Immersion oil

Abstract

The invention is directed to an immersion oil for microscopy. The immersion oil includes an ester or ether with tricyclodecane structure as a main constituent and one or more high-boiling liquids as minor constituents. The immersion oil is free of halogens and exhibits a high UV-transmissibility and is characterized by low intrinsic fluorescence because the components utilized can be vacuum distilled.

Description

BACKGROUND OF THE INVENTION

A substantial portion of the immersion oils offered today which have a refractive index of greater than 1.5 include chlorinated paraffin as a main constituent. Chlorinated paraffins are, however, considered to be a dangerous working substance and furthermore exhibit a poor environmental compatibility.

Halogen-free immersion oils are available in addition to immersion oils on the basis of chlorinated paraffin. The main problem in the manufacture of halogen-free immersion oils is the unfavorable relationship of the refractive index and dispersion for most of the halogen-free liquids having refractive indices having a value of greater than 1.5. The Abbe number, which describes the dispersion, deviates in such immersion oils often significantly from the range specified for DIN 58884 for the Abbe number of 44.+-.5 (DIN) and the range ISO 8036/1 for the Abbe number 44.+-.3 (ISO). Known halogen-free immersion oils, which have an Abbe number greater than 41, are either unsatisfactory with respect to their UV-transmissibility or exhibit an intrinsic fluorescence which is too great. Halogen-free immersion oils having values for the Abbe number in the upper tolerance range of the above-mentioned two standards (that is, with an Abbe number v.sub.e >45) are not known.

European patent publication 0,209,621 discloses, in addition to halogen-containing immersion oils, also embodiments for halogen-free immersion oils. Two embodiments for halogen-free immersion oils contain tricyclodecanol as a minor constituent. With respect to the UV-transmissibility (for wavelengths below 400 nm) no information is provided by this patent publication. Furthermore, the viscosity has values of 1,000 and 2000 mm.sup.2 /s at 25.degree. C. is too great for most applications, that is, the use thereof can very easily cause air bubbles to become included.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a base substance for the production of immersion oils for microscopy with which immersion oils having Abbe numbers between 40 and 50 can be produced while also having low intrinsic fluorescence and high UVA-transmissibility and being free of halogen.

The immersion oil of the invention is for microscopy and includes: as a main constituent, the tricyclodecane derivative or derivatives of substances having the basic structure of the tricyclodecane.

The immersion oil of the invention includes, as main constituents, tricyclodecane derivatives or derivatives of substances having base structures of the tricyclodecanes. The portion of the tricyclodecane derivative and/or the derivative of substances having base structures of tricyclodecanes has at least 50% by weight of the total immersion oil in the embodiments wherein the immersion oil is a two-substance mixture and at least 40% by weight for those embodiments wherein the immersion oil is a three-substance or multi-substance mixture. The immersion oil can also contain several tricyclodecane derivatives. In such cases, the sum of all tricyclodecane derivatives have at least 40% by weight of the immersion oil.

The invention proceeds from the recognition that tricyclodecane derivatives or derivatives of substance having the base structure of the tricyclodecanes exhibit a relatively high refractive index while at the same time having a high Abbe number and are therefore superbly suitable as a main component for the immersion oil. The relatively high refractive index while at the same time providing a high Abbe number is because of the ring structure of the tricyclodecanes (TCD). An immersion oil containing a TCD-derivative or derivative of substances having TCD base structure as a main constituent can therefore be free of halogen.

The derivatives of tricyclodecane as well as the substances with tricyclodecane base structures are preferably ester compounds or ether compounds. Here, esters and ethers of tricyclodecane as well as of tricyclodecane-oligomers and tricyclodecane-polymers can be considered. Also, one or several hydrogens of tricyclodecane skeletons can be substituted by other organic residues in addition to the esters and ethers of monomers, oligomers and polymers of tricyclodecanes.

In the preferred embodiments, the main constituents of the immersion oils comprise tricyclodecanemethylolester or tricyclodecanemethylolether as these liquids can be vacuum distilled because of their molecular structure and therefore provide a high degree of purity. Immersion oils having minimum intrinsic fluorescence can be produced from tricyclodecanemethylol esters and tricyclodecanemethylol ethers. The production of immersion oils to the standard values for the refractive index takes place simply by mixing the TCD methylolesters or the TCD methylolethers with suitable high boiling liquids such as softeners, paraffin oils, polypropylene glycols, et cetera.

For the production of TCD-esters and TCD-ethers, the readily available TCD-alcohols, namely, TCD-alcohol M (=8(9)-hydroxymethyltricyclo�5.2.1.0.sup.2,6 !decane) and TCD alcohol DM (=3(4), 8(9)-dihydroxymethyltricyclo�5.2.1.0.sup.2,6 !decane) which are available from Hoechst AG, Frankfurt, Germany. The tricyclodecanemethylolesters or di-(tricyclodecanemethylol)esters can be synthesized via esterification of these alcohols with dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, malonic acid, succinic acid, malic acid, glutaric acid, adipic acid or sebacic acid in accordance with conventional esterification methods.

Di-(TCD-methylol)adipate has been shown to be especially suitable as a main constituent for immersion oils. Here, the percent by weight of the di-(TCD-methylol)adipate is at least 60%. As further components for adjusting the refractive index, butylbenzylphthalate and/or di-(propyleneglycol-1,2)dibenzoate can, for example, be added. The di-(TCD-methylol)adipate is likewise odorless as the other di-(TCD-methylol)ester in contrast to tricyclodecane alcohols and has no significant irritation with respect to human skin.

DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE INVENTION

There are many substances having the base structure of the tricyclodecanes whose ester derivatives or ether derivatives can be considered for the immersion oil of the invention. The structure formulas of such substances are shown in FIGS. 1a to 1c. The substances shown can be a TCD-monomer (FIGS. 1a and 1b) or a TCD-oligomer or a TCD-polymer (see FIG. 1c) for which the ring structure repeatedly occurs n-times. The ring structure is enclosed by brackets in FIG. 1c. One or several hydrogen atoms of the TCD-skeleton can, furthermore, and as shown in FIGS. 1a and 1b, be substituted by a residual R. Examples of suitable residuals R are presented in Table III. The substitution of the hydrogen by residual R has only a subordinate influence on the physical characteristics which are important for immersion oils.

