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US3558535A - Coating compositions comprising an epoxidized fatty ester of a cyclic polyol and an acidic polyester - Google Patents

Coating compositions comprising an epoxidized fatty ester of a cyclic polyol and an acidic polyester Download PDF

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Publication number
US3558535A
US3558535A US782496*A US3558535DA US3558535A US 3558535 A US3558535 A US 3558535A US 3558535D A US3558535D A US 3558535DA US 3558535 A US3558535 A US 3558535A
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acid
coating compositions
present
cyclic polyol
epoxidized fatty
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Brian M Rushton
Oliver A Ossanna
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NL SPENCER KELLOG Inc
Ashland LLC
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Ashland Oil Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • Y is O-, S, or -CH R is an epoxidized fatty radical, such as those derived from tall oil fatty acids.
  • composition of matter comprising the above epoxidized fatty esters and an acidic polyester. These compositions of matter are useful as coating compositions and paint substitutes, when applied to substrates.
  • compositions of matter comprising epoxidized fatty esters of cyclic polyols and acidic polyesters. These compositions of matter are useful as coating compositions for a wide variety of substrates.
  • Coating compositions which are a mixture of reactive components are known in the art.
  • One form of such coating compositions is that wherein one component is an acidic polyester and the other component is an epoxide. Because of the reactivity of these two components with one another, it is not practical to premix them in a single container which can be stored, sold and shipped, since immediately upon mixing, the acidic polyester begins to react with the epoxide with a consequent gradual increase in the viscosity of the mixture. This increase in viscosity eventually results in gellation, and finally renders the entire mixture a solid, intractable mass.
  • coating compositions which provide cured films having Patented Jan. 26, 1971 increased hardness. It is also desirable to employ coating systems which provide films which. cure in shorter times. Considerable effort has been expended in attempting to piovide coating systems which cure to films having greater hardness in shorter lengths of time, however, many of these attempts have resulted in formulations having other undesirable properties such as a decreased pot life of the mixture of components, or a reduction in the flexibility of the cured film.
  • a further object of the present .invention is to provide novel coating compositions which when applied to a substrate cure in a short time to hard films.
  • a still further object of the present invention is to provide novel coating compositions which when applied to a substrate cure in a short time to flexible films.
  • Yet another object of the present invention is to provide novel coating compositions having an extended pot life which when applied to substrates cure in a short time to hard, flexible films.
  • composition comprising an epoxide which is coreactive with an acidic polyester.
  • the epoxides useful in the present invention can be described as the epoxidized reaction product of a cyclic polyol and a fatty acid.
  • the cyclic polyols which can be employed preferably have at least three hydroxyl groups, and most preferably have four or five hydroxyl groups attached to the cyclic ring.
  • the hydroxyl groups can be attached directly to the cyclic ring but are preferably present in the form of lower alkylol groups and most preferably present in the form of methylol groups.
  • the cyclic ring of the cyclic polyol can contain from four to ten carbon atoms but preferably contains six.
  • the ring of the cyclic polyol can contain one or more hetero atoms such as sufur, oxygen or nitrogen.
  • the ring of the cyclic polyol is carbocyclic and contains only carbon and hydrogen.
  • the ring of the cyclic polyol is most preferably saturated.
  • the cyclic ring can also contain other substituents which do not materially alter the hydrocarbon nature of the ring, examples of which include, among others, hydroxyl groups and halogen atoms such as chlorine or bromine.
  • One preferred cyclic polyol useful in the present invention is 2,2,6,6-tetramethylolcyclohexanol; others are 3,3,5,5 tetramethylol 4-hydroxypyran and 3,3,5,5-tetramethylol-4-hydroxythiopyran.
  • the preferred epoxides useful in the present invention are those of Formula I:
  • the unsaturated fatty acids useful in the present invention are those having sufficient unsaturation as indicated by their iodine value such that when reacted with the cyclic polyols they can be epoxidized to yield the novel epoxides of the present invention having the desired oxirane value.
  • the iodine value of these fatty acids is at least 50 and is preferably between 90 and 275.
  • the unsaturation is present in the form of one or more double bonds in the fatty radicals of the fatty acids.
  • Suitable fatty acids having one double bond include among others, obtusilic acid, caproleic acid, linderic acid, lauroleic acid, tsuzuic acid, phsteric acid, myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, vaccenic acid, gadoleic acid, cetoleic acid, erucic acid, selacholeic acid, and xirnenic acid.
  • Suitable fatty acids having a plurality of double bonds include among others linoleic acid, linolenic acid, a-eleostearic acid, ,8- eleostearic acid, parinaric acid, arachidonic acid, and clupanodonic acid. Mixtures of the above described acids with one another and with saturated fatty acids can also be employed as long as the fatty acid mixture has a sufficiently high iodine value to give epoxidized fatty acid esters of the desired oxirane content.
  • the iodine value of these fatty acid mixtures is generally at least 50 and is preferably between 90 and 275.
  • saturated fatty acids which can be used in a mixture with the above described unsaturated fatty acids include among others caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, benenic acid, and lignoceric acid.
  • caprylic acid capric acid
  • lauric acid myristic acid
  • palmitic acid palmitic acid
  • stearic acid arachidic acid
  • benenic acid lignoceric acid
  • fatty acids having an odd number of carbon atoms such as those derivable from hydrocarbon sources are completely suitable for use in the present invention
  • preferred fatty acids are those derived from the naturally occurring fats and oils examples of which include among others linseed oil, tung oil, castor oil, dehydrated castor oil, saffiower oil, soya oil, cottonseed oil, olive oil, cocoanut oil, and tall oil which is preferred.
  • the epoxides useful in the present invention are generally prepared by a two step process which comprises first reacting the cyclic polyol with the fatty acid to form an ester, and then epoxidizing this ester.
  • the first step of the process can be carried out according to known esterification procedures and under conditions Well-known in the art. In general it is only necessary to combine the cyclic polyol and the fatty acid in stoichiometric amounts and heat the reaction mixture to a temperature between 100 and 350 C. until the reaction is complete as is evidenced by cessation of evolution of water of reaction.
