• 한국산업보건학회지
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• 제23권4호
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• pp.341-347
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• 2013

Objectives: The aim of this study is to investigate the differences in airborne TDI concentrations based on the filter collection method and liquid collection method and to compare airborne TDIs concentrations by sampling method change when using the filter collection method in the spray-painting process. Methods: For the sample measurement, the filter collection method(OSHA#42) and liquid collection method(NIOSH#5522) were used; for the sampling method, the full-period single sampling and full-period consecutive sampling methods were used. The samples were collected in spray-painting and drying process locations. Results: In all samples collected from the spray-painting and drying process locations through the filter collection and liquid collection methods, greater amounts of 2,6-TDI than 2,4-TDI were detected. When the TDI collection concentrations based on the sampling methods were compared, the concentrations of 2,4-TDI and 2,6-TDI collected by the consecutive sampling method were higher than the concentrations of 2,4-TDI and 2,6-TDI collected by the single sampling method for both the filter collection method and liquid collection method used in the spray-painting process. These differences were statistically significant. Conclusions: When TDI collection concentrations based on the sample measurement methods were compared, the concentration of 2,4-TDI and 2,6-TDI collected through the liquid collection method were higher than the concentrations of 2,4-TDI and 2,6-TDI collected by the filter collection method, and the differences were statistically significant. In the drying process, no difference was shown in the collection concentrations of 2,4-TDI and 2,6-TDI with the two measurement methods.

• 한국산업보건학회지
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• 제16권3호
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• pp.222-232
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• 2006

Objectives: The objective of this study was to propose the total isocyanate analytical method which involves derivation of 2,4-toluene diisocyanate(2,4-TDI), 2,6-toluene diisocyanate(2,6-TDI), 4,4'-methylenediphenyl diisocyanate(4,4'-MDI) and 1,6-hexamethylene diisocyanate(1,6-HDI) using 2-chlorobenzyl alcohol(2-CBA) or 2,4-dichlorobenzyl alcohol(2,4-DCBA), and analyzing of hydrolysate of the synthesized urethane with the gas chromatography(GC)/flame ionization detector(FID), GC/pulsed discharge ionization detector-electron capture detector(PD-ECD) and GC/mass selective detector(MSD). Methods: Urethanes were synthesized by reacting 2,4-TDI, 2,6-TDI, 4,4'-MDI and 1,6-HDI to 2-CBA or 2,4-DCBA. Urethanes was verified by TLC, HPLC/UVD and GC/MSD. For field application, the most suitable condition that 2-CBA coated in glass fiber filter removed completely and urethanes were not removed was searched. 2-CBA generated from hydrolysis of urethanes according to hydrolysis conditions. Diisocyanates were collected on field air and analyzed. Results: Urethanes which were white and solid phase synthesized by reacting 2,4-TDI, 2,6-TDI, 4,4'-MDI, 1,6-HDI and 2-CBA or 2,4-DCBA. And urethanes were verified by TLC, HPLC/UVD and GC/MSD. The most suitable conditions to remove 2-CBA coated in glass fiber filter were $87^{\circ}C$ and 20 mmHg and urethanes were not removed under same condition. Hydrolysis yields of urethanes were 99 % to 111 %. 2-CBA, the hydrolysate of urethanes was analyzed by GC/FID, GC/PD-ECD and GC/MSD. Conclusions: Simultaneous analysis of 2,4-TDI, 2,6-TDI, 4,4'-MDI and 1,6-HDI deriving with 2-CBA and 2,4-DCBA, along with a total isocyanate analysis, was feasible with GC/FID, GC/PD-ECD and GC/MSD. This result will be a guide of further study on total isocyanate analysis.