The starting point for the ester synthesis can be TCD-alcohols (wherein X identifies an alcohol residual, preferably OH or CH.sub.2 OH) or TCD carboxylic acids (wherein X identifies a carboxylic acid residual, preferably (COOH).sub.2. Examples of TCD-alcohols known in the literature are presented in Table IV. Here, TCD-monoalcohols, TCD-dialcohols as well as TCD-trialcohols can be used. The TCD-alcohol DM (dialcohol) and the TCD-alcohol M (monoalcohol) are, however, preferred because of their large-scale availability. The corresponding TCD-esters can be produced by converting the TCD-alcohols with a carboxylic acid in accordance with conventional synthesis methods. Suitable monocarboxylic acids, dicarboxylic acids or tricarboxylic acids are presented in Table V. The subsequent purification of the TCD-esters takes place with vacuum or high vacuum distillation. The temperature stability and the high boiling point of the di-(tricyclodecanemethylol)ester (boiling point over 200.degree. C. at a pressure of 10.sup.-5 mbar) is of special significance. From this, excellent vacuum distillation results.

One can proceed from TCD-carboxylic acids as an alternative to ester synthesis from TCD-alcohols. Suitable TCD-monocarboxylic acids and TCD-dicarboxylic acids known from the literature are presented in Table VI. In this case, the esterification takes place by conversion with a monofunctional or a higher alcohol. Suitable alcohols are presented in Table VII.

In the same manner as with the synthesis of the TCD-esters, the corresponding ethers can be produced via conversion of the TCD-monoalcohols in accordance with conventional ether synthesis methods. The TCD-monoalcohols are presented in Table IV.

BRIEF DESCRIPTION OF THE DRAWINGS

In FIG. 2, the structure of di-(TCD-methylol)esters in general are shown and, in FIG. 3, the structures of di-(TCD-methylol)adipate are shown. The TCD-groups can themselves have the structures shown in FIGS. 1a to 1c with the residuals R presented in Table III.

The physical characteristics of several preferred di-(TCD-methylol)esters are presented in Table Ia with the characteristics being important for the immersion oils. The refractive index n.sub.e >1.5 and the simultaneously high Abbe number v.sub.e >=46 (v.sub.e =47 for the di-(TCD-methylol)malinate) and even Abbe numbers v.sub.e >50 for the other given di-(TCD-methylol)esters are essential for the superb suitability of aliphatic di-(TCD-methylol)esters as the main constituent of immersion oils. Furthermore, the excellent UV-transmissibility of the di-(TCD-methylol)esters is significant. This excellent UV-transmissibility is only for wavelengths under 320 nm for a 10 mm layer thickness at less than 10% transmission.

Table Ib shows a comparison of the physical characteristics of an immersion oil of the invention and known halogen-containing and halogen-free immersion oils. The composition of the immersion oil of the invention is presented under number 11 in Table II.

In Table II, the compositions and the physical characteristics of 14 preferred mixtures of a di-(TCD-methylol)ester and one or several high-boiling liquids is presented. The percent by weight of the di-(TCD-methylol)ester for the two component mixtures is between 68 and 98.5 percent by weight and, for the 3-component mixtures, between 51 and 70 percent by weight. As shown by the numerical values for the Abbe number and for the viscosity, almost any desirable viscosity value between 100 mm.sup.2 /s and 6000 mm.sup.2 /s for Abbe numbers in the range of 39 to 50 can be adjusted. Mixtures having viscosities in the range of 400 mm.sup.2 /s to 600 mm.sup.2 /s and therefore the embodiments 6, 11 and 12 are especially preferred for most applications.

In principle, the immersion oil can be put together from several di-(TCD-methylol)esters as a main constituent and several high-boiling liquids as a minor constituent to adjust the refractive index. The starting substances for a low residual fluorescence must be prepared in high purity and the usable quantities are relatively low. For this reason, the two-substance mixture is especially preferred when lower production costs are wanted.

German patent application P 196 08 081.9, filed Mar. 2, 1996, on which the claim of priority herein is based, is incorporated herein by reference.

It is understood that the foregoing description is that of the preferred embodiments of the invention and that various changes and modifications may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims.