  • the cyclic polyol is 2,2,6,6-tetramethylolcyclohexanol at least 4 and preferably 4.5 moles of fatty acid are employed per mole of cyclic polyol.
  • esterification reaction catalysts such as for example dibutyl tin oxide can be employed to hasten the reaction.
  • stabilizers such as for example triphenylphosphite can be employed to inhibit the formation of color bodies at temperatures usually required for complete esterification.
  • the second step of the process wherein the above-described ester is epoxidized can be conducted under conditions and according to procedures Well-known in the art, such as by mixing the reaction product with a lower carboxylic acid such as acetic or propionic acid and a stoichiometric amount or a slight excess, such as up to 40 mole percent, of hydrogen peroxide in the presence of an epoxidation catalyst such as, for example, sulfuric acid or the sulfonated styrene-divinyl benzene copolymers, examples of which include, among others Dowex 50WX8, Duolite C-20, and Duolite C 3, a methylene sulfonic acid resin.
  • a lower carboxylic acid such as acetic or propionic acid
  • a stoichiometric amount or a slight excess, such as up to 40 mole percent of hydrogen peroxide in the presence of an epoxidation catalyst
  • an epoxidation catalyst such as, for example
  • the reaction can be conducted at subatmospheric, superatmospheric or, more conveniently, at atmospheric pressure and at temperatures between 75 and 200 F.
  • the reaction is carried out until the epoxidized polyol has an oxirane value of at least 3% and preferably from 3 to 10%.
  • Other epoxidation procedures used in the art for the epoxidation of triglycerides would also be expected to yield the epoxides of the present invention.
  • the fatty acid esters of cyclic polyols can be reacted with suitable peracids to yield the epoxides of the present invention.
  • suitable peracids include, among others, perbenzoic acid, performic acid and peracetic acid or a mixture of such peracids.
  • the peracids can be made in situ or, alternatively, preformed.
  • novel epoxides of the present invention form excellent coating compositions when mixed with acidic polyesters.
  • the preferred acidic polyesters are those having an acid number of at least 50 and preferably at least 160. They can be described generally as the esterification reaction product of a polyhydric alcohol and a polycarboxylic acid, said reaction product comprising a polyester of Formula 111:
  • n is an integer equal to at least two; R is a polyhydric alcohol residue; and R is a polycarboxylic acid residue.
  • Acidic polyesters useful in the present invention can III F, be prepared by esterifying a reaction mixture of a polycarboxylic acid and a polyhydric alcohol, wherein the reaction mixture preferably has an initial ratio of carboxy groups to hydroxyl groups of between 1:1 and 3:1 and preferably between 1.8:1 and 22:1.
  • the reaction mixture is heated at esterification temperatures of between about and 350 C. until the reaction is complete as indicated by cessation of evolution of water of reaction.
  • suitable acidic polyesters is given in U.S. Pat. 3,218,274, and in particular in Examples I through X inclusive thereof.
  • polycarboxylic acids suitable for the synthesis of the acidic polyesters useful in the present invention include among others maleic acid, tri-mellitic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, fumaric acid, itaconic acid, their extant anhydrides and mixtures thereof.
  • the most preferred acid is phthalic anhydride.
  • a portion of the polycarboxylic acid is a halogenated polycarboxylic acid such as tetrachlorophthalic acid, or more preferably hexachloroendornethylene tetrahydrophthalic acid, available under the trade name Chlorendic Acid or Chlorendic Anhydride.
  • a halogenated polycarboxylic acid such as tetrachlorophthalic acid, or more preferably hexachloroendornethylene tetrahydrophthalic acid, available under the trade name Chlorendic Acid or Chlorendic Anhydride.
  • the acidic polyesters useful in the present invention can also be those which have been rendered organic solvent soluble by various means, such as those given above as suitable reactants for the cyclic polyols.
  • the synthesis of these aciidc polyesters is described in detail in U.S. patent application Ser. No. 570,761, filed Aug. 8, 1966, now abandoned, and in particular in Examples 1 through 29 inclusive thereof.
  • the acidic polyesters useful in the present invention can also be those which are vinyl-modified, the synthesis of which is described in detail in U.S. patent application Ser. No. 661,189, filed Aug. 17, 1967, now U.S. Pat.
  • the coating compositions of the present invention are prepared by simply mixing the above-described acidic polyesters with the above-described epoxides. Mixing can be effected by any convenient means such as by means of a handheld spoon or a mechanical homogenizer.
  • the coating compositions of the present invention can have a Weight ratio of the epoxide to the acidic polyester of between 2:1 and 2:5 and preferably between 2:1 and 2:3, and most preferably 1:1.
  • Solvents can be present in admixture with epoxide, the acidic polyester, and the coating composition, in order to give the resultant solution a viscosity which will facilitate application of the coating composition to the substrate.
  • the solvent can comprise from less than 30 to over 70 weight percent of the solution although when employed it is preferably present within these ranges.
  • suitable solvents include among others methanol, ethanol, xylene and mineral spirits.
  • the coating compositions of the present invention can be modified by the addition of compatible materials such as pigments, extenders, plasticizers, ultraviolet light absorbents, and coloring agents.
  • the coating compositions of the present invention can be cured by raising them to a temperature below the degradation temperature of the coating such as 50 to 150 C.
  • the acidic polyester used in the coating composition of the present invention contains chlorendic acid or chlorendic anhydride, the coating composition will cure at ambient temperatures.
  • the coating compositions of the present invention can be cured by air drying or oven baking.
  • compositions of the present invention comprising acidic polyesters and epoxides can be employed as coatings for wood, ceramic, ferrous metals, nonferrous metals, and the like.
  • these novel coating composi tions can be used to protect the coated substrate from the adverse eifects of weather, water, and air.
  • useful objects as wooden and metal boats, lawn chairs, houses, barns, and the like, can be advantageously coated with these novel compositions.
  • the term acid number refers to the number of milligrams of potassium hydroxide necessary to completely neutralize one gram of the nonvolatile content of the composition tested.
