유약으로의 이용(3) The use in ceramic glaze

상기에서 제조된 세라믹안료(실시예1,2,3,4, 비교예1,2,3,4)는 도자기 유약으로 이용하여 발색도를 확인하였으며, 그 결과는 도 2 내지 도 5와 같이 나타났다. 도 2 내지 도 5는 각 세라믹안료를 석회유(제겔식이 0.3264 KNaO, 0.4040 Al2O3, 3.5526 SiO2 , 0.6588 CaO, 0.0019 Fe2O3, 0.0148 MgO으로 표현되는 석회유임)에 석회유의 6중량% 첨가하여 만든 도자기 유약을 도사지 소지에 바른 후 1260℃에서 1시간 소성한 것을 촬영한 사진이다.The ceramic pigments prepared above (Examples 1, 2, 3, 4, Comparative Examples 1, 2, 3, 4) were used as porcelain glaze to check the color development, and the results are shown in FIGS. 2 to 5. . 2 to 5 shows each ceramic pigment in lime oil (Zegel's formula 0.3264 KNaO, 0.4040 Al 2 O 3 , 3.5526 SiO 2 , 0.6588 CaO, 0.0019 Fe 2 O 3 , lime oil expressed in 0.0148 MgO) 6% by weight of lime oil was applied to ceramic porcelain glaze on the dosing material after firing at 1260 ℃ for 1 hour.

(4)발색도 평가(4) color evaluation

세라믹안료 자체의 발색도는 도 1에서 보는 바와 같이 본 발명에 따른 실시예1,2,3,4가 종래의 비교예1,2,3,4에 비해 떨어지는 것을 확인할 수 있다. 하지만, 세라믹안료를 도자기 유약으로 사용할 때는 도 2 내지 도 5에서와 같이 본 발명에 따른 실시예1,2,3,4가 같은 조건의 종래의 비교예1,2,3,4에 비해 발색도는 물론 채도에서도 좋은 것을 확인할 수 있으며, 특히 고온단계의 소성온도가 1200℃일 때 더욱 진하게 발현되는 것을 확인할 수 있다. 한편, 실시예와 비교예를 비교할 때 CrCl3와 Cr2O3를 동량 사용함에도 실시예에서 발색도가 우수한 것으로 나타나므로, 결국 적은 양의 Cr을 갖고서도 더욱 유리한 효과를 나타낸다고 할 수 있다. 이와 같은 결과에 따라, CrCl3가 Cr2O3에 비해 발색제로서 더욱 효과적이라고 할 수 있다. As shown in FIG. 1, the color of the ceramic pigment itself can be confirmed that Examples 1, 2, 3, and 4 according to the present invention are inferior to the conventional Comparative Examples 1, 2, 3, and 4. However, when the ceramic pigment is used as a porcelain glaze, as shown in Figs. Of course, it can be confirmed that even in the saturation, especially when the firing temperature of the high temperature step is more intensely expressed at 1200 ℃. On the other hand, even when using the same amount of CrCl 3 and Cr 2 O 3 when comparing the Example with the comparative example, the color development degree in the Example is excellent, it can be said that even with a small amount of Cr has a more advantageous effect. As a result, it can be said that CrCl 3 is more effective as a coloring agent than Cr 2 O 3 .

도 1은 종래의 세라믹안료와 본 발명에 따른 세라믹안료를 비교하여 보여주는 사진이다.1 is a photograph showing a comparison between the conventional ceramic pigments and the ceramic pigments according to the present invention.

도 2 내지 도 5는 종래의 세라믹안료와 본 발명에 따른 세라믹안료를 도자기유약으로 사용하는 경우를 비교하여 보여주는 사진이다. 2 to 5 are photographs showing a comparison between the conventional ceramic pigments and the ceramic pigments according to the present invention as a ceramic glaze.

Claims (6)

말라야이트(Malayaite, CaSnSiO5)에 Cr이 고용된 안료로서, 발색제로 CrCl3를 사용한 것을 특징으로 하는 핑크계열의 세라믹안료.Cr-based ceramic pigment, characterized in that CrCl 3 is used as a colorant as Cr is a solid solution in Malayaite (CaSnSiO 5 ). 제1항에서,In claim 1, CrCl3, SnO2, CaO, SiO2를 각각 0.001~0.04:0.99925~0.97:1:1의 몰비로 조성하여 합성한 것을 특징으로 하는 핑크계열의 세라믹안료.Pink-based ceramic pigments, characterized in that the composition was synthesized by the composition of CrCl 3 , SnO 2 , CaO, SiO 2 in a molar ratio of 0.001 to 0.04: 0.99925 to 0.97: 1: 1. 제2항에서,In claim 2, 상기 조성물에 광화제를 더 첨가하여 합성한 것을 특징으로 하는 핑크계열의 세라믹안료.Pink-based ceramic pigments, characterized in that by further adding a mineralizer to the composition. (a)CrCl3, SnO2, CaO, SiO2를 0.001~0.04:0.99925~0.97:1:1의 몰비로 조성하여 혼합하는 단계;(a) mixing and mixing CrCl 3 , SnO 2 , CaO, and SiO 2 in a molar ratio of 0.001 to 0.04: 0.99925 to 0.97: 1: 1; (b)상기 (a)단계의 혼합 조성물을 산화분위기에서 소성하는 단계; 그리고,(b) firing the mixed composition of step (a) in an oxidizing atmosphere; And, (c)상기 (b)단계의 소성물을 분쇄하는 단계;(c) pulverizing the fired product of step (b); 를 포함하여 이루어지는 것을 특징으로 하는 세라믹안료 제조방법.Ceramic pigment manufacturing method comprising a. 제4항에서,In claim 4, 상기 (a)단계는 광화제와 휘발성 알코올 중 하나 이상을 더 첨가하여 혼합한 후 건조하는 과정으로 이루어지는 것을 특징으로 하는 세라믹안료 제조방법.The method (a) is a ceramic pigment manufacturing method comprising the step of drying after further adding and mixing at least one of a mineralizer and a volatile alcohol. 제4항 또는 제5항에서,The method of claim 4 or 5, 상기 (b)단계는 700~1000℃에서 2~6시간 유지한 후 1150~1300℃에서 1~4시간 유지하는 과정으로 이루어지는 것을 특징으로 하는 세라믹안료 제조방법.The step (b) is a ceramic pigment manufacturing method comprising the process of maintaining for 1 to 4 hours at 1150 ~ 1300 ℃ after maintaining for 2 to 6 hours at 700 ~ 1000 ℃.
KR1020080070613A 2008-07-21 2008-07-21 Pink pigment using crcl3 and process for producing the same Ceased KR20100009811A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102660271A (en) * 2012-04-28 2012-09-12 昆明理工大学 Multicolour long-afterglow luminescent material for single matrix and preparation method thereof
CN104119892A (en) * 2013-04-26 2014-10-29 海洋王照明科技股份有限公司 Silicate luminescent material cladding metal nanoparticle and preparation method thereof
CN119191709A (en) * 2024-08-30 2024-12-27 华南理工大学 A kind of tin sphene crystal glaze and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102660271A (en) * 2012-04-28 2012-09-12 昆明理工大学 Multicolour long-afterglow luminescent material for single matrix and preparation method thereof
CN104119892A (en) * 2013-04-26 2014-10-29 海洋王照明科技股份有限公司 Silicate luminescent material cladding metal nanoparticle and preparation method thereof
CN119191709A (en) * 2024-08-30 2024-12-27 华南理工大学 A kind of tin sphene crystal glaze and preparation method thereof

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