TABLE Ia__________________________________________________________________________Physical Characteristics of Di (TCDmethylol)-esters__________________________________________________________________________ Dispersion Viscosity Refractive Indices (Abbe - at at 20.degree. C. No.) .zeta.e 20.degree. C.Substance n.sub.D (589,3 nm) n.sub.D (546,1 nm) DIN 58 884 DIN 51 562__________________________________________________________________________Di-(TCDmethylol)phthalate 1.5497 1.5533 39 ca. 280000 mPa*sDi-(TCDmethylol)malonate 1.5166 1.5191 51 1900 mm.sup.2 /sDi-(TCDmethylol)suoccinate 1.5149 1.5173 51 1600 mm.sup.2 /sDi-(TCDmethylol)glutarate 1.5137 1.5161 51 1300 mm.sup.2 /sDi-(TCDmethylol)adipate 1.5118 1.5142 51 1100 mm.sup.2 /sDi-(TCDmethylol)sebaoate 1.5057 1.5082 51 800 mm.sup.2 /sDi-(TCDmethylol)maleinate 1.5258 1.5284 47 9000 mm.sup.2 /sFor Comparison: 1.5169 105192 52 1100 mPa*sTCD-Alcohol M__________________________________________________________________________ Limit of UV - Permeability at d = 10 mm OtherSubstance T .ltoreq. 10% Characteristics__________________________________________________________________________Di-(TCDmethylol)phthalate at 319 nmDi-(TCDmethylol)malonate at 276 nm Boiling Point:180-185.degree. C. and Absorption Bands at 302 nm at 10.sup.-5 mbarDi-(TCDmethylol)suoccinate at 287 nmDi-(TCDmethylol)glutarate at 286 nmDi-(TCDmethylol)adipate at 262 nm Boiling Point:220-225.degree. C. at 10.sup.-5 mbar Pourpoint: -20.degree. C. (ISO 3016) Flash Point (COC): 265.degree. C. (ISO 2592) Density D.sub.20 = 1.090 g/cm.sup.3 (DIN 51 757)Di-(TCDmethylol)sebaoate at 260 nmDi-(TCDmethylol)maleinate at 317 nm Boiling Point: 226.degree. C. at 1013 mbarFor Comparison: at 238 nm Pourpoint: -24.degree. C. Flash Point (COC): 130.degree. C.TCD-Alcohol M Density D20 = 1.044g/cm.sup.3__________________________________________________________________________ TABLE Ib__________________________________________________________________________Physical Data of Immersion Oils Immersion Oil of the Invention CARL ZEISS Cargille Cargille Cargille according to Immersion Oil Immersion Oil lmmersion Oil Immersion Oil Tab. II, 518 C Type A Type B Type DF Nr. 11__________________________________________________________________________Chemical Basis Chlorinated aliphatic aliphatic Chlorinated Di-(TCDmethylol)- paraffins, Hydrocarbons, Hydrocarbons, Paraffins, alkyl- adipate Phthalic acid ester Terphenyls, Terphenyls, phthalate, Butylbenzyl-phthalate hydrated hydrated Butylbenzyl- Terphenyls Terphenyls phthalatecontaining yes no no yes nohalogensn.sup.23.sub.D 1.5151 1.5150 1.5150 1.5152 1.5152n.sup.23.sub.e 1.5180 1.5181 1.5180 1.5183 1.5180Dispersion .zeta.e 43.5 41 42.5 41.5 45.5Kinematic 460 180 1700 440 560Viscosity at20.degree. C. (mm.sup.2 /s)UV-Permeabilityat d = 10 mm (%)Transmission(against water).cndot. at 420 nm 94 86 88 96.5 >99.cndot. at 400 nm 89 65 78 94 99.cndot. at 380 nm 78 46 60 89 98.cndot. at 365 nm 64 18 37 81 97.cndot. at 350 nm 41 <5 <5 70 93.cndot. at 330 nm <8 <0.1 <0.1 45 85Residualfluorescence(mg/l quinine sulfateequivalent amount).cndot. F 365/450 nm 0.15-0.25 0.42 0.40 0.21 0.020.cndot. F 405/485 nm 4.5-6.5 140 140 5.8 0.65__________________________________________________________________________ TABLE II__________________________________________________________________________Embodiments for halogen-free Immersion Oils Weight Refractive indices Dispersion Viscosity portions at 23.degree. C. (Abbe-No.) at 20.degree. C.Example Components (Wt-%) n.sub.D (589.3 nm) n.sub.e (546.1 nm) .zeta.e (mm.sup.2 /s)__________________________________________________________________________1 Di-(TCDmethylol)phthalate 7.0 Polypropyleneglycol (1,2) 400 30 1.5150 1 .5181 40 60002 Di-(TCDmethylol)phthalate 58 Dioctylphthalate 42 1.5150 1.5182 39 9603 Di-(TCDmethylol)malonate 98.5 Paraffin oil 1.5 1.5150 1.5176 50 14004 Di-(TCDmethylol)malonate 97.5 Dioctylphthalate 2.5 1.5150 1.5176 50 13505 Di-(TCDmethylol)succinate 88.5 Butylbenzylphthalate 11.5 1.5150 1.5177 48 8106 Di-(TCDmethylol)succinate 70 Butylbenzylphthalate 24.5 1.5150 1.5179 44 440 Dioctylsebacate 5.57 Di-(TCDmethylol)succinate 66.5 Dibenzylether 22.0 1.5150 1.5180 42 100 Dioctylsebacate 11.58 Di-(TCDmethylol)maleinate 84 Paraffin oil 16 1.5150 1.5178 48 25009 Di-(TCDmethylol)maleinate 89.5 Dioctylsebacate 10.5 1.150 1.5178 47 180010 Di-(TCDmethylol)glutarate 90 Butylbenzylphthalate 10 1.5150 1.5177 49 82011 Di-(TCDmethyloI)adipate 83 Butylbenzylphthalate 17 1.5150 1.5178 45 56012 Di-(TCDmethylol)adipate 71.5 Di-(propyleneglycol- 28.5 1.5150 1.5179 43 510 1,2)dibenzoate13 Di-(TCDmethylol)sebacate 68 Butylbenzylphthalate 32 1.5150 1.5180 42 300__________________________________________________________________________ TABLE III______________________________________Organic Groups (FIGS. 1a and 1b)______________________________________X = CH.sub.2 OH,COOHR = H,CH.sub.3,C.sub.2 H.sub.5,C.sub.3 H.sub.7,C.sub.4 H.sub.9,C.sub.5H.sub.11C.sub.6 H.sub.13,C.sub.7 H.sub.15,C.sub.8 H.sub.17,C.sub.9 H.sub.19,C.sub.10 H.sub.21CH.sub.2CHCH.sub.2,CHCH.sub.2,CHCHCH.sub.3CH.sub.2CHCHCH.sub.3,OHOCH.sub.3,OC.sub.2 H.sub.5,OC.sub.3 H.sub.7,OC.sub.4 H.sub.9,OC.sub.5 H.sub.11,OC.sub.6 H.sub.13 ##STR1## ##STR2## ##STR3## ##STR4## ##STR5## ##STR6## ##STR7## ##STR8## ##STR9## ##STR10## ##STR11## ##STR12## ##STR13## ##STR14## ##STR15## ##STR16## ##STR17## ##STR18## ##STR19## ##STR20## ##STR21## ##STR22## ##STR23## ##STR24## ##STR25## ##STR26## ##STR27## ##STR28## ##STR29##______________________________________ TABLE IV__________________________________________________________________________TCD - Alcohols__________________________________________________________________________TCD-(Mono)alcohols: ##STR30## ##STR31## ##STR32## ##STR33## ##STR34##TCD-Di-Alcohols: ##STR35## ##STR36## ##STR37## ##STR38## ##STR39## ##STR40##TCD - tri-Alcohols ##STR41## ##STR42##__________________________________________________________________________ TABLE V__________________________________________________________________________TCD - Carboxylic acids__________________________________________________________________________TCD-(Mono)Carboxylic acids: ##STR43## ##STR44## ##STR45##TCD-Dicarboxylic Acids: ##STR46## ##STR47## ##STR48##__________________________________________________________________________

