CA1112246A - Bis-azidophthalic acid derivatives - Google Patents
Bis-azidophthalic acid derivativesInfo
- Publication number
- CA1112246A CA1112246A CA313,230A CA313230A CA1112246A CA 1112246 A CA1112246 A CA 1112246A CA 313230 A CA313230 A CA 313230A CA 1112246 A CA1112246 A CA 1112246A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/008—Azides
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Abstract of the Disclosure The compounds according to the invention have the formula Ia or Ib (Ia) or (Ib) in which R is a divalent organic radical. The novel bis-azidophthalic acid derivatives are suitable for the pro-duction of photo-curable mixtures. The novel compounds, and their mixtures, have better heat stability and oxidation resistance than known systems, whilst retaining equally good photosensitivity.
Two different methods of preparation of the com-pounds are described.
Two different methods of preparation of the com-pounds are described.
Description
~ 2~ ~
The present inven-tion relates to novel bis-azido-phthalic acid derivatives and to processes for their pre-paration The bis-azidophthalic acid derivatives according to -the invention can be used to produce photo-curable (photo-crosslinkable) mixtures The literature discloses that azidophenyl deriva-tives, such as 4,4'-diazidostil~ene, disodium 4,4'-diaæidostilbene-2j2' disulphonic acid, 4,4'-diazidobenzo-phenone, 4,4'-diazidochalcone, 2,6-di-(4'~azidobenzal)~
cyclohexanone, 2,6 di-(4'-azidobenzal)-4-methylcyclohexan-one, 4,4'-diazidobenzalacetone and bis-(4'-azidocinnamyl-idene)-cyclopentanone can be used as sensitisers for poly-mers for phototechnical purposes, for example in so-called photoresists, or as photosensitive components in colloid layers, such as gelatin or casein, for the production of so-called tanned images in photography, or in reprographic processes (c.f., for example, U.S. Patent Specifications
The present inven-tion relates to novel bis-azido-phthalic acid derivatives and to processes for their pre-paration The bis-azidophthalic acid derivatives according to -the invention can be used to produce photo-curable (photo-crosslinkable) mixtures The literature discloses that azidophenyl deriva-tives, such as 4,4'-diazidostil~ene, disodium 4,4'-diaæidostilbene-2j2' disulphonic acid, 4,4'-diazidobenzo-phenone, 4,4'-diazidochalcone, 2,6-di-(4'~azidobenzal)~
cyclohexanone, 2,6 di-(4'-azidobenzal)-4-methylcyclohexan-one, 4,4'-diazidobenzalacetone and bis-(4'-azidocinnamyl-idene)-cyclopentanone can be used as sensitisers for poly-mers for phototechnical purposes, for example in so-called photoresists, or as photosensitive components in colloid layers, such as gelatin or casein, for the production of so-called tanned images in photography, or in reprographic processes (c.f., for example, U.S. Patent Specifications
2,852,379, 2,940,853 and 3,749,713, German Patent Specific-ation 752,852, Russian Patent Specification 503,855 and Bri-tish Patent Specification 892,811).
These previously known azido-phenyl derivatives have disadvantages, since the heat s-tability and oxida-tion resistance of the compounds, or of mixtures containing these compounds, is not entirely satisfactory . It was there-fore the objec-t of the invention -to provide novel substances having ilnproved heat stabil~ty and oxidation resistance, whils-t possessing photosensi-. .
, z~
~ 2 --tivity as good as that of the abovementioned known sub-stances.
The novel bis-azidophthalic acid derivatives have --the formula Ia or Ib CONH - R - NHOC ~ (Ia~
COOH HOOC ~
N3 ~~3 or ~ N - R - N ~ tIb) N~ 3 in which R is alkylene having 2-12 C atoms, which is unsubstituted or substituted by one or two phenyl groups, cycloalkyl groups having 5-8 C atoms or aralkyl groups having 7 or 8 C atoms, or is phenylene, naphthylene, biphenylene, cyclohexylene, dicyclohexylmethane or ~ z ~ which are unsubstituted or substituted by one alkyl group having 1-4 C-atoms or one -OH, -COO-M
or -SO3 M group per ring, Z is -O-, -S-, -SO2-, -CH2-, -CO-, -~CH- or -~- , M is a hydxogen ion, an alkali H3 H3 + /Xl metal cation, the pyridinium cation or NH\X2 , Xl and X2 independently of one another are hydrogen or alkyl having 1-12 C atoms and X3 is hydrogen, al~yl having 1-L2 C atoms or benzyl.