  • the iodine number refers to the number of grams of iodine absorbed under standard conditions by 100 grams of the nonvolatile content of the composition.
  • the oxirane value is the Weight percentage of oxiraneoxygen present in the nonvolatile content of the composition.
  • Polyester A This example illustrates the synthesis of an acidic polyester, termed Polyester A, which is useful in the present invention.
  • Polyester B This example illustrates the synthesis of an acidic polyester, termed Polyester B, which is useful in the present invention.
  • EXAMPLE 3 This example illustrates the synthesis of an epoxidized fatty acid ester of a cyclic polyol useful in the present invention termed Epoxide C.
  • the contents of the flask constitute a fatty acid ester.
  • the fatty acid ester (1000 g.) produced as described above and Items E, F and G are charged to a round bottom flask fitted with a stirrer, reagent addition tube and Friedrich condenser.
  • the flask is immersed in a water bath at 118 F.
  • Item H is then added slowly and uniformly over a period of 45 minutes.
  • the water bath is adjusted to maintain the temperature of the flask and its contents at 140 F. for the remainder of the reaction. Stirring is continued for 15 hours, after which time the contents of the flask are filtered to remove Item P which is present in the form of beads.
  • Item F may be reused as a catalyst in future epoxidations.
  • Epoxide C has the following characteristics:
  • Heptane 300 Items A and B are charged to a round bottom flask fitted with a stirrer, a reagent tube, and a Friedrich condenser. The flask is immersed in a water bath at 96 F. Item C which had been treated with sodium acetate to remove traces of sulfuric acid which may be present, is added slowly and uniformly over a period of one hour. The temperature rises to 100 F. and the Water bath is adjusted to maintain this temperature for the remainder of the reaction. Stirring is continued for hours. The contents of the flask separate into an aqueous and a nonaqueous phase.
  • the nonaqueous phase contains the epoxide.
  • the nonaqueous phase is diluted with Item D and separated from the aqueous phase.
  • the nonaqueous phase is then Washed twice with volumes equal to that of the nonaqueous phase with (1) hot 5% aqueous sodium carbonate solution, (2) hot water. Volatiles are removed from the oil by stem stripping at reduced pressure.
  • Epoxide D has the following characteristics:
  • EXAMPLE 5 This example illustrates the synthesis of an epoxidized fatty acid ester of a cyclic polyol termed Epoxide F.
  • Example 3 The procedure of Example 3 is followed employing the same materials, quantities and conditions with the exceptions that Item F, the resin catalyst is that recovered from a previous epoxidation and the total epoxidation reaction time is 19 hours.
  • the four polyester components of column 1 are each mixed with the epoxides of column 2 in the ratios shown in column 3.
  • the pot life of these mixtures is determined and recorded in column 4.
  • a 3 mil thick coating of each mixture is brushed on a glass substrate and permitted to cure in atmospheric air at a constant temperature of 20 C.
  • Various tests are conducted on the curing and cured films and the results thereof recorded in columns 5 through 10. After the film has cured for 24 hours it is found to have a thickness of 1.5 mils.
  • the non-transfer time is measured by applying light finger pressure to the coated substrate at regular intervals until the coating on the substrate does no transfer to the finger. The elapsed time from the time of application of the coating until there is no transfer recorded.
  • VG Very GoodNo discernable efiect.
  • VG- Very Good MinusFilm shows a very slight indentation.
  • G Good-Film shows an indentation, but the substrate does not show through.
  • G Good Minus-Film shows a deeper indentation, but the substrate does not show through.
  • F Fair-Substrate shows through in spots.
  • P Poor-Substrate shows through along scratch.
  • EXAMPLE 8 This example illustrates some of the excellent physical properties possessed by mixtures of polyester components and epoxy components of the present invention when applied to a substrate and subsequently baked.
  • the four polyester components of column 1 are each mixed with the epoxide of column 2 in the ratios shown in column 3. Each of these mixtures is sprayed on a tin substrate until the resultant coating is 6 mils thick. The coated substrate is then placed in an oven at 121 C. for 30 minutes. The coated substrate is 40 then removed and cooled whereupon the thickness of the coating if found to be 3 mils. Certain tests are preformed on the coating of this substrate and their results recorded in columns 4 through 8 of Table II.
  • EXAMPLE 9 This example illustrates the synthesis of an epoxidized fatty acid ester of a cyclic polyol containing one hetero oxygen atom.
  • EXAMPLE 11 This example illustrates the advantageous properties of the coating compositions of the present invention produced from different epoxides.
  • composition of matter comprising:
  • composition of claim 1 wherein the cyclic polyol has a saturated carbocyclic ring.
  • composition of claim 1 wherein A has the wherein R is an epoxidized fatty radical.
  • composition of claim 4 wherein the epoxidized fatty radical A contains from 8 to 27 carbon atoms.
  • composition of claim 4 wherein the oxirane value of A is at least 3%.
  • composition of claim 4 wherein the fatty radical R is derived from tall oil fatty acid.
  • composition of claim 1 wherein the weight ratio of A:B is between 2:1 and 2:5.
  • composition of claim 1 wherein B is the esterification reaction product of a polyhydric alcohol and a p'olycarboxylic acid said reaction product comprising a polyester of the formula:
  • n is at least two and R is a polyhydric alcohol residue, and wherein R is a polycarboxylic acid residue.
  • composition of claim 9 wherein the esterification reaction mixture has an initial ratio of carboxyl groups to hydroxyl groups of betwen 1:1 and 3:1.
  • composition of claim 9 wherein a portion of said polycarboxylic acid is a halogenated polycarboxylic acid.
  • composition of claim 11 wherein the halogenated polycarboxylic acid is hexachloroendomethylene tetrahydrophthalic acid.
  • composition of claim 9, wherein the polyhydric alcohol comprises pentaerythritol.
  • composition of claim 9 wherein the polycarboxylic acid comprises phthalic anhydride.