Literature Sources

B.Cornils, R. Payer: Derivate des Dicyclopentadiens--aktuelle Schlusselverbindungen Chemiker--Zeitung 98 70-76 (1974) O. Roelen, K. Buchner et. al., Ruhrchemie Ag, Oberhausen: DBP 934 889 (1955) Verfahren zur Herstellung von Estern und bzw. oder Polyestern der Tricyclodekanreihe. O. Roelen, K. Buchner et. al., Ruhrchemie AG, Oberhausen: DAS 1036 849 (1956) Verfahren zur Herstellung von als Schmiermittel, Weichmacher oder Polyester geeigneten Estern des Di-(tricyclo-�5.2.1.0.sup.2,6 !decyl)-8,8'ather4,4'-dimethylols, bzw. der Di-(tricyclo-�5.2.1.0.sup.2,6 !decyl-)-8,8'-ather4,4'-dicarbonsaure. J. Bartlett, R. Brodkey et. al.: U.S. Pat. No. 2,814,639 (1957) Dimethylol--Tricyclodecanol Esters and Process. British Petroleum Co. Ltd. Brit. Pat. 847 592 (1960) New Polyesters and their method of preparation. TABLE VI__________________________________________________________________________Carboxylic Acid for the Synthesis of TCD - EstersMonocarboxylic Acids:formic acid 2,2-dimethyl-4-pentene acidacetic acid 2-hexene acidpropionic acid 3-hexene acidn/isobutyric acid 2-heptene acidn/iso-valeric acid 6-heptene acidhexanoic acid 2-octene acidheptanoic acid 4-ethyl-2-octene acidoctanoic acid 2-nonene acidnonanoic acid 2-decene aciddecanoic acid ethoxy acetic acidundecanoic acid 3-ethoxy-propionic aciddodecanoic acid L-menthoxy-acetic acidpivalic acid cyclopropanecarboxylic acid 2-methylcyclopropane carboxylic acid2-methylbutyric acid cyclobutane carboxylic acid3-methylbutyric acid cyclopentane carboxylic acid2,2-dimethylbutyric acid cyclohexane carboxylic acid3,3-dimethylbutyric acid cycloheptane carboxylic acidtertiary butyl acetic acid cyclooctane carboxylic acid2-ethyl butyric acid cycloundecanoic carboxylic acid2-methyl valeric acid cyclopentyl acetic acid3-methyl valeric acid cyctohexyl acetic acid4-methyl valeric acid 3-cyclopentyl propionic acid2,2-dimethyl valeric acid tetrahydrofurane-2-carboxylic acid2-propyl valeric acid tetrahydrofurane-3-carboxylic acid2-methyl hexanoic acid 2-tetrahydroxyfurane acetic acid2-ethyl hexanoic acid 1 (2,3,4) methyl-1-cyclohexane carboxylic acidDi-(n-propyl-)acetic acid 4-cyclohexyl butyric acidcrotonic acid 2-cyclohexyl butyric acidvinylacetic acid (.alpha.-�ethyl!cyclohexane acetic acid)2-methyl crotonic acid 2-norborane acetic acid3,3-dimethyl acrylic acid tricyclo�5.2.1.0.sup.2,6 !decane-2carboxylic acid(3-methyl crotonic acid) tricyclo�5.2.1.0.sup.2,6 !decane-3(4)carboxylic acid2-pentene acid (TCD-acid S)4-pentene acid Tricyclo�5.2.1.0.sup.2,6 !decane8(9)carboxylic acid2-methyl-2-pentene acid Adamantane carboxylic acid1-adamantane acetic acid 2-phenylcyclopropane-1-carboxylic acid3-cyclohexene-1-carboxylic acid 1 -phenylcyclobutane carboxylic acid4-cycloheptene-1 -carboxylic acid 1-phenyl-1 -cyclohexane carboxylic acid4-cyclooctene-1-carboxylic acid cyclohexylphenyl acetic acid1 -cycloundecene-1-carboxylic acid diphenyl acetic acidexo-bicyclo�2.2.1!hept-5-ene-2carboxylic acid 3,3-diphenylpropionic acid(exo-5-Norbornene-2-carboxylic acid) 2,2-diphenylpropionic acid5-norbornene-2-acrylic acid 4-phenylvaleric acid3-camphor carboxylic acid 5-phenylvaleric acid2-cyclopentene-1yl-acetic acid phenoxy acetic acid2,2,3,3-tetramethylcyclopropane carboxylic acid 3-phenoxypropionic acid4-acetylbutyric acid 2-phenoxybutyric acid3-methyl-2-oxovaleric acid 4-phenoxybutyric acid4-methyl-2-oxovaleric acid 11-phenoxyundecanoic acid5-acetylvaleric acid 3-benzoylpropionic acid2-oxopentanoic acid 4-benzoylbutyric acid2-oxohexanoic acid 5-benzoylvaleric acid7-oxooctanoic acid 2-phenyllevulinic acid5-oxodecanoic acid o-toluic acetic acid7-oxodecanoic acid m-toluic acetic acid2-ethylhexoxy acetic acid p-toluic acetic acid3,6-dioxa heptanoic acid di-p-toluic acetic acid3,6,9-trioxa decanoic acid 1-indane carboxylic acid3-methoxycyclohexanoic carboxylic acid 1,2,3,4-tetrahydro-1(2)-naphthalene carboxylic acid4-methoxycyclohexanoic carboxylic acid 2-methoxyphenyl acetic acidphenyl acetic acid 3-methoxyphenyl acetic acid2-phenyl propionic acid 4-methoxyphenyl acetic acid3-phenylpropionic acid p-ethoxyphenyl acetic acidbenzoic acid 3-(o-methoxyphenyl)propionic acid2(3,4)-methylbenzoic acid 3-(p-methoxyphenyl)propionic acid(toluic acid) 4-(p-methoxyphenyl)butyric acid2(3,4)biphenylcarboxylic acid 1 -m-toluiccyclopentanoic carboxylic acid1(2)-naphthalene carboxylic acid 1-(p-toluic)-1-cyclopropane carboxylic acid2-phenylbutyric acid 1-(p-toluic)-1-cyclobutane carboxylic acid3-phenylbutyric acid 1-(p-toluic)-1-cyclopentane carboxylic acid4-phenylbutyric acid 1-(p-toluic)-1-cyclohexane carboxylic acid1-phenylcyclopentane carboxylic acid 1-(p-methoxyphenyl)-1-cyclopropane carboxylic acid.alpha.