• 한국산업보건학회지
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• 제4권2호
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• pp.137-147
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• 1994

This study was designed to identify and quantitate airborne isocyanate simultaneously by HPLC. These samples were collected using 1-(2-pyridyl)piperazine(1-2PP) coated glass fiber filter from polyurethane painting works at 8 wood furniture factories in Kimpo and Inchun. The results obtained were as follows : 1. The most suitable mobile phase condition of simultaneously analyzing isocyanates was 0.01 M ammonium acetate buffer ACN(70/30) adjusted to pH 6.2 from the beginning of the analysis to 20 min and 0.01 M ammonium acetate buffer/ACN(50/50) adjusted to pH 6.2 from 21 min to 40 min using the gradient mode. The peaks of isocyanates were able to obtain within 30 min. 2. The recovery efficiencies for 2,6-TDI, 2,4-TDI, HDI and MDI urea derivates spiked at the target concentration on coated glass fiber tillers were 91.00, 93.42, 91.31 and 94.21 %, respectively. 3. The qualitative analysis of the isocyanates samples from polyurethane spray painting works in wood furnture factories identified Ihree isocyanates, 2,6-TDI, 2,4-TDI and MOI. And their concentration ranges were 0-312.6, 0-56.3 and $0-62.1{\mu}g/m^3$, respectively. A disadvantage of using the colorimetric method for isocyanate analysis is its inability of separating isocyanates. This study identified such three isocyanates as 2,6-TDI, 2,4-TDI and MDI from polyurethane spray painting works in wood furniture factories. These isocyanates were successfully quantitated by HPLC by modifying the mobile phase condition and switching to gradient mode.

• Elastomers and Composites
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• 제44권3호
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• pp.329-335
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• 2009

4종류의 새로운 형태의 열방성 액정폴리우레탄을 4,4'-Bis(5-hydroxypentoxy)biphenyl (BP5)와 2,6-tolylene diisocyanate (2,6-TDI), 2,5-tolylene diisocyanate (2,5-TDI), 및 2,4-tolylene diisocyanate (2,4-TDI), 1,4-phenylene diisocyanate (1,4-PDI) 의 중부가 반응에 의해 합성하였다. 단량체 BP5은 스멕틱상을 형성하였으며 1,4-PDI/BP5을 제외한 나머지 폴리우레탄에서는 모두 액정성을 나타내었다. 생성된 폴리우레탄의 구조는 FT-IR과 ^1H$ NMR 스펙트럼으로 확인하였고 열적 성질은 DSC와 편광현미경으로 관찰하였다.

• Toxicological Research
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• 제14권4호
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• pp.525-533
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• 1998

The covalent interactions of toluenediisocyanate (TDI) with macromolecules were investigated both in vitro and in vivo. In vitro incubations of 2,4- and 2,6-TDI with DNA or proteins resulted in dose-dependent formation of TDI-protein and TDI-DNA adducts. TDI-treated DNA was highly resistant to enzymatic digestion and thermal hydrolysis, but was readily hydrolyzed under acidic conditions by releasing its corresponding toluenediamine (TDA), suggesting that TDI caused the crosslinking of DNA. Reaction of TDI with albumin and globin resulted in the formation of several adducts, and some adducts were formed in blood of TDI-treated rats in a dose-dependent fashion. Administration of TDI to rats resulted also in a dose-dependent binding of TDI to hepatic tissue. Levels of TDI-albumin adducts were 10 times higher than those of TDI-globin adducts; the biological half lives of TDI-albumin and TDI-globin adducts were 1.2 and 12.5 days, respectively. Globin adducts were detected up to 28 days after the treatment. Hepatic TDI protein adducts were persistent for a substantial period whereas the levels of hepatic TDI-DNA adduct were decreased rapidly. These results indicate that the isocyanato group of TDI is not readily hydrolyzed under physiological conditions, is transported to other organs, and is bound to DNA and/or proteins without further metabolic activation. As the adducted products degrade in the body, TDA is released and introduced to the liver. TDA may additionally bind to hepatic tissue after metabolic activation. Thus, the toxic effect of TDI exposure is considered to persist during the lifetime of the adducted biological macromolecules.