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Abstract

AN EPOXIDIZED FATTY ACID ESTER OF A CYCLIC POLYOL SUCH AS THAT OF THE FORMULA:

R1-COO-CH2-C(-CH2-O-X)<(-CH(-OH)-C(-CH2-O-X)2-CH2-Y-CH2-)

WHEREIN:

X IS H OR

-CO-R1

Y IS -O-, -S-, OR -CH2-, R1 IS EPOXIDIZED FATTY RADICAL, SUCH AS THOSE DERIVED FROM TALL OIL FATTY ACIDS. A COMPOSITION OF METTER COMPRISING THE ABOVE APOXIDIZED FATTY ESTERS AND AN ACIDIC POLYESTER. THESE COMPOSITIONS OF MATTER ARE USEFUL AS COATING COMPOSITIONS AND PAINT SUBSTITUTES, WHEN APPLIED TO SUBSTRATES.

Description

United States Patent 3,558,535 COATING COMPOSITIONS COMPRISING AN EPOXIDIZED FATTY ESTER OF A CYCLIC POLYOL AND AN ACIDIC POLYESTER Brian M. Rushton, Minneapolis, and Oliver A. Ossanna, Bloomington, Minn., assignors to Ashland Oil, Inc., Ashland, Ky., a corporation of Kentucky No Drawing. Filed Sept. 10, 1968, Ser. No. 782,496 Int. Cl. C07d 7/00; C09d 3/64, 3/74 US. Cl. 260--22 Claims ABSTRACT OF THE DISCLOSURE An epoxidized fatty acid ester of a cyclic polyol such as that of the formula:
Y is O-, S, or -CH R is an epoxidized fatty radical, such as those derived from tall oil fatty acids.
A composition of matter comprising the above epoxidized fatty esters and an acidic polyester. These compositions of matter are useful as coating compositions and paint substitutes, when applied to substrates.
CROSS REFERENCE TO RELATED APPLICATION Ser. No. 782,497, entitled Epoxidized Fatty Acid Esters, is filed concurrently herewith and the disclosure of which is incorporated herein by reference.
DISCLOSURE This invention relates to compositions of matter comprising epoxidized fatty esters of cyclic polyols and acidic polyesters. These compositions of matter are useful as coating compositions for a wide variety of substrates.
Coating compositions which are a mixture of reactive components are known in the art. One form of such coating compositions is that wherein one component is an acidic polyester and the other component is an epoxide. Because of the reactivity of these two components with one another, it is not practical to premix them in a single container which can be stored, sold and shipped, since immediately upon mixing, the acidic polyester begins to react with the epoxide with a consequent gradual increase in the viscosity of the mixture. This increase in viscosity eventually results in gellation, and finally renders the entire mixture a solid, intractable mass. The time interval which occurs between the mixing of the two components and the point at which the viscosity becomes so great that the mixture can no longer be applied, i.e., the pot life, is a limiting characteristics of these coating compositions. Consequently these coating compositions are sold in two packages, one package containing the acidic polyester and the other package containing the epoxide. Examples of such systems are disclosed in US. Pat. 3,218,274 the disclosure of which is incorporated herein by reference.
While these coating compositions have found wide use in the art for many applications it is desirable to employ coating compositions which provide cured films having Patented Jan. 26, 1971 increased hardness. It is also desirable to employ coating systems which provide films which. cure in shorter times. Considerable effort has been expended in attempting to piovide coating systems which cure to films having greater hardness in shorter lengths of time, however, many of these attempts have resulted in formulations having other undesirable properties such as a decreased pot life of the mixture of components, or a reduction in the flexibility of the cured film.
It is therefore an object of the present invention to provide novel coating compositions free of the disadvantages of known coating compositions.
A further object of the present .invention is to provide novel coating compositions which when applied to a substrate cure in a short time to hard films.
A still further object of the present invention is to provide novel coating compositions which when applied to a substrate cure in a short time to flexible films.
Yet another object of the present invention is to provide novel coating compositions having an extended pot life which when applied to substrates cure in a short time to hard, flexible films.
Additional objects and advantages of the present invention will be apparent to those skilled in the art .by reference to the detailed description thereof which follows.
The above and other objects are accomplished by providing a composition comprising an epoxide which is coreactive with an acidic polyester.
The epoxides useful in the present invention can be described as the epoxidized reaction product of a cyclic polyol and a fatty acid. The cyclic polyols which can be employed preferably have at least three hydroxyl groups, and most preferably have four or five hydroxyl groups attached to the cyclic ring. The hydroxyl groups can be attached directly to the cyclic ring but are preferably present in the form of lower alkylol groups and most preferably present in the form of methylol groups. The cyclic ring of the cyclic polyol can contain from four to ten carbon atoms but preferably contains six. In one embodiment of the present invention the ring of the cyclic polyol can contain one or more hetero atoms such as sufur, oxygen or nitrogen. In another embodiment the ring of the cyclic polyol is carbocyclic and contains only carbon and hydrogen. The ring of the cyclic polyol is most preferably saturated. The cyclic ring can also contain other substituents which do not materially alter the hydrocarbon nature of the ring, examples of which include, among others, hydroxyl groups and halogen atoms such as chlorine or bromine. One preferred cyclic polyol useful in the present invention is 2,2,6,6-tetramethylolcyclohexanol; others are 3,3,5,5 tetramethylol 4-hydroxypyran and 3,3,5,5-tetramethylol-4-hydroxythiopyran.
The preferred epoxides useful in the present invention are those of Formula I:
I H CH 8 to 27 carbon atoms and most preferably contains from 12 to 22 carbon atoms.