.~a. ~,...
' ' ~
:
.
2~
These previously known azido-phenyl derivatives have disadvantages, since the heat s-tability and oxida-tion resistance of the compounds, or of mixtures containing these compounds, is not entirely satisfactory . It was there-fore the objec-t of the invention -to provide novel substances having ilnproved heat stabil~ty and oxidation resistance, whils-t possessing photosensi-. .
, z~
~ 2 --tivity as good as that of the abovementioned known sub-stances.
The novel bis-azidophthalic acid derivatives have --the formula Ia or Ib CONH - R - NHOC ~ (Ia~
COOH HOOC ~
N3 ~~3 or ~ N - R - N ~ tIb) N~ 3 in which R is alkylene having 2-12 C atoms, which is unsubstituted or substituted by one or two phenyl groups, cycloalkyl groups having 5-8 C atoms or aralkyl groups having 7 or 8 C atoms, or is phenylene, naphthylene, biphenylene, cyclohexylene, dicyclohexylmethane or ~ z ~ which are unsubstituted or substituted by one alkyl group having 1-4 C-atoms or one -OH, -COO-M
or -SO3 M group per ring, Z is -O-, -S-, -SO2-, -CH2-, -CO-, -~CH- or -~- , M is a hydxogen ion, an alkali H3 H3 + /Xl metal cation, the pyridinium cation or NH\X2 , Xl and X2 independently of one another are hydrogen or alkyl having 1-12 C atoms and X3 is hydrogen, al~yl having 1-L2 C atoms or benzyl.
.~a. ~,...
' ' ~
:
.
2~
- 3 Alkylene group~ R can be straight -chain or branched~
Examples of cycloalkyl and aralkyl substituents ~or alkylene groups R are cyclo~entyl,cyclohexyl, cyclooctyl or benzyl groups.
Examples of such alkylene groups R are ~he 1,2-ethylene, 1,3- or 1,2-propylene, 1,4- or 1,3-butylene, pentamethylene, hexamethylene, Z-methyl-4-dimethylhexane, ~-dlmethyl-4~methylhe~an~, l,lO~dicyclohaxyldecan~, 1,10 dicyclooctyldecane, l,10-di-isopropyldecane, l,l,lO,10-tetramethyldecane, l,10-diethyl-1/lO-dimethyldecane, octa-methylene, decamethylene and dodecamethylene group~.
Unsubstituted straight-chain or branched alkylene groups having 2-12, and especlally 2-10, C atom~ are pre-erred.
Alkyl groups Xl, X2 and X3 may be straight-chaln or branched. Preferably, they are straight-chain alkyl groups havlng 1-4 C atoms. Suitable alkyl substituents are, ln particular, methyl and ethyl. I~ M is a HN\Xl group, Xl and X2 are preferably alkyl groups havlng l-4 C atom~
and X3 is preferably an alkyl group having 1-4 C atoms, or the benzyl group.
Preferred substi~uents -C00 M or -S03 M are those in which R is a hydrogen ion, an alkali metal cation, a benzyldialkylammonium ca~ion or a trialkylammonium cation, with l 4 C atoms in each alkyl moiety. Part-icularly preferred meanings of ~ are a hydrogen ion, a sodium .., ~i cation or a potassium ca-tion, Phenylene, naphthylene, biphenylene, cyclohexylene and dicyclohexylrnethane groups and ~ z ~
groups, are preferably unsubsti-tuted. Preferred bridge members Z are -0~, -S02- and -CH2-, The N3 groups are preferably in each case 30ined to the benzene ring in the ortho-position to a carbonyl, carboxyl or carboxamide group.