• 월간산업보건
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• 통권328호
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• pp.55-59
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• 2015

톨루엔-2,4-디이소시아네이트, 톨루엔-2,6-디이소시아네이트 각각 또는 두 이성체 혼합물(TDI)에 대하여 TLV-TWA는 0.005 ppm, TLV-STEL은 0.02 ppm으로 직업적 노출기준을 권고하고 있다. 본 수치는 호흡기에 대한 영향과 과민성 반응에 대한 높은 발생 가능성을 최소화하기 위한 것이다. 산업현장에서 증기상 TDI 물질은 점막, 호흡기계에 심한 자극을 일으켜 천식과 같은 증후군 등 급성 발작을 유발한다. 고농도에 노출시 심한 기관지 경련, 폐렴, 폐부종, 두통, 불면증과 기관지염으로 이어질 수 있다. TDI에 상당 부분 노출되면 대부분의 사람들은 위와 같은 건강 영향을 경험하게 된다. 심지어 처음 노출되었을 경우에도 발생된다. TDI 노출 관련 연구자들은 일반 근로자들이 0.02 ppm 수준 정도로 가끔 노출되는 경우 건강 영향을 받지 않으나, 0.02 ppm이 무영향 수준으로 간주될 수 있는 그 어떠한 증거도 없다고 결론을 내렸다. TDI에 일단 감작되면 몇몇 근로자들은 노출 중단 후에도 몇 년 동안 건강 영향 증세가 지속된다. 따라서 감작제 표기는 호흡 노출을 통한 알레르기성 감작 증세의 명확한 증거로서 권고된다. A4(비발암성 물질) 표기는 생쥐와 흰쥐들을 대상으로 수행된 위장관 투여 연구와 흡입 연구들을 통해 얻어진 동물 노출 데이터에 근거하여 설정되었다. 불충분한 데이터로 피부 표기는 권고되지 않았다.

• 공업화학
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• 제8권2호
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• pp.339-346
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• 1997

액정 polyurethane은 DMF 용매중 1,4-bis(6-hydroxyhexoxy)benzene (BHB6)과 2,5-tolylene diisocyanate (2,5-TDI)를 중부가 반응에 의해서 합성하였다. 고유점도는 0.26, $0.42d{\ell}/g$였다. 생성된 polyurethane의 열적성질 및 구조확인은 DSC, 편광현미경, X-ray회절 그리고 $^1H$-NMR 및 FT-IR에 의해 확인하였다 특히 분자량이 서로 다른 polyurethane 2,5-TDI/BHB6의 열적성질 및 물성에 대해서 비교 검토하였다. 고유점도가 [${\eta}$]=0.26인 polyurethane 2,5-TDI/BHB6는 monotropic 액정성을 나타내었다. 이러한 것은 구조적으로는 mesogen을 포함하고 있지 않다. 예를 들면 LCPU-L(저분자량)은 $T_{I-LC}$(등방성액체상전이점-액정) 및 $T_{LC-K}$(액정-결정)은 $122^{\circ}C$부터 $89^{\circ}C$까지 관찰되었다.

• Korean Chemical Engineering Research
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• 제48권5호
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• pp.615-620
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• 2010

본 실험은 다섯 종류의 새로운 형태의 액정성 폴리우레탄을 4,4'-Bis(3-hydroxypropoxy)biphenyl (BP3)와 2,6-tolylene diisocyanate(2,6-TDI), 2,5-tolylene diisocyanate(2,5-TDI), 2,4-tolylene diisocyanate(2,4-TDI), 1,4-phenylene diisocyanate(1,4-PDI) 및 hexamethylene diisocyanate(HDI)의 중부가 반응에 의해 합성하였다. 단량체 BP3은 스멕틱상을 형성하였으며 HDI/BP3을 제외한 나머지 폴리우레탄에서는 모두 단방성 액정성을 나타내었다. 그러나 메틸 치환기를 가지고 있지 않는 1,4-PDI/BP3에서는 DSC 및 편광현미경에서도 액정상을 전혀 관찰할 수 없었다. 합성된 화합물의 구조는 FT-IR 및 $^1H$-NMR에 의해 확인하였으며, 그들의 열적 상전이온도 및 안정성들은 DSC, 편광현미경 및 x-선 회절에 의해 조사하였다.