-cyclopentyl-phenyIacetic acid 1-(p-methoxyphenyl)-1-cyciopentane carboxylic acid1-phenyl-1 -cyclopropane carboxylic acid 1-(p-methoxyphenyl)-1-cyclohexane carboxylic acid4-ethoxy--3-methoxyphenyl acetic acid octanedioic acid(3,4-dimethQxyphenyl)acetic acid (suberic acid)(2,5-dimethoxyphenyl)acetic acid nonanedioic acid3(3,4-dimethoxyphenyl)propionic acid (azelaic acid)3,4,5-trimethoxyphenyl acetic acid decanedioic acid1-naphthyl acetic acid (sebacic acid)2-naphthyl acetic acid undecanedioic acid(2-naphthoxy)acetic acid dodecanedioic acid2,3-/2,6/3,4/2,4/2,5-dimethylbenzoic acid tridecanedioic acid2(3,4)-methoxybenzoic acid (brassylic acid)2,342,6/3,4/2,4/2,5-dimethoxybenzoic acid tetradecanedioic acid2(2,4)-ethoxybenzoic acid methylmalonic acidp-tert.-butyl-benzoic acid dimethylmalonic acidp-n-butoxybenzoic acid ethylmalonic acidp-cyciohexyloxybenzoic acid propylmalonic acid4-acetylbenzoic acid diethylmalonic acid3-methoxy-4-methyl-benzoic acid butylmalonic acid3,4(methylenedioxy)benzoic acid (2-cyclopentene-1-yl)malonic acid(piperonylic acid) phenylmalonic acid3,4,5-trimethoxybenzoic acid benzylmalonic acid2,4,6-trimethoxybenzoic acid methylsuccinic acid2,4,5-trimethoxybenzoic acid methylene succinic acid2-benzylbenzoic acid (itaconic acid)o-phenoxybenzoic acid 1-octadecenylsuccinic acid2-bibenzylcarboxylic acid 2,2dimethylsuccinic acid(o-phenethylbenzoic acid) 2,3dimethylsuccinic acid1-methylindene-2-carboxylic acid 2-methylglutaric acid9-fluorene carboxylic acid 3-methylglutaric acidxanthene-10-carboxylic acid 2,2-dimethylglutaric aciddicarboxylic acids:malonic acid 3,3-dimethylglutarlc acidsuccinic acid 2,4-dimethylglutaric acidmaleic acid 2,3-dimethylglutanic acid(toxii acid) 2,3-dimethylmaleic acid (cis)fumaric acid 2,3-dimethylfumaric acid (trans)glutaric acid methylmaleic acidglutacon acid (citraconic acid)adipic acid methylfumaric acid3-hexenediacid (hydromuconic acid) (mesaconic acid)heptanedioic acid (pimelic acid) phenylmaleic acid2-ethyl-2-methylsuccinic acid cyclohexane-1,4-dicarboxylic acidphenylsuccinic acid 4-methylhexahydrophthalic acid3-methyladipic acid 1,1-cyclohexanediacetic acid2,5-dimethyladipic acid cis/trans-4-cyclohexene-1,2-dicarboxylic acidhydroxysuccinic acid exo/endo-5-norbornene-2,3-dicarboxylic acid(DL-malic acid) methyl-5-norbornene-2,3-dicarboxylic acid2-hydroxy-2-isopropylsuccinic acid exo-7-oxabicyclo�2.2.1!hept-5-ene-2,3-dicarboxylic acidsulphosuccinic acid =exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic acid3-hydroxy-3-methylglutaric acid 1,3-adamantanediacetic acid2,2,5,5-tetramethyladipic acid phthalic acid2-oxoglutaric acid isophthalic acid(ketoglutaric acid) terephthalic acid2-oxoadipic acid 4-methylphthalic acid(.alpha.-ketoadipic acid) 2-methoxyisophthalic acid3-oxoadipic acid 5-methylisophthalic acid(.beta.-ketoadipic acid) 5-tert.butylisophthalic acid4-oxoheptanedioic acid 3-phenylglutaric acid(4-ketopimelic acid) TCD-carboxylic acid DS =acetonedicarboxylic acid tricycio�5.2.1.0.sup.2,6 !decane-3(4),8(9)-dicarboxyl ic acid(3-oxoglutaric acid) 8,8'-di(tricyclo�5.5.1.0.sup.2,6 !decyl)ether-3,6-dioxaoctanedioic acid 3(4),3'(4')-dicarboxylic acid(3,6-dioxasuberic acid) tetramethylterephthalic acid3,6,9-trioxaundecanedioic acid o,m,p-phenylenedioic acetic aciddiglycolic acid o,m,p-phenylenedioxydioic acetic acid(oxadiethanoic acid) o,m,p-carboxyphenoxyacetic acidDL-tartaric acid p-phenylenedipropionic acid 2,5-dihydroxybenzol-1,4-diacetic acid2,2'-thiodiacetic acid diphenyldisulfid-2,2'-dicarboxylic acid(thiodiglycolic acid) (2,2'-dithiosalicylic acid)3,3'-thiodipropionic acid diphenylcarboxylic acid3,3'-dithiodipropionic acid 1,5-decalindicarboxylic acidcyclopropane-1,1-dicarboxylic acid (5-dihydroxydecahydronaphthalene)cyclobutane-1,1-dicarboxylic acid 1,8-naphthalic acidcyclobutane-1,2-dicarboxylic acid (naphthalene-1,8-dicarboxylic acid)3,3�tetramethyleneglutaric acid 2,3-naphthaiene-dicarboxylic acidcyclopentane-1,2-dicarboxylic acid 1,4-naphthalene-dicarboxylic acidcamphoric acid 2,6-naphthalene-dicarboxylic acidcyclohexane-1,2-dicarboxylic acid 1,5-naphthalene-dicarboxylic acidcyclohexane-1,3-dicarboxylic acidTricarboxylic Acids:1,2,3-propane tricarboxylic acid citric acid(tricarballylic acid) 1,2,4-benzoltricarboxylic acid2-methyl-1,2,3-propanetricarboxylic acid (trimellitic acid)(.alpha.