Conventional lithography, the predominant and still gr owing printing technology, requires use of dampening water, which is troublesome to control. Thus, to eliminate dampening water from lithographic printing, development of waterless planographic printing, which utilizes ink-repellent silicone rubber, had been attempted.
In order to develop a commercially feasible wat erless planographic printing plate, a method of imaging silicone rubber layer was the most important key. A new technology, namely photoinduced adhesion between a specific silicone rubber layer and a specific photosensitive layer, has been found and applied to the positive-working Toray Waterless Plate. The plate consists of a base, a photosensitive layer, and an overlying silicone rubber layer. The plate surface is covered with a thin transparent protecting film. Upon exposure, adhesion between the two layers increases. Then the protecting film is peeled off and the plate surface is wet with a developer that is capable of swelling silicone rubber. The swollen silicone rubber layer becomes wrinkled and can be easily rubbed off in unexposed areas, while it remains in exposed areas.
The negative-working Toray Waterless Plate has also been developed, based on photoinduced release between a specific silicone rubber layer and a specific photosensitive layer. These plates, together with automatic processor, deletion method and inks, present a new type of printing technology which has excellent characteristics in terms of productivity and print quality

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Fine CaS particles were prepared from H2S and Ca(0C₂H₅)₂ in ethanol, diethyl ether or benzene solution. Crystal shape of the CaS obtained in ethanol was spherical and 0.3-, 3 pm in diameter. With increasing reaction temperature, the particle sizes tend to decrease. Crystal shape of the CaS obtained in diethyl ether or benzene was granular and 0.2-7 μm in size. Microstructure examination by TEM indicated that all CaS particles obtained in this method were composed of primary particles with 4, --20 nm in size. It was recognized that the CaS contained free sulfur and an ethoxyl group residue.

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In order to obtain hydrogen trititanate H₂Ti₃O₇ crystals with more active ion-exchange ability from acid treatment of Na₂Ti₃O₇, the synthesis of Na₂Ti₃O₇ was carried out by the hydrolysis of mixed NaOH and Ti, (OPri)₄ ethanol solution without using sodium alkoxide and rather than by melting methods. The ethanol solution of NaOH was mixed with titanium isopropoxide and the mixed solution was hydrolyzed by H₂O-C₂H₅OH solution. The conditions for hydrolysis to obtain Na₂TiaO₇ were investigated. NaOH is known to dissolve about 12 wt%in C₂H₅0H at 28°C. However, the mole ratio Ti/Na of hydrolysis precipitates was not much different from that of the starting solutions when mole ratio 3.0≥Ti/Na≥1.5. Amounts of NaOH remained in ethanol solution after hydrolysis reaction were increased by increase of mole ratio Na/Ti. In the case of mole ratio Ti/Na. l.5, the exothermal peak for crystallization of the dried precipitates was observed to be in the temperature range between 650°C and 670°C by DTA. All products synthesized from mixed NaOH and Ti(OPri)₄. ethanol solutions on these hydrolysis conditions were found to form crystals of Na₂Ti₃O₇single phase after calcination at the temperature above 800°C and below 1130°C (the incongruent melting temperature of Na₂Ti₃O₇ into Na₂Ti₆O₁₃ and melts). Pillarlike well-grown Na₂Ti₃O₇crystals of length from about 1 μm to 30 μm were found by SEM observation when mole ratio 1.5 ≥ Ti/Na≥1.35.

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When the iron concentration in iron-barium glaze was increased, the color of the glaze fired in an oxidizing atmosphere (OF) changed from yellow to yellowish brown or d ark brown, while that of the glaze fired in a reducing atmosphere (RF) changed from blue-gre en to green or black spotted with russet and silver color. In order to clarify the relation between the color and the chemical state of iron in the glaze, diffuse reflectance UV-vis. spect r oscopy (DRS), X-ray powder diffraction (XRD) and MOssbauer spectroscopy were applied.
The valence state of iron in a low concentration range was identified b y DRS (Fig.4). When the iron concentration exceeded a critical value, a part of iron separated as crystallin e iron oxides in the glassy phase. XRD analyses showed that these oxides in the O F and RF glazes were mainly a-Fe₂O₃ and Fe₃O₄, respectively (Fig.5).⁵⁷Fe-MOssbauer spectra reveal e d that iron dissolved in the glassy phase was in a four-coordinated trivalent high -spi n state in the case of OF glazes and that, in the case of RF glazes, a part of the iron was in a six-coordinated divalent high-spin state (Figs.6, 8). t Studies on Chemical State of Iron-Barium Glaze. I.