The unsaturated fatty acids useful in the present invention are those having sufficient unsaturation as indicated by their iodine value such that when reacted with the cyclic polyols they can be epoxidized to yield the novel epoxides of the present invention having the desired oxirane value. The iodine value of these fatty acids is at least 50 and is preferably between 90 and 275. The unsaturation is present in the form of one or more double bonds in the fatty radicals of the fatty acids. Examples of suitable fatty acids having one double bond include among others, obtusilic acid, caproleic acid, linderic acid, lauroleic acid, tsuzuic acid, phsteric acid, myristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, vaccenic acid, gadoleic acid, cetoleic acid, erucic acid, selacholeic acid, and xirnenic acid. Examples of suitable fatty acids having a plurality of double bonds include among others linoleic acid, linolenic acid, a-eleostearic acid, ,8- eleostearic acid, parinaric acid, arachidonic acid, and clupanodonic acid. Mixtures of the above described acids with one another and with saturated fatty acids can also be employed as long as the fatty acid mixture has a sufficiently high iodine value to give epoxidized fatty acid esters of the desired oxirane content. The iodine value of these fatty acid mixtures is generally at least 50 and is preferably between 90 and 275. Examples of saturated fatty acids which can be used in a mixture with the above described unsaturated fatty acids include among others caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, benenic acid, and lignoceric acid. Thus it is apparent that in Formula 11 1 the various R s can be the same or different fatty radicals. While fatty acids having an odd number of carbon atoms such as those derivable from hydrocarbon sources are completely suitable for use in the present invention the preferred fatty acids are those derived from the naturally occurring fats and oils examples of which include among others linseed oil, tung oil, castor oil, dehydrated castor oil, saffiower oil, soya oil, cottonseed oil, olive oil, cocoanut oil, and tall oil which is preferred.
The epoxides useful in the present invention are generally prepared by a two step process which comprises first reacting the cyclic polyol with the fatty acid to form an ester, and then epoxidizing this ester.
The first step of the process can be carried out according to known esterification procedures and under conditions Well-known in the art. In general it is only necessary to combine the cyclic polyol and the fatty acid in stoichiometric amounts and heat the reaction mixture to a temperature between 100 and 350 C. until the reaction is complete as is evidenced by cessation of evolution of water of reaction. When the cyclic polyol is 2,2,6,6-tetramethylolcyclohexanol at least 4 and preferably 4.5 moles of fatty acid are employed per mole of cyclic polyol. It is believed that the hydroxyl group attached to the ring is more difiicult to esterify and in any case a suitable epoxide results when only the methylol groups are esterified to produce the tetra ester and the tetra ester is then epoxidized as described below. Known esterification reaction catalysts such as for example dibutyl tin oxide can be employed to hasten the reaction. Known stabilizers such as for example triphenylphosphite can be employed to inhibit the formation of color bodies at temperatures usually required for complete esterification.
Likewise the second step of the process wherein the above-described ester is epoxidized can be conducted under conditions and according to procedures Well-known in the art, such as by mixing the reaction product with a lower carboxylic acid such as acetic or propionic acid and a stoichiometric amount or a slight excess, such as up to 40 mole percent, of hydrogen peroxide in the presence of an epoxidation catalyst such as, for example, sulfuric acid or the sulfonated styrene-divinyl benzene copolymers, examples of which include, among others Dowex 50WX8, Duolite C-20, and Duolite C 3, a methylene sulfonic acid resin. The reaction can be conducted at subatmospheric, superatmospheric or, more conveniently, at atmospheric pressure and at temperatures between 75 and 200 F. The reaction is carried out until the epoxidized polyol has an oxirane value of at least 3% and preferably from 3 to 10%. Other epoxidation procedures used in the art for the epoxidation of triglycerides would also be expected to yield the epoxides of the present invention. Thus the fatty acid esters of cyclic polyols can be reacted with suitable peracids to yield the epoxides of the present invention. Suitable peracids include, among others, perbenzoic acid, performic acid and peracetic acid or a mixture of such peracids. The peracids can be made in situ or, alternatively, preformed.
As previously stated, the novel epoxides of the present invention form excellent coating compositions when mixed with acidic polyesters. The preferred acidic polyesters are those having an acid number of at least 50 and preferably at least 160. They can be described generally as the esterification reaction product of a polyhydric alcohol and a polycarboxylic acid, said reaction product comprising a polyester of Formula 111:
wherein n is an integer equal to at least two; R is a polyhydric alcohol residue; and R is a polycarboxylic acid residue.
Acidic polyesters useful in the present invention can III F, be prepared by esterifying a reaction mixture of a polycarboxylic acid and a polyhydric alcohol, wherein the reaction mixture preferably has an initial ratio of carboxy groups to hydroxyl groups of between 1:1 and 3:1 and preferably between 1.8:1 and 22:1. The reaction mixture is heated at esterification temperatures of between about and 350 C. until the reaction is complete as indicated by cessation of evolution of water of reaction. Detailed description for the preparation of suitable acidic polyesters is given in U.S. Pat. 3,218,274, and in particular in Examples I through X inclusive thereof.
Examples of polycarboxylic acids suitable for the synthesis of the acidic polyesters useful in the present invention include among others maleic acid, tri-mellitic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, fumaric acid, itaconic acid, their extant anhydrides and mixtures thereof. The most preferred acid is phthalic anhydride. In an especially preferred embodiment of the present invention a portion of the polycarboxylic acid is a halogenated polycarboxylic acid such as tetrachlorophthalic acid, or more preferably hexachloroendornethylene tetrahydrophthalic acid, available under the trade name Chlorendic Acid or Chlorendic Anhydride.
Examples of polyhydric alcohols which can be employed to form the acidic polyesters useful in the present invention include among others ethylene glycol, propylene glycol, glycerol, trimethylolethane, trimethylolpropane, sorbitol and preferably pentaerythritol, dipentaerythritol, tripentaerythritol, and mixtures thereof.
The acidic polyesters useful in the present invention can also be those which have been rendered organic solvent soluble by various means, such as those given above as suitable reactants for the cyclic polyols. The synthesis of these aciidc polyesters is described in detail in U.S. patent application Ser. No. 570,761, filed Aug. 8, 1966, now abandoned, and in particular in Examples 1 through 29 inclusive thereof.
The acidic polyesters useful in the present invention can also be those which are vinyl-modified, the synthesis of which is described in detail in U.S. patent application Ser. No. 661,189, filed Aug. 17, 1967, now U.S. Pat.