Preferred compounds are those of the formula Ia, and especially those of the formula Ib, in which R is un~
substituted straight-chain or branched alkylene having 2-12, and especially 2-10, C atoms, unsubstituted phenyl-ene, biphenylene or an unsubstituted diphenyl ether, diphenylmethane or diphenylsulphone radical, or the 3,3'-dimethyl-dicyclohexylmethane radical.
~ Particularly preferred compounds according -to the invention are the compound cf the formula VI
C0 0 ~ ~ ~ ~ (VI) the compound of the formula VII
CO . ~CO
\ ~ ` ~ \CO~
"--- 5 ~
and the compound of the formula VIII
CO CH . CH CO
\ ~ C~2 N ~ ~VIII) I CO CO I
The compounds of the formula Ia and Ib can be pre-pared by reacting a compound of the formula II
~ CO (II) in a molar ratio of at least 1:2 with a diamine of the formula III
H2N-R-NH2 (I~I) to give a compound o~ the formula Ia 0 - NH - R - NH - OC ~ ~Ia) . ~ COOH HOOC ~
R being as de~ined under ~ormula Ia or Ib, and, if desired, subsequently cyclising the compound of the ~ormula Ia.
The reaction of the anhydride of the formula II
with the diamine of the ~ormula III is advantageously carried out in an organic medium, at temperatures between about 0C and 120C depending on the nature of the re-actants.
Advantageously, the anhydride o~ the ormula II
is employed in stoichiometric amount or in slight excess over the diamine of the formula III, for example in up to about 20% molar excess.
Suitable organic solvents are, in par~icular, .
aprotic solvents Examples of suitable aprotic orgar~c sol-vents are aliphatic or aromatic hydrocarbons which may or may not be chlorinated, such as benzene, toluene, methyl-ene chloride, chloroform, carbon tetrachloride, 1,1,~-trichloroethane, 1,2-dichloroethylene and chlorobenzene;
aliphatic and cycloalipha-tic ke-tones, such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone;
cyclic ethers, such as tetrahydrofuran, tetrahydropyran and dioxane; cyclic amides, such as N-methyl-2-pyrroli-done, N-acetyl~2-pyrrolidone and N-methyl-~-caprolac-tam;
N,N-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, such as N,N-dimethyl-formamide, N,N~dimethylacetamide, N,N-diethylamide and N,N-dimethylmethoxyacetamide; alkyl esters of aliphatic mono-carboxylic acids, having a total of 2-6 carbon atoms, such as methyl, ethyl and n-butyl formate or acetate; hexa-methylphosphoric acid triamide (hexametapol); N,N,N',N'-tetrame-thylurea; tetrahydrothiophene dioxide (sulpholan);
and dialkylsulphoxides, such as dimethylsulphoxide or diethylsulphoxide. Mixtures of such solvents can also be employed.
The cyclisation of the compounds of the formula Ia can be carried out in a manner known per se, by chemical means,i.e. with addition of dehydrating agents known per se. Depending on the nature of the reactants, the re-action conditions and the solvent employed, the cyclisation can, especially at elevated temperatures, also be carried out without adding a dehydrating agent, the water formed advantageously being removed azeotropically.
The cyclisation is in general carried out at temperatures be-tween about 40 and 120C, preferably at 70-90C, in the presence of a dehydrating agent and in -the presence or absence o~ an aprotic organic solven-t.
Suitable dehydrating agents are, in particular, anhydrides of aliphatic monocarboxylic acids, having ~-5 C a-toms, which are unsubstitu-ted or substituted by halogen atoms or alkyl group,s, such as acetic anhydride, propionic anhydride, .
butyric anhydride, valeric anhydrlde, trichloroacetic anhydride and trlmethylacetic anhydride, The pre-~erred dehydrating agent is acetic anhydride, According to a preferredprocess, the compoun~s of the formula Ib can also be prepared directly, in a par-ticularly simple manner, by reacting a compound of the formula IV
~ R - N \ ~ (IV) Ql Ql in which R is as defined under formula Ia or Ib and Ql is a halogen atom, such as chlorine, fluorine or bromine, or is a nitro group, in an inert organic solvent, at a temperature between about 0 and 120C, preferably between about 70 and 100C, with an azide of the formula V
Mnl+ (N3 )n~ ~V) in which n is 1 or 2 and Ml is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation.