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Thermal change in the chemical state of iron which determines color of glaze, has been investigated in order to clarify a more effective firing condition in a reducing atmosphere. No phase separation was observed in the heating process of iron-barium glaze containing 5.7 wt% α-Fe₂O₃b y X-ray diffraction (XRD). TG-DTA measurements of the m ixture of starting materials showed that double decomposition of alkaline-earth (Mg, Ca, Ba) carbonates with aluminosilicate took place at 620-930°C. This temperature range is lower than the temperature range (950-1050°C) where reducing atmosphere is introduced in the popular firing method. The changes such as broadening, disappearance and appearance, of diffraction peakes, which are observed by XRD in the quenched glaze are ascribed to th e double decomposition of carbonates with aluminosilicates. MOssbauer spectra of the same samples indicate that Fe⁺ in α-Fe₂O₃ begin to dissolve at about 930°C and are entirely dissolved into glass structure at 1100°C. This result is supported by the broadening and disappearance of peaks of α-Fe₂0₃ in XRD of the same glazes (Fig.3). Studies on Chemical State of Iron-Barium Glaze II. II

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The effects of temperature on the degreee of dissolution of Fe³⁺ were studied on the basis of thermal change in solid state of glaze, in order to find an optimum firing condition in reducing atmosphere. Reducing gases containing hydrogen and carbon monoxide were pro- 1 1 aucea Dy thermal decomposition of methanol vapor (Fig.1). Yields of Fe²⁺ products were determined from ⁵⁷Fe-Mossbauer spectra. No Fe²⁺ products were obtained by holding the sFaem²⁺p le at 750°C, because the amounts of reducing gases were ins ufficient. The yield of species increased in the order of holding temperatures, 1030, 850, 1120, 940, and 1260°C on heating stage. In the reduced glaze at 940°C on cooling, the yield was less than those. at 940 and 1260°C on heating. This suggests that Fe³⁺ in α-Fe ₂0₃ are more sensitive than those dissolved in glass structure and that even the dissolved Fe" ions are reduced more easily at higher temperatures. Peak narrowing on the MOssbauer spectra (Figs.5 d) and 6b)) and growth of new peakes (d=3.45, 3.15, 3.11, 3.81, 4.26, 5.90, 2.60ÅA) on X-ray powder diffraction patterns suggest the production of pellyite [Ba₂Ca(Mg, Fe, Zn, Co)₂Si₆0₁₇] at 940°C in the glaze, which is consistent with the peculiar increase of Fe²⁺ yiel d. Studies on Chemical State of Iron-Barium Glaze. III.

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Kinetics of the ligand substitution of [Fe^III(phen)₃]³⁺ by edta has been investigated with the rotating ring-disc electrode, method. [Fe^III (phen)₃]³⁺ was produced in the presence of edta by the oxidation of [Fe^II(phen)₃]²⁺ at the disc. By analyzing the ring current due to its reduction using digital simulation technique, the substitution rate was found to be a second-order rate law with respect to the concentration of [Fe^III (phen)₃]³⁺ and edta but independent on that of phen. This suggests that the substitution of the first phen molecule is the rate-determining step. The pH dependence of the rate constant can be explained by the mechanism that the reactions with edta and all dissociated species have an inherent rate constant. The rate constant obtained at pH=3 was 8.2 x 10²m ol^-1dm³s^-1 (20°C) and the activation energy was 73 kJrnol^-1.

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Total and water-soluble concentrations of 8 minor constituents were determined for 41calcite-free coral aragonite samples collected from six islands in the Pacific Ocean (Fig.1). Average water-insoluble concentrations are Mg: 980 ppm, Sr: 7900 ppm, Na: 3800 ppm, K: 56 ppm, SO₄^2-: 5700 ppm, PO₄^3-: 63 ppm, F: 840 ppm and Cl: 340 ppm, respectively. No significant variations in these constituent concentrations are found among representative 3coral species, Acropora, Porites and Favia (Table 3). The concentrations of minor constituents in uplifted reef coral aragonite samples (age: ca.10⁵ y. ) are similar to those of living coral aragonite ones (Table 5). This result indicates that these constituents are not easily removed by the interaction with interstitial waters during diagenetic processes, as far as aragonite structure is preserved.

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The reactions of dimethyl N-(N²-cyanoamidino)carbonimidodithioate ( 1) with amines were investigated and several 1-substituted hydrotriazines were prepared. Compound (1) reacted with primary amines below room temperature to give N-substituted N'-(N²-cyanoamidino)-S-methylisothiourea (5) which easily cyclized to 1-su bstituted 4amino-2-imino-6-methylthio-1, 2-dihydro-1, 3, 5-triazines (2 ) by warming up to 30°C. The reaction of (1) with aniline hydrochloride in ethanol yielded 1-phenylhydrotriazine (2 d), whereas in dioxane 2-amino-4-methylthio-6-phenylamino-1, 3, 5-triazine (6) was obtained. (2) reacted with amines in the presence of acid and with cyanamide in the presence of alkali to produce corresponding 1, 2-disubstituted isomelamines in good yield.