3,463,749, issued Aug. 26, 1969, and in particular in Examples 2 through 7 inclusive thereof.
The coating compositions of the present invention are prepared by simply mixing the above-described acidic polyesters with the above-described epoxides. Mixing can be effected by any convenient means such as by means of a handheld spoon or a mechanical homogenizer. The coating compositions of the present invention can have a Weight ratio of the epoxide to the acidic polyester of between 2:1 and 2:5 and preferably between 2:1 and 2:3, and most preferably 1:1. Solvents can be present in admixture with epoxide, the acidic polyester, and the coating composition, in order to give the resultant solution a viscosity which will facilitate application of the coating composition to the substrate. In general the solvent can comprise from less than 30 to over 70 weight percent of the solution although when employed it is preferably present within these ranges. Examples of suitable solvents include among others methanol, ethanol, xylene and mineral spirits. The coating compositions of the present invention can be modified by the addition of compatible materials such as pigments, extenders, plasticizers, ultraviolet light absorbents, and coloring agents. The coating compositions of the present invention can be cured by raising them to a temperature below the degradation temperature of the coating such as 50 to 150 C. When the acidic polyester used in the coating composition of the present invention contains chlorendic acid or chlorendic anhydride, the coating composition will cure at ambient temperatures. Thus the coating compositions of the present invention can be cured by air drying or oven baking.
The compositions of the present invention comprising acidic polyesters and epoxides can be employed as coatings for wood, ceramic, ferrous metals, nonferrous metals, and the like. When applied by such procedures as dipping, brushing, or spraying, these novel coating composi tions can be used to protect the coated substrate from the adverse eifects of weather, water, and air. Thus, such useful objects as wooden and metal boats, lawn chairs, houses, barns, and the like, can be advantageously coated with these novel compositions.
As used herein the term acid number refers to the number of milligrams of potassium hydroxide necessary to completely neutralize one gram of the nonvolatile content of the composition tested. The iodine number refers to the number of grams of iodine absorbed under standard conditions by 100 grams of the nonvolatile content of the composition. The oxirane value is the Weight percentage of oxiraneoxygen present in the nonvolatile content of the composition.
The invention may be better understood by reference to the following examples in which all parts and percentages are by weight unless otherwise indicated. These examples are illustrative of certain embodiments designed to teach those skilled in the art how to practice the invention and to represent the best mode contemplated for carrying out the invention, and are not intended to limit the scope of the invention in any manner.
EXAMPLE 1 This example illustrates the synthesis of an acidic polyester, termed Polyester A, which is useful in the present invention.
The following quantities of the following materials are combined as described.
Items A through D are charged to a three-necked flask fitted with a mechanical agitator, reflux condenser, nitrogen inlet tube, thermometer, and water trap. The reaction mixture is heated for a period of one hour to 260- 290 F. and held at this temperature until an acid value of 170-185 is obtained. The mixture is heated an additional minutes. The flask and its contents are cooled and Items E, F and G added. Additional F is added to adjust the nonvolatile content to 60%.
EXAMPLE 2 This example illustrates the synthesis of an acidic polyester, termed Polyester B, which is useful in the present invention.
The following quantities of the following materials are combined as described.
uantit Material (grams l Item:
A Technical pentactythritol-.- 82.9 B Phthalic anhydride 147.0 0.... Ohlorcndic acid 192.0 D... Xylene 277.7 E Chlorendic acid 192. 0 F. Methyl isobutyl ketone. 49. 7 G. Cellosolve acetate 69. 6 H- n-Butanol 9. 9
EXAMPLE 3 This example illustrates the synthesis of an epoxidized fatty acid ester of a cyclic polyol useful in the present invention termed Epoxide C.
The following quantities of the following materials are combined as described.
Quantity Material (grams) Item A 2,2,6,6tetramethylolcyclohexanol 1, 320 33. Tall oil fatty acids G, 720 0.- Dibutyl tin oxide..... 8. 04 D Triphenyl phosphite 8. 04 E.. Glacial acetic acid 147. 8 F. Dowex 50WX8. G. Heptane 1, 000 Hydrogen peroxide (50% H202). 414
Items A through D are charged to a round bottom flask fitted with a reagent addition tube, a thermometer, a stirrer and a reflux condenser having a Dean-Stark water separation trap. The flask and its contents are heated to 215 C. and enough toluene is added to maintain a smooth reflux at that temperature. Reflux is continued for 14 hours until no more water is evolved and the acid value has dropped to 2 or less. The flask and its contents are cooled to 80 C., and the reflux condenser and Dean- Stark trap are replaced by a vacuum take-01f adapter. The flask is evacuated to approximately 10 mm. Hg
and the temperature of the contents of the flask held between 80 C. and 100 C. for 30 minutes. The flask and its contents are cooled to room temperature and the vacuum is released. The contents of the flask constitute a fatty acid ester.
