释放显影促进剂的成色剂(DAR成色剂)的合成和照相性能研究

释放显影促进剂的成色剂即DAR成色剂,是一类以提高感光度为目的的功能性成色剂.DAR成色剂自20世纪80年代初期开发研究至今,对彩色感光材料向高感、微粒方面发展起了举足轻重的作用.DAR成色剂的典型结构可表示为:Cp-L-A,其中Cp代表成色剂母体、L是吸附基团、A是显影促进基团.成色剂母体可以是黄、品、青成色剂和无色化合物4种;吸附基团一般为含氮杂环衍生物,它的主要作用是吸附在卤化银颗粒表面,吸附基团吸附能力的强弱直接影响DAR成色剂的使用效果;显影促进基团常用的是β酰基苯肼类化合物,它的作用是促进显影.     

不同显影促进基团对DAR成色剂照相性能的影响

研究了带有不同取代基的显影促进基团对DAR成色剂照相性能的影响.通过比较3个母体及吸附基团相同而显影促进基团不同的DAR成色剂的照相性能,发现不同酰基取代的显影促进基团对DAR成色剂的照相性能有较大的影响,其中带三氟乙酰基取代的显影促进基团的DAR成色剂的照相性能最佳.     

甲酰肼型增强基团DAR成色剂的合成及照相性能研究

DAR成色剂(Development Accelerator Releasing Coupler)是近年来研制开发的一类以提高感光度为目的功能性成色剂.由于它在与显影剂氧化物(QDI)发生反应生成染料的同时,释放出显影加速剂,从而起到强化显影的功效,提高了感光度^[1].DAR成色剂通常由成色剂母体,吸附基团和增强基团三部分组成.其中吸附基团的功效在于吸附在卤化银表面控制显影增强基团防止其串层,它的吸附能力强弱直接影响DAR的使用效果,增强基团起到强化显影的作用.     

一种新型功能性显影促进剂的合成及表征

合成了以2-氨基——巯基-1,3,4-噻二唑为吸附基团,4,4-二甲基-1-苯基-3-吡唑啉酮为增强基团的新型功能性显影促进剂,其结构经IR、¹H-NMR、MS和元素分析等得到确证.由于其结构的独特性,可望在促进显影的同时而不导致灰雾增大.可将其直接用来促进显影,或者将其与卤代成色剂母体反应得到DAR成色剂后再用于促进显影.     

新型DAR黄成色剂的合成

以黄成色剂为母体,环状酰肼为显影促进基团,分别以6-氨基苯并咪唑和苯基巯基三氮唑为吸附基团,合成了2种新型DAR成色剂,产率分别为60.8%和48.2%。其结构经IR、1HNMR、MS和元素分析测试技术得到确证。实验结果表明,合成的DAR成色剂在提高感光度时不会增大灰雾密度。     

新型DAR成色剂的合成与照相性能研究

本文合成了两个新型DAR成色剂,其结构经IR,¹H-NMR和MS得到确证.照相性能试验结果表明:DAR成色剂D₁能提高感光度20%,而DAR成色剂D₂在目前的显影条件下没有提高感光度的作用.通过分析其结构,找到了结构与照相性能之间的关系.     

一种新型无色DAR成色剂的合成与应用

以N,N' 双 (2 氯 5 正十二烷氧基羰基)苯基丙二酰胺为母体,以2,5 二巯基 1,3,4 噻二唑为吸附基团,以2 三氟乙酰基苯肼作为增强基团合成了一种新型无色DAR成色剂,通过了IR,1HNMR和MS的认证.实验证明,该DAR成色剂能够提高感光度,并且耐老化性能良好.     

DIAR成色剂的最新进展

本文分别从定时基团、抑制基团、成色母体和分子结构这4方面介绍了近十几年来DIAR成色剂的最新进展,特别介绍了一些具有新结构和新功能的DIAR成色剂的情况.抑制基团是这几年发展最快的,一些具有好的照相性能的抑制基团被合成;为了提高DIAR成色剂的层间效应,设计出了双定时的DIAR成色剂;溶出型的DIAR成色剂得到进一步的改进,从而能够被广泛地应用.     

DAR成色剂研究进展

本文综述了DAR成色剂的研究进展,特别是DAR成色剂的结构和作用机理.     