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The reaction of phenylhydrazine with eight ketones and three 1, 3-dicarbonyl compounds in an aqueous solution of sodium periodate was investigated. The reaction with 2-butanone gave 3-phenylhydrazono-2-butanone and 2-phenyl-2-phenylazobutane, in addition to 2-phenylhydrazonobutane as the major product. Phenylazo group was regioselec tively introduced on the tertiary carbon in branched ketones. Cyclic ketones gave indole derivatives as miner products in addition to normal phenylhydrazones.1, 3-Dicarbonyl compounds afforded 1-phenylpyrazoles bearing various substituents on C-4. Oxidation Reaction of Phenyihydrazine with Sodium Periodate. V.

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In order to elucidate the predominant factors for the confo rmational change of chicken ovotransferrin (OTf), which has one metal-binding site in each of amino (N) and carboxyl (C) terminal domains, induced by, metal binding, the effects of the coordinated metal ions on the diffusion coefficients (D) of the metal-OTf complexes were investigated by means of dynamic light scattering technique using various lanthanoid (Ln³⁺) ions with a high affinity for C metal-binding site. The D values of the OTf complexes increased with increasing amounts of bound Ln³⁺ up to (Ln³⁺)/(0Tf) (=R) =1.2, and then gradually changed, leveling off above R=2, regardless of the species of Ln³⁺ metals. The behavior of D values with increasing degree of saturation of bound metals was related to that of the C-site complexes compared to the N-site complexes. In addition, the D values of the saturated OTf complexes incredsed with decreasing ionic radii of Ln³⁺. These results suggested that the sto kes radii of the OTf complexes appreciably depend on the ionic radii of bound Ln³⁺ and that the contraction of the OTf molecules originates from a predominant metal binding to the C-site compared to the N-site.

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Poly (oxy-1, 4-phenyleneiminocarbonyl-1, 4-phenyleneoxy-1, 4-phenylenecarbonylimino-1, 4phenylene) (PB-BA) was prepared by low-temperature solution polycondensation of bis(4aminophenyl) ether with bis[4-(chlaroformyl)phenyl] ether in the presence of lithium carbonate as the acid accepter in N-methyl-2-pyrrolidone (NMP).
Tensile properties of PB-BA were compared with those of poly(oxy-1, 4-phenyleneiminocarbonyl1, 4-phenylenecarbonylimino-1, 4-phenylene) (P-1) and poly(oxy-1, 4-phenylenecarbonylimino1, 4-phenyleneiminocarbony1-1, 4-phenylene) (P-2) which are similar to the structure of PB-BA. It was difficult to enhance the tensile properties of PB-BA films by cold and heat drawing at a constant temperature.
Therefore, t he films were drawn in a NMP/water mixture (70: 30, v/v, 40°C) and then were heat-treated (the temperature was raised from room temperature to 250°C at the heating rate of 12-13°C/min. ). The values of birefringence, tensile modulus, strength at break and breaking energy of the drawn-heat-treated films (sample C 5 )) were 288 x 10^-3, 9.1 GPa, 730 MPa and 2.8 x 10⁷ J m^-3.
The values of birefringence, tensile modulus, strength at break and breaking energy ot sample ( 5)J were changed to 265 x 10^-3, 7.9 GPa, 520 MPa and 1.9 x 107J m^-3 after 2 h of heat aging at 350°C in air. These results showed the high-temperature durability of the drawn and heat-treated materials.

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Hydroxymethylation of melamine-, with formaldehyde ( F) was kinetically investigated in aqueous chloroacetate buffers at pH 3 52-2.79 and 40°C. The second-order rate constant k, shown by initial rate Ro=k[MH_F]₀[F]₀ was given by k-k'=-K_HA[HA]+K'_p[HA]²/[A^-];(or K''_p[HA][H⁺]);here, MHf and k' are the free base of melamine, a nd the rate constant Kin'' p[HA][H+]unbuffered media and HA and A-, the acidic constituent and basic constituent of buffer, respectively. The second term of the kinetic equation, K'p-reaction (or k"p, -reaction) was revealed in this study. The relative contribution of the k_HA-reaction( the first term of the kinetic equation) and the K'p-reactionw as estimated by using the obtained k HAa, ndk'p-values. Acid-catalyzed hydroxymethylation mechanism was mainly discussed for "Ambiguities in Kinetic Data".Studied on Formaldehyde Resin. XXXII.