The fatty acid ester (1000 g.) produced as described above and Items E, F and G are charged to a round bottom flask fitted with a stirrer, reagent addition tube and Friedrich condenser. The flask is immersed in a water bath at 118 F. Item H is then added slowly and uniformly over a period of 45 minutes. The temperature allowed to rise to 140 F. The water bath is adjusted to maintain the temperature of the flask and its contents at 140 F. for the remainder of the reaction. Stirring is continued for 15 hours, after which time the contents of the flask are filtered to remove Item P which is present in the form of beads. Item F may be reused as a catalyst in future epoxidations. The liquid filtrate separates into an aqueous and a non-aqueous phase. The non-aqueous phase contains the epoxide. The phases are separated and the nonaqueous phase is washed three times with volumes equal to that of the nonaqueous phase of (1) hot water, (2) hot 5% aqueous sodium carbonate solution, (3) hot water. Volatiles are then removed from the washed nonaqueous phase by steam stripping at reduced pressure. The resultant product termed Epoxide C has the following characteristics:
Acid number-0.2 Iodine value-4.48 Oxirane content-5 .7 2% Color (G 1 Viscosity-19.9 stokes Item B, the tall oil fatty acids, employed in this example have an iodine value of 130 a saponification number of 200 and analyze as follows:
Material- Weight percent Stearic acid 2.6 Oleic acid 51.2 Linoleic acid (nonconjugated) 38.5 Impurities 7.7
- Total 100.0
EXAMPLE 4 Acid number 0.7 Iodine value 18.3 Percent oxirane 4.8
A portion of this partially epoxidized fatty acid ester was then epoxidized further according to the following procedure:
Quantity Material (grams) Item:
A Partially epoxidized fatty acid ester 625 B Heptane 125 (l Preformed peracctic acid (40%) 106. 1) Heptane 300 Items A and B are charged to a round bottom flask fitted with a stirrer, a reagent tube, and a Friedrich condenser. The flask is immersed in a water bath at 96 F. Item C which had been treated with sodium acetate to remove traces of sulfuric acid which may be present, is added slowly and uniformly over a period of one hour. The temperature rises to 100 F. and the Water bath is adjusted to maintain this temperature for the remainder of the reaction. Stirring is continued for hours. The contents of the flask separate into an aqueous and a nonaqueous phase. The nonaqueous phase contains the epoxide. The nonaqueous phase is diluted with Item D and separated from the aqueous phase. The nonaqueous phase is then Washed twice with volumes equal to that of the nonaqueous phase with (1) hot 5% aqueous sodium carbonate solution, (2) hot water. Volatiles are removed from the oil by stem stripping at reduced pressure. The resultant product termed Epoxide D has the following characteristics:
EXAMPLE 5 EXAMPLE 6 This example illustrates the synthesis of an epoxidized fatty acid ester of a cyclic polyol termed Epoxide F.
The procedure of Example 3 is followed employing the same materials, quantities and conditions with the exceptions that Item F, the resin catalyst is that recovered from a previous epoxidation and the total epoxidation reaction time is 19 hours.
The product termed Epoxide F has the following characteristics:
Acid number 3.1
Iodine value-4.08 Oxirane content-5.48% Color (G)l Viscosity-18 stokes EXAMPLE 7 This example illustrates some of the excellent physical properties possessed by mixtures of acidic polyesters and epoxides of the present invention and of their air dried films.
Referring to Table I the four polyester components of column 1 are each mixed with the epoxides of column 2 in the ratios shown in column 3. The pot life of these mixtures is determined and recorded in column 4. A 3 mil thick coating of each mixture is brushed on a glass substrate and permitted to cure in atmospheric air at a constant temperature of 20 C. Various tests are conducted on the curing and cured films and the results thereof recorded in columns 5 through 10. After the film has cured for 24 hours it is found to have a thickness of 1.5 mils.
TABLE I Solids Tack Sward Hardness 5 Polyester Epoxide ratio by Pot Nonfreeness 4 Xylol Alkali Mar component (designawei ht 1 life 1 transfer 3 (500g. 7a 24 hr. 7b one Week resistance 6 resistance 7 resis- (designation) tion) (unit ess) (hi-s.) (min) (hrs.) (N o.) (No.) (No.) (N o.) tance 5 50/ 50 25 5 2% 50 54 5 8 G- 50/ 50 25 5 1% 5(3 60 7 8 G- 45/ 55 10 5 48 48 1 7 G- /55 28 10 4% 54 60 2 7 G- 1 The first number indicated the weight in dicates the weight in grams of the designated epoxide of column 2.
grams of the designated polyester component of column 1 and the second number in- 2 This is the time measured from the moment of mixing the polyester component and the epoxy component until the first sign of gellation occurs. In actual practice these mixtures become diflicult to apply prior to this latter time because of their increased viscosity.
3 The non-transfer time is measured by applying light finger pressure to the coated substrate at regular intervals until the coating on the substrate does no transfer to the finger. The elapsed time from the time of application of the coating until there is no transfer recorded.
4 This is a quantitative test for tack-free properties. The numbers represent the time in hours at which the film attained equvalent degree of tack-freeness as determined by a 500 g. Zapon test. 5 This is a standard test for hardness measured in this case in column 7a, 24 hrs, after application and in column 7b one Week after application. All samples were stored in air at 20 C. for the indicated periods. The greater numbers indicate harder fihns.
This test is performed as follows. A l-inch Week. After 10 minutes the 10=No discernible eifect. 8=Surface of film not as shiny as untreated surface. 5=Some disintegration of surface of film. 0= Complete disintegration of film, underlying substrate visible.
puddle of xylol at 20 C. is placed on the surface of the film which has cured for one puddle is removed with a clean cloth and the underlying film surface visually graded as follows:
7 This test is performed exactly as the xylol resistance test recorded in column 8 with the single exception that the xylol is replaced with an equal weight of a 10 Weight percent aqueous solution of sodium hydroxide.
' This test is performed on the coated substrate after one week of storage in air at 20 C. The surface of the film is scraped lightly with the thumbnail and the scraped surface visually graded as follows:
VG=Very GoodNo discernable efiect. VG- =Very Good MinusFilm shows a very slight indentation.
G=Good-Film shows an indentation, but the substrate does not show through. G=Good Minus-Film shows a deeper indentation, but the substrate does not show through.
F=Fair-Substrate shows through in spots. P =Poor-Substrate shows through along scratch.
EXAMPLE 8 This example illustrates some of the excellent physical properties possessed by mixtures of polyester components and epoxy components of the present invention when applied to a substrate and subsequently baked.
Referring to Table II the four polyester components of column 1 are each mixed with the epoxide of column 2 in the ratios shown in column 3. Each of these mixtures is sprayed on a tin substrate until the resultant coating is 6 mils thick. The coated substrate is then placed in an oven at 121 C. for 30 minutes. The coated substrate is 40 then removed and cooled whereupon the thickness of the coating if found to be 3 mils. Certain tests are preformed on the coating of this substrate and their results recorded in columns 4 through 8 of Table II.