-methyl-tricarboxylic acid) 1,3,5-benzoltricarboxylic acid1,3,5-pentane tricarboxylic acid (trimesitic acid)1,2,3-propenetricarboxylic acid(aconitic acid)__________________________________________________________________________ TABLE VII__________________________________________________________________________Alcohols for the Synthesis of TCD - Esters and/or EthersMono - Alcohols:methanol 3-octanol 3-methyl-4-octanolethanol 4-octanol 4-methyl-3-nonanoln/iso-propanol 2-nonanol 2-methyl-3-nonanoln/iso-butanol 3-nonanol 2-methyl-4-nonanolsec-butyl alcohol 4-nonanol 3-methyl-4-nonanoltert-butyl alcohol 5-nonanol 2-methyl-2-pentanol1-pentanol 2-decanol 3-methyl-3-pentanol1-hexanol 3-decanol 3-ethyl-3-pentanol1-heptanol 4-decanol 2,4-dimethyl-2-pentanol1-octanol 5-decanol 2,3-dimethyl-3-pentanol1-nonanol 2-methyl-2-butanol1-decanol (tert. amylic alcohol) 2,2,4-tnmethyl-3-pentanol2-methyl-2-hexanol1-undecanol 3-methyl-2-butanol 3-methyl-3-hexanol1-dodecanol 3,3-dimethyl-2-butanol 2,3-dimethyl-3-hexanol2-methyl-1 -butanol 2,3-dimethyl-2-butanol 2,5-dimethyl-2-hexanol2,2-dimethyl-1-propanol 3-methyl-2-pentanol 3,4-dimethyl-3-hexanol(neopentylalcohol) 4-methyl-2-pentanol 3,5-dimethyl-3-hexanol2-methyl-1 -propanol 3-ethyl-2-pentanol 2-methyl-2-heptanol3-methyl-1-butanol 2-methyl-3-pentanol 3-methyl-3-heptanol2,2-dimethyl-1-butanol 2,2-dimethyl-3-pentanol 3-ethyl-3-heptanol3,3-dimethyl-1-butanol 2,4-dimethyl-3-pentanol 4-methyl-4-heptanol2-ethyl-1-butanol 3-methyl-2-hexanol 4-methyl-4-octanol3-methyl-1-pentanol 2-methyl-3-hexanol 4-methyl-4-nonanol4-methyl-1 -pentanoi 5-methyl-3-hexanol 3,5,5-trimethylhexanol2,2-dimethyl-1-pentanol 4-ethyl-3-hexanol (isononylic aicohol2,3-dimethyl-1-pentanol 3,4-dimethyl-2-hexanol crotylic alcohol2-ethylhexanol 2,2-dimethyl-3-hexanol 3-methyl-2-butene-1-ol2-ethyl-2-propylhexanol 2,5-dimethyl-3-hexanol 3-butene-1-ol2-pentanol 6-methyl-2-heptanol 2-methyl-3-butene-2-ol3-pentanol S-ethyl-2-heptanol 4-pentene-1-ol2-hexanol 4-methyf-3-heptanol 4-pentene-2-ol3-hexanol S-methyl-3-heptanol 1-pentene-3-ol2-heptanol 3-methyl-4-heptanol 3-pentene-2-ol3-heptanol 2,2-dimethyl-3-heptanol 4-methyl-3-pentene-2-ol4-heptanol 2,4-dimethyl-3-heptanoI 4-methyl-1-pentene-3-ol2-octanol 2-methyl-3-octanol 2-methyl-4-pentene-2-ol2,3-dimethyl-4-pentene-2-ol cyclo octanemethanol2-hexene-1-ol cyclo undecanemethanol4,4-dimethyl-2-methylene-1-pentanol cyclo dodecanemethanol2-ethyl-2-hexene-1-ol 2-norbornanemethanol4-hexene-3-ol 3-methylnorbornane-2-methanol1 -hexene-3-ol 1-adamantanemethanol5-hexene-3-ol 6,6-dimethylbicyclo�3.1.1!hept-2-ene-2-ethanol (napol)3-ethyl-5-hexene-3-ol3,5-dimethyl-5-hexene-3-ol 1-methyl cyclopentanol3-heptene-1-ol 1-ethyl cyclopentanol1-heptene-3-ol 1-(n-propyl)-1-cyclopentanol2-heptene-4-ol 1-(n-butyl)-1-cyclopentanol2-methyl-1-heptene-3-ol 2-cyclohexene-1-ol4-methyl-1-heptene-4-ol 1 -methylcyclohexanol1-octene-3-ol 2-methylcyclohexanol1-octene-4-ol 2-ethylcycIohexanol3,7-dimethyl-6-octene-l-ol 3-methylcyclohexanol(citronellol) 4-methylcyclohexanolcyclo butane-1-ol 4-ethylcyclohexanolcyclopropylmethylcarbinol 4-tert. butylcyclohexanoldicyclopropylcarbinol 2,3-dimethylcyclohexanolcyclobutanol 2,5-dimethylcyclohexanolcyclopentanol 2,4-dimethylcyclohexanolcyclohexanol 2,6-dimethylcyclohexanolcycloheptanol 3,5-dimethylcycIohexanolcyclooctanol 3,4-dimethylcycIohexanolcyclopentylmethanol 3,3,,5-trimethylcyclohexanol2-cyclopentylethanol dl-menthol1 cyclopentylethanol p-menth-1-ene-9-ol3-cyclopentyl-1-propanol isopulegolcyclohexylmethanol bornyl alcohol, isoborneol2-methylcyclopentanol myrtanol1-cyclohexylethanol 1-methylcyclooctanol1-cyclohexyl-1-propanol cyclododecanol1-cyclohexyl-1-butanol norborneol (endo/exo)2-cyclohexylethanol3-cyclohexene-1-methanol 5-norbornene-2-ol3-cyclohexene-1-ethanol borneolcycloheptanemethanolTCD-alcohol A 1-phenyl-1-pentanol= 5-hydroxy-tricyclo �5.2.1.0.sup.2,6 !decane cyclopropylphenylcarbinol3(4)-hydroxy4ricyclo�5.2.1.026!decane 1 cyclopropyl--methylbenzylalcoholTCD-alcohol M cyclohexylphenylcarbinol= 8-hydroxymethylcyclo�5.2.1.0.sup.2,6 !decane 1-phenyl-1-cyclohexanol3(4)-hydroxymethyl-tricyclo�5.2.1.0.sup.2,6 !decane 2-phenyl-1-cyclohexanolTCD alcohol E benzhyd rol= 8(9)-hydroxy-tricyclo�5.2.1.0.sup.2,6 !dec-3-ene 1,1-dlphenylethanol5-hydroxy-tricyclo�5.2.1.0.sup.2,6!dec-3-ene .alpha.