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The copper salt of acetic acid, hexanoic acid, decanoic acid, myristic acid, stearic acid, or behenic acid was added to polymerize butyl titanate in the presence of crushed silica gel. I t has photocatalytic property. Each of the resulting polymers, when studied by IR spectra and magnetization measurement, has different structure depending upon the chain length of carboxylic acid used. The rate of hydrogen generation from 1: 1 water/methanol mixtu re when the copper-butyl titanate polymer is used as catalyst, has shown that the polymer with the copper(II) salt of longer chain carboxylate yields more hydrogen per second. The rate of (light-excited polymer ground state polymer) observed by ESR method is faster when the chain of carboxylic acid is longer. These results suggest that when copper carboxylate of longer chain is added to the titanate polymer, the rate of electron transfer from copper (II)-titanate system to the substrate molecule is faster

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The oxotitanium phthalocyanines having α-phase and β-phase were investigated with the differences of crystal phase using X-ray powder diffraction, spectroscopic, nuclear magnetic and photoelectroscopic methods. The TiOPc was quite different from bivalent metal phthalocyanines. The TiOPc have characteristic X-ray powder diffraction patterns, i. e., the orientation of the (010) face with a-phase and the (001) face with a-phase, respectively, were very high compared with other faces. Because of the larger intermolecular force, the visible absorption peak of a-phase shifted toward longer wavelength. The infrared spectra in 700--800 nm region showed the vibrational energy in IR region of β-phase was larger than that of α-phase. Solid-state ¹³C-NMR spectra suggested β-phase has high regularity on its nuclear magnetic resonances. The XPS spectra of TiOPc gave the proportion of carbon at benzene ring and bonded to nitrogen in TiOPc molecule. The β-phase has much adsorped oxygen than α-phase, because of its longer distances of each molecules. For the TiOPc, the transformation of crystal phases from thermally metastable a-phase to stable p-phase were suggested by the analysis of the heated samples at various temperatures.

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In order to obtain novel derivatives of tetrapyrazinoporphyrazine ( 2 ) in a pure state, symmetrically alkyl-substituted compound ( 2 ) were synthesized. Diaminomaleonitrile (DAMN) was refluxed in ethanol with 3, 4-hexanedione to give 2, 3-dicyano-5, 6-diethylpyrazine (5 b).2, 3-Diethyl-6 H-pyrrolo[3, 4-b]pyrazine-5, 7-diimine (3 b) was prepared by passing a stream of gaseous ammonia through the methanolic solutions of (5 b) in the presence of sodium methoxide. Compound (3 b) was then refluxed in 2-(dimethylamino)ethanol to give 2, 3, 9, 10, 16, 17, 23, 24-octaethyltetrapyrazinoporphyrazine (2 b). The structure of (2 b) is confirmed by IR, '1-I-NMR, MS, electronic spectrum, and elemental analysis. DAMN was refluxed in ethanol with various a-diketones to give 2, 3-dicyano-5, 6-dialkylpyrazines (5 c)-(5 g): alkyl =n-C3H7, n-C₇H₁₅, n-C₉H₁₉, n-C₁₁H₂₃. Compound (5 c)was heated to reflux in methanol in the presence of 1, 8-diazabicyclo[5.4. O]uncieb-7-ene (DBU) to give (2 c). Compound (5 d)-(5 g) were similarly treated with DBU to give (2 d)-(2 g) respectively.
Octaalkyltet rapyrazinoporphyrazines (2b)-(2 g) thus obtained showed high solubilities to organic solvents such as chloroform. They could be purified either by column chromatograph y or by recrystallization. Different from corresponding alkyl-substituted phthalocyanines, they showed no tendency to aggregate in chloroform.

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The hydrogen-isotope exchange reaction between ethanol and a solid acid (Amberlite IRC-50) labeled with tritium has been observed at 30--80°C. The acidity (acidity based on kinetic logic) at each temperature has been obtained with the A"-McKay plot based on the respective data obtained. The following result has been clarified on the basis of both the acidities obtained in the present work and the acidities (of several materials) obtained previously: it seems that the reactivity of OH group (or COOH group) included in a m onomer differs from the reactivity of that bonded to a polymer chain.

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The adsorption capacity of the titled chelating resin for Pd(II) was about 1.8 mmol/g-R on a dry basis. The rate of adsorption was high and adsorption equilibrium was attained within 15 minutes. The chelating resin showed a good adsorption ability for Pd(II) in the pH 0.5-4.5 region and the selective separation of Pd(II) from other di- and trivalent metal ions is possible by using HC1 solution. The Pt(W) and Pd(II) loaded on the resin can be separated from each other by the elution with 1.0 moll NaOH, followed with 0.5mol/l NaOH- 1.0 wt% KCN solution. The recovery of Pd(II) from sea water and prepared solution containing a large amount of several metal ions was carried out and the concentration ratio for Pd(II) by this resin was excellent.

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