30 to give a product with the properties:
Acid number1.9 Hydroxyl value-17.7 Iodine value115.5 Color (G)4 Viscosity-2.5 stokes which is then epoxidized as in Example employing the following materials:
Quantity Material (grams) Item:
E. Glacial acetic acid 327 Dowex WX8 200 Heptane 850 Hydrogen peroxide (50% H202 805 1 Measured in accordance with note 1 of Table I. 2 Measured in accordance with note 5 of Table I.
3 Measured on a tin plate, 3 x 10, in accordance with PG 1302 from Gardner Laboratories, Inc. 4 Measured in accordance with note 6 of Table I. 5 Measured in accordance with note 7 of Table I. Measured in accordance with note 8 of Table I.
EXAMPLE 9 This example illustrates the synthesis of an epoxidized fatty acid ester of a cyclic polyol containing one hetero oxygen atom.
The procedure of Example 3 is followed employing the same conditions, times and reactants, except that the following quantities of the following materials are employed:
Quantity Material (grams) Item:
.. 3,3,5,5-tetramethylol-4-hydroxypyran (71. 5% aqueous solution) 1, 860 B Tall oil fatty acids (l, 720 Dibutyl tin oxide 8. 6 D Triphenyl phosphite 8. G
to give a product with the following properties: Acid number-3.35
Iodine value-49 Oxirane (percent)5.7
Color (G)l Viscosity-31 stokes EXAMPLE 10 This example illustrates the advantageous properties of the coating compositions of the present invention produced from ditferent expoxides.
The procedures of Examples 7 and 8 are repeated employing the same quantities of the same components and the same times and conditions with the single exception that Epoxide D is first replaced by Epoxide C. Films having equally advantageous properties result.
EXAMPLE 11 This example illustrates the advantageous properties of the coating compositions of the present invention produced from different epoxides.
The procedures of Examples 7 and 8 are repeated employing the same quantities of the same components and the same times and conditions with the single exception that Epoxide D is replaced by Epoxide E. Films having equally advantageous properties result.
Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described above and as defined in the appended claims.
What is claimed is:
1. A composition of matter comprising:
(a) An epoxidized fatty ester of a cyclic polyol wherein the cyclic ring is saturated and consists of 4-10 carbon atoms and -1 hetero-atoms selected from the group consisting of sulfur, oxygen, and nitrogen; said cyclic polyol containing at least 3 hydroxyl groups attached directly to the ring or as lower alkylol groups;
(b) a polyester having an acid number of at least 50.
2. The composition of claim 1 wherein the cyclic polyol has a saturated carbocyclic ring.
3. The composition of claim 1 wherein A has the wherein R is an epoxidized fatty radical.
4. The composition of claim 1 wherein A has the Y is O-, S-, or 2 R is an epoxidized fatty radical.
5. The composition of claim 4 wherein the epoxidized fatty radical A contains from 8 to 27 carbon atoms.
6. The composition of claim 4 wherein the oxirane value of A is at least 3%.
7. The composition of claim 4 wherein the fatty radical R is derived from tall oil fatty acid.
8. The composition of claim 1 wherein the weight ratio of A:B is between 2:1 and 2:5.
9. The composition of claim 1 wherein B is the esterification reaction product of a polyhydric alcohol and a p'olycarboxylic acid said reaction product comprising a polyester of the formula:
wherein n is at least two and R is a polyhydric alcohol residue, and wherein R is a polycarboxylic acid residue.
10. The composition of claim 9, wherein the esterification reaction mixture has an initial ratio of carboxyl groups to hydroxyl groups of betwen 1:1 and 3:1.
11. The composition of claim 9, wherein a portion of said polycarboxylic acid is a halogenated polycarboxylic acid.
12. The composition of claim 11, wherein the halogenated polycarboxylic acid is hexachloroendomethylene tetrahydrophthalic acid.
13. The composition of claim 9, wherein the polyhydric alcohol comprises pentaerythritol.
14. The composition of claim 9 wherein the polycarboxylic acid comprises phthalic anhydride.
15. The composition of claim 9, wherein the esterification reaction mixture further comprises a fatty monocarboxylic acid.
References Cited UNITED STATES PATENTS 2,476,922 7/1949 ShOkal et al. 260348 2,870,166 1/1959 Kubler 260345.8 2,967,840 1/1961 Phillips et a1 26022 3,168,534 2/1965 Payne 260345.8 3,218,274 11/1965 BOller et a1. 260-22 3,463,749 8/1969 Taft 26022 FOREIGN PATENTS 1,085,872 7/1960 Germany 260348 DONALD E. CZAIA, Primary Examiner R. W. GRIFFIN, Assistant Examiner US. Cl. X.R.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 558, 535 Dated January 26, 1971 Inventor(s) Brian M. Rushton and Oliver A. Ossanna It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 11, line 19, "(a)" should be --A-- line 26, "(b)" should be --B- Column 12., line 15,
Signed and sealed this 18th day of July 1972.
(SEAL) Atteat:
EDWARD M.FLETCHER,J'R. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882168A (en) * 1970-09-07 1975-05-06 Hoechst Ag Photopolymerizable compounds
EP0135477A1 (en) * 1983-08-23 1985-03-27 Ciba-Geigy Ag Polyglycidyl ethers
US5079129A (en) * 1986-08-06 1992-01-07 Ciba-Geigy Corporation Negative photoresist based on polyphenols and epoxy compounds or vinyl ethers
US5300380A (en) * 1986-08-06 1994-04-05 Ciba-Geigy Corporation Process for the production of relief structures using a negative photoresist based on polyphenols and epoxy compounds or vinyl ethers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3882168A (en) * 1970-09-07 1975-05-06 Hoechst Ag Photopolymerizable compounds
EP0135477A1 (en) * 1983-08-23 1985-03-27 Ciba-Geigy Ag Polyglycidyl ethers
US5079129A (en) * 1986-08-06 1992-01-07 Ciba-Geigy Corporation Negative photoresist based on polyphenols and epoxy compounds or vinyl ethers
US5300380A (en) * 1986-08-06 1994-04-05 Ciba-Geigy Corporation Process for the production of relief structures using a negative photoresist based on polyphenols and epoxy compounds or vinyl ethers

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