-benzylbenzhydrol1-adamantanol o-phenyethylbenzylalcohol2-adamantanol 2-methoxybenzylalcoholdecahydro-1 (2)-naphthol 3-methoxybenzylalcoholdi-2-norbornylmethanol 4-menthoxybenzylalcohol2-methoxyethanol 4-methylbenzylalcohol2-ethoxyethanol p-tert. butylbenzylatcohol2-propoxyethanol p-butoxybenzylalcohol2-butoxyethanol p-dimethylbenzytalcohol3-ethoxy-1-propanol p-methyl-.alpha.-(n-propyl)benzylalcohol3-methoxy-1-butanol 4,4'-dimethoxybenzylalcohol2-isopropyloxyethanol o-phenoxybenzylalcohol1 ,3-diethoxy-2-propanol p-methoxy-.alpha.-methylbenzylalcohotdiethyleneglycolmonomethylether p-methoxy-.alpha.-ethylbenzylalcohol(methyldiglycol) .alpha.-cyclopropyt-p-methylbenzylalcoholdiethyleneglycolmonoethylether (cyclopropyl-p-toluic carbinol)(ethyldiglycol) .alpha.-cyclopropyl-.alpha.,p-dimethytbenzylalcoholdiethyteneglycolmonobutylether .alpha.-cyctopropyl-p-methoxybenzylalcohol(butyldiglycol) 2,3-dimethoxybenzylalcohol4-ethoxy-1-decalol 2,4-dimethoxybenzylalcohol3-hydroxytetrahydrofurane 3,4-dimethoxybenzylalcoholtetrahydroxyfurfurylalcohol 3,5-dimethoxybenzylalcoholtetrahydropyrane-2-methanol 3,4-methylenedioxyphenylmethanol2,2-dimethyl-1,3-dioxolane (Piperonylic alcohol)(solketal) 3,4,5-trimethoxybenzylalcoholdiacetonealcohol 4-biphenylmethanolbenzylalcohol (p-phenylbenzylalcohol).alpha.-methytbenzylalcohol m(p)-benzyloxybenzylalcohot.alpha.,.alpha.-dimethylbenzylatcohol 1,2,3,4-tetrahydro-1-naphthot.alpha.-ethylbenzytalcohol benzo-2,3-dihydroxypyrane-4-ot1-phenyl-1-butanol (4-chromanol)2-hydroxymethyl-1 ,4-benzodioxane 2-phenyl-1-propanol1(2)-naphthalenemethanol .beta.-ethylphenethylalcohol9-fluorenemethanol 3-phenyl-1-propanol1-fluorenemethanol 3,3-diphenyl-i-propanol9-hydroxyfluorene benzyl-tert. butanol1-acenaphthenol 2-phenoxyethanoldibenzosuberol 1-naphthalinethanol9-anthracenemethanol 1(o-benzylphenoxy)-2-propanolphenethylalcoholDialcohols (Dioles)ethylenegycol 1,12-dodecanediol1,2-propanediol cyclohexane-1,1-dimethanol1,3-propanediol 3-cyclohexene-1,1-dimethanol2,2-dimethyl-1,3-propanediol 1,5-cyclooctanediol(neopentylglycol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol2,2-diethyl-1,3-propanediol 1,2-cyclohexanediol2-ethyl-2-methyl-1,3-propanediol 1,3-cyclohexanediol2-methyl-2-propyl-1,3-propanediol 1,4-cyclohexanediol2-n-butyl-2-ethyl-1,3-propanediol 1,2-cycloheptanediol1,4-butenediol 1,2-cyclododecanediol2-methyl-1,4-butanediol 1,4-decalenediol1,3-butanediol 1,5-decalenediol1,2-butanediol TCD-alcohol DM2,3-butanediol = 3(4),B(9)-bis(hydroxymethyl)tricyclo�5.2.1.02!dec anepinacol 3(4),8(9)-bis(hydroxymethyl)tricyclo�5.2.1.0.sup.2, 6 !decane(1,3-dimethyl-2,3-butanediol) TCD-alcohol OM1,5-pentanediol 8-hydroxy-4(5)hydroxymethyl4ncyclo�5.2.1.0.sup.2,6 !decane2,4-pentanediol 3,4-dihydroxytricyclo�5.2.1.0.sup.2,6 !decane2-methyl-2,4-pentanediol di-TCD-alcohol M)ether1,6-hexanediol = di(tricyclo�5.2.1.0.sup.2,6 !decyl-8,8'-ether-3(4 ))dimethylol2,5-hexanediol di-TCD-alcohol A)ether2-ethyl-1,3-hexanediol = di (tricyclo�5.2.1.0.sup.2,6 !decyl-8,8'-ether-3( 4),3'(4'))diol2,5-dimethyl-2,5-hexanediol 5,9-cyclododecanedien-1,2-diol1,7-heptanediol 2-butene-1,4-diol1,8-octanediol 3-hexene-2,5-diol1,9-nonanediol 1,2-cyclobutanedimethanol1,10-decanediol 1,4-cyclohexanedimethanol5-norbornene-2,2-dimethanol 4(2-hydroxyethoxy)-1-decatoldiethyleneglycol 2,4-dihydro-2H-pyrane-2,2-dimethanoltriethyleneglycol 1,2-benzoldimethanoltetraethyleneglycol 1,3-benzoldimethanolpolyethyleneglycol 1,4-benzoldimethanoldipropyleneglycol tetramethyl-p-xylol--,&-diolpolypropyleneglycol 2,2-diphenyl-1,3-propanediolpolyletrahydrofurane 1-phenyl-1,2-ethanediol(poly- 1,4-butanediol) (styreneolycol)Polvalcohols (Polvoles)glycerol pentaerylhritetrimethylolethane dipentaerylhritetrimethylolpropane meso-erylhritol2-hydroxymethyl-2propyl-1,3propanediol TCD-atcohol TO1,2,6-trihydroxyhexane = 8(9),3(4)-tri-hydroxy-tricyclo�5.2.1.0.sup.2,6 !decane2,5-dimethyl-1,2,6-hexanetriol 8-hydroxy-4,4-dihydroxymethyl-tricycto�5.2.1.0.sup. 2,6 !decane__________________________________________________________________________