The literature [Tetrahedron Letters, 12, 1305 -1309 (1966)] discloses that 3-nitrophthalic anhydride can be converted to 3-azidophthalic anhydride by means of sodium azide in the presence of an inert organic solvent at a temperature of 110C, However, 4-nitrophthalic anhydride and 3-chlorophthalic anhydride cannot be con-verted to the corresponding azide by this method, It is therefore surprising that, according to the invention, both the bis-(3-nitrophthalimides) and the bis-(4-nitro-phthalimides) of the formula IV, and the corresponding 3-and 4-halogen compounds can be converted to the corres-ponding azides with good to very good yields and in some cases even at lower temperatures, A prior expensive , , ,.. . . , . , , , . . ~,.. ..
--separa-tion of the starting rna-terials into the 3- and 4-isomers is therefore not necessary in the process accord-ing to the invention.
Preferably, Q1 is the nitro group A quaternary ammonium cation Ml is, for exarnple, a tetraalkylammonium cation or benzyltrialkyla~monium cation with each alkyl moiety having 1-12 and especially-1-4 C atoms~in partiaular the te-tramethylamtnonium cation and the trimethylbenzylammonium cation.
~ xamples of suitable alkali metal azides and alkaline earth metal azides are lithium, sodium, potass-ium, calcium, magnesium and barium azide. . The use of alkali metal azides, in particular of sodium azide, is preferred.
The azide of the formula V is advantageously em-ployed in excess, for example in a molar excess o~ about 5-50% and preferably of about 10-30%.
Sui-table inert organic solvents are, in particular, polar solvents, for exarnple lower aliphatic alcohols, for instance those having upto 6 C atoms, such as methanl, ethanol, propanol, isopropanol, butanols and pentanols;
dibenzyl ethers and dialkyl ethers with each alkyl moi-ety having 1-4 C atoms, such as diethyl ether, di-n-propyl ether and di-isopropyl ether; cyclic ethers, such as tetrahydrofuran, tetrahydropyran and dioxane; diethylene glycol dialkyl ethers and triethylene glycol dialkyl ethers with each alkyl moiety having 1-4 C atoms, such as diethylene glycol diethyl ether and di-n-butyl ether, and triethylene glycol dimethyl ether; aliphatic and aromatic nitriles, such as alkylnitriles having 2-5 C atoms in the alkyl moiety, for example acetonitrile, propionitrile, butyronitrile and benzonitrile; and also aprotic polar organic solvents of the abovementioned type, such as cyclic amides, N,N-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, dialkylsulphoxides, hexame-thylphosphoric acid triamide (hexametapol) and -tetra-hydrothiophene dioxide (sulpholan) , . :, . , .
~, _ g~
Mixtures of such solvents can also be used Preferred solvents are dialkylsulphoxides, es-pecially dimethylsulphoxide, and N,N dialkylarnides of aliphatic monocarboxylic acids having 1-3 C atoms in.the acid moiety, especially N,N-dimethylformarnide and N,N-dimethylacetamide.
The starting materials of the formula II to V are known or can be prepared by methods known per se. Com-pounds of the f`ormula IV can, for example, be obtained in accordance with known methods by reacting 3- or 4-nitro-phthalic anhydride or the corresponding halogen compounds with a diamine of the formula III and then cyclisin~ the resulting amidocarboxylic acid.
The azidophthalic a-nhydrides of the formula II
are described in U.S Patent Specification 3,002,00~, The compounds of the formula Ia and Ib can be isolated, with or without purification, by conventional means, for example by stripping off the solvent or con-centrating the reaction solution or suspension in vacuo and then washing the reaction product with water or a suitable inert organic solvent, such as methanol, ethanol 7 dioxane, diethyl ether, methylene chloride or chloroform.
In general, the amidocarboxylic acids