• IMMUNE NETWORK
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• 제2권3호
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• pp.158-165
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• 2002

Background: Toluene diisocyanate (TDI) can cause contact allergy and occupational asthma, but the mechanism underlying sensitization to this chemical compound remains controversal. Also the correlation of mast cell with contact hypersensitivity (CHS) and the role of mast cell in the TDI-induced CHS is unknown. This issue was investigated by administrating TDI on the skin of genetically mast cell-deficient WBB6F1/$J-Kit^{W}/Kit^{W-v}$ ($W/W^{V}$) and congenic normal WBB6F1/J-Kit+/+ (+/+) mice. Methods: To development of animal model of TDI-induced CHS and to investigate the correlation of mast cell with CHS and the role of mast cell in the TDI-induced CHS, $W/W^V$ and +/+ mice were sensitized with TDI on the back skin at day 1 and day 8, and then challenged with 1% TDI on the ear at day 15. At 1, 2, 4, 8, and 24 hours after 1% TDI challenge, the ear thicknesses were measured. It was investigated the histologic changes of dermis in the ear of $W/W^V$ and +/+ mice at 24 hours after 1% TDI challenge. Results: TDI induced a significant ear swelling response in $W/W^V$ and +/+ mice. TDI induced the significant infiltrations of polymorphonuclear leukocytes and eosinophils in $W/W^V$ and +/+ mice, but not of mast cells in normal mice. And TDI increased a characteristic extent of mast cell degranulation in normal mice. There were no significant differences in the ear swelling and the infiltrations of polymorphonuclear leukocytes and eosinophils of normal versus $W/W^V$ mice, either at baseline or after TDI-induced CHS. Conclusion: From the above results, TDI can be used as a murine CHS model, and the mast cells may not be essential in TDI-induced CHS.

• 광물과 암석
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• 제35권4호
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• pp.457-467
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• 2022

전자현미분석기를 이용한 규산염 유리의 정량화학조성 분석 시 알칼리 원소, 특히 Na이 전자빔에 의해 분석 영역 밖으로 이동(migration)하면서 X선 측정 세기가 시간에 따라 감소하는 현상은 오래 전부터 알려져 왔다. EPMA로 규산염 유리의 Na 함량을 정확하게 측정하기 위해서는 전자빔에 의한 Na 이동을 최소화하는 분석방법을 적용하거나 Na 이동에 따른 X선 측정 세기의 감소 효과를 보정해 주어야 한다. 본 연구에서는 X선 세기의 시계열 변화 곡선을 이용해 Na 이동에 의한 X선 감소를 보정할 수 있는 Probe for EPMA 소프트웨어의 Time Dependent Intensity(TDI) 보정 기능을 이용해 규산염 유리 표준시료 8종의 Na을 분석하였다. 일반적인 지질시료 분석 조건인 15 kV 가속전압, 20 nA 전류 세기 하에서 TDI 보정의 정확도를 검증하였다. 연구 결과 20 ㎛ 크기의 큰 전자빔을 사용했을 때는 Na 감소가 거의 일어나지 않아 보정 없이도 Na의 함량을 정확하게 측정할 수 있었다. 빔의 크기가 10 ㎛ 이하일 때는 Na 감소가 일어나 최대 -55%에 달하는 큰 오차가 발생하는데 TDI 보정을 적용해 이 오차를 ±10% 이내로 줄일 수 있다. Na X선 시계열 변화의 초기 측정값에 가중치를 주고 변화 추세를 선형적으로 가정하는 방법을 사용하면 상대오차를 ±6% 이내로 더 줄여 정확한 Na₂O 함량을 얻을 수 있었다. 따라서 알칼리 원소가 많이 포함된 유리질 시료에서 분석 영역이 충분히 크지 못해 작은 전자빔을 사용해야만 한다면 적절한 TDI 보정을 반드시 해주어야 정확한 조성을 얻을 수 있다.