一种新型功能性显影促进剂的照相性能和抗老化性研究

研究了新型功能性显影促进剂照相性能与作用机理.照相性能试验结果表明:显影促进剂M能明显提高感光度而且具有良好的抗老化性能;染料吸收光谱的结果表明:它的使用不影响主成色剂成色染料的吸收光谱.     

DAR黄成色剂的合成

本文以α-新戊酰基-2-氯-5-[3-(2,4-二特戊基苯氧基)丁酰胺基]乙酰苯胺为母体,以2,5-二巯基-1,3,4-噻二唑为吸附基团,分别以1-甲酰基-2-(4-氨基)苯肼,1-乙酰基-2-(4-氨基)苯肼和1-三氟乙酰基-2-(4氨基)苯肼为增强基团合成了3种DAR黄成色剂.并通过IR,¹HNMR,MS确证了它们的结构.     

新型主体青成色剂Cp-DY的合成及感光性能

照相性能;新型主体青成色剂Cp-DY的合成及感光性能     

Interplay between two-electron and four-electron donor carbonyl groups in oxophilic metal systems: highly unsaturated divanadocene carbonyls

The divanadocene carbonyls Cp2V2(CO)n (n = 5, 4, 3, 2, 1; Cp = eta5-C5H5) have been studied by density functional theory using the B3LYP and BP86 functionals. The global minimum for Cp2V2(CO)5 with a V[triple bond]V distance of 2.452 A (BP86) is essentially the same as the structure of the known Cp2V2(CO)5 determined by X-ray diffraction. The global minimum of Cp2V2(CO)4 is a triplet electronic state with a V[triple bond]V distance of 2.444 A (BP86). However, slightly higher energy singlet Cp2V2(CO)4 structures are found either with a V[triple bond]V distance of 2.547 A (BP86) and one four-electron donor bridging CO group or with a V[quadruple bond]V distance of 2.313 A (BP86) and all two-electron donor bridging CO groups. Comparison is made between Cp2V2(CO)3 and the recently synthesized quintuply bonded RCrCrR (R = bulky aryl group) complexes of Power and co-workers. Four-electron donor bridging carbonyl groups become more prevalent upon further decarbonylation, leading ultimately to three singlet Cp2V2(eta2-mu-CO)2 isomers as well as triplet, quintet, and septet structures of Cp2V2(CO) with extremely low nu(CO) frequencies around 1400 cm(-1). Our most remarkable structural finding is the extremely short vanadium-vanadium distance (1.80 A, BP86) predicted for the singlet structure of Cp2V2(CO).     

Possible effects on the polyethene chain structure of trimethylaluminum coordination to zirconocene catalysts

Ethene was polymerized with the catalytic systems L₂ZrCl₂/MAO/TMA (where L = Cp, Me₅Cp, or Me₄Cp; Cp = η⁵‐cyclopentadienyl; MAO = methylaluminoxane; and TMA = trimethylaluminum) at 60 °C, 2 bar, and Al_TMA/Zr ratios of 0–2700. The polymerization activity was reduced with the addition of TMA for L = Cp but was almost unaffected for the methyl‐substituted catalysts. Increasing the TMA concentration resulted in a lower molecular weight of the polymer, with the largest effect for L = Me₅Cp. A gel permeation chromatography analysis of the polymers revealed a high molecular weight shoulder and a nearly bimodal distribution for L = Me₅Cp at high TMA concentrations. A possible explanation of such a shoulder in terms of long‐chain branching was ruled out by dynamic viscosity measurements. The origin of this effect more likely stemmed from competition between chain transfer to aluminum and β‐hydrogen transfer reactions at two different sites, one TMA‐sensitive and one TMA‐insensitive. Polymerizations at various pressures and temperatures substantiated this assumption. A clue to the underlying mechanism came from investigations of chain transfer to TMA studied with density functional calculations. Complexation of Me₃Al to Zr was much stronger for L = Cp than for L = Me₅Cp. However, the overall chain‐transfer barrier was much higher for L = Cp. These results agreed both with the reduced activity for L = Cp and with the strongly reduced molecular weight for L = Me₅Cp observed with the addition of TMA. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3566–3577, 2001