Claims

1. An immersion oil for microscopy, the immersion oil comprising:

as a main constituent, the tricyclodecane derivative or derivatives of substances having the basic structure of the tricyclodecane;

said tricyclodecane derivative or derivatives being esters or ethers of tricyclodecanes or said tricyclodecane derivatives being esters or ethers of substances having base structures of tricyclodecanes; and,

said immersion oil further including minor constituents comprising one or more high-boiling liquids.

2. The immersion oil of claim 1, wherein said substances are tricyclodecanepolymers or tricyclodecaneoligomers.

3. The immersion oil of claim 1, wherein the main constituent is selected from the group consisting of tricyclodecane-methylolesters and tricyclodecanemethylolethers.

4. The immersion oil of claim 1, wherein said immersion oil further comprises minor constituents comprising one or more high-boiling liquids.

5. The immersion oil of claim 4, wherein the high-boiling liquids are selected from the group consisting of paraffin oil, softeners, polypropylglycol, butylbenzylphthalate, dioctylphthalate, dioctylsebacate and di-(propyleneglycol-1.2)dibenzoate.

6. The immersion oil of claim 1, wherein the portion of the tricyclodecane derivative or the derivative of substances having the base structure of the tricyclodecane is greater than 50% by weight.

7. The immersion oil of claim 1, wherein the portion of the tricyclodecane derivative or the derivative of substances having the base structure of the tricyclodecane is greater than 60% by weight.

8. Di-(tricyclodecanemethylol)adipate produced by esterification of 8(9)-hydroxymethyltricyclo �5.2.1.0.sup.2,6 !decane and adipic acid followed by vacuum distillation of the esters obtained.

9. An immersion oil for microscopy, the immersion oil comprising:

as a main constituent, the tricyclodecane derivative or derivatives of substances having the basic structure of the tricyclodecane; and,

said main constituent being selected from the group consisting of: di-(tricyclodecane methylol)adipate, di-(tricyclodecane methylol)phthalate, di-(tricyclodecane methylol)malonate, di-(tricyclodecanemethylol)succinate, di-(tricyclodecane methylol)maleinate, di-(tricyclodecanemethylol)glutarate and di-(tricyclodecanemethylol)sebacate.

10. The immersion oil of claim 9, wherein said immersion oil further comprises minor constituents comprising one or more high-boiling liquids.

11. The immersion oil of claim 10, wherein the high-boiling liquids are selected from the group consisting of paraffin oil, softeners, polypropylglycol, butylbenzylphthalate, dioctylphthalate, dioctylsebacate and di-(propyleneglycol-1.2)dibenzoate.

12. The immersion oil of claim 9, wherein the portion of the tricyclodecane derivative or the derivative of substances having the base structure of the tricyclodecane is greater than 50% by weight.

13. The immersion oil of claim 9, wherein the portion of the tricyclodecane derivative or the derivative of substances having the base structure of the tricyclodecane is greater than 60% by weight.

14. Di-(tricyclodecanemethylol)adipate having the formula: ##STR49##

15. An immersion oil for microscopy, the immersion oil comprising:

as a main constituent, di-(tricyclodecanemethylol)ester or di-(tricyclodecanemethylol)ether or substances having the basic structure of di-(tricyclodecanemethylol)esters or di-(tricyclodecanemethylol)ethers.

16. The immersion oil of claim 15, wherein the main constituent is selected from the group consisting of: di-(tricyclodecane methylol)adipate, di-(tricyclodecane methylol)phthalate, di-(tricyclodecane methylol)malonate, di-(tricyclodecanemethylol)succinate, di-(tricyclodecane methylol)maleinate, di-(tricyclodecanemethylol)glutarate and di-(tricyclodecanemethylol)sebacate.

17. The immersion oil of claim 15, wherein said immersion oil further comprises minor constituents comprising one or more high-boiling liquids.

18. The immersion oil of claim 17, wherein the high-boiling liquids are selected from the group consisting of paraffin oil, softeners, polypropylglycol, butylbenzylphthalate, dioctylphthalate, dioctylsebacate and di-(propyleneglycol-1.2)dibenzoate.

19. The immersion oil of claim 15, wherein the portion of the di-(tricyclodecanemethylol) ester or ether or substances having the basic structure of di-(tricyclodecanemethylol) esters or ethers is greater than 50% by weight.

20. The immersion oil of claim 15, wherein the portion of the di-(tricyclodecanemethylol) ester or ether or substances having the basic structure of di-(tricyclodecanemethylol) esters or ethers is greater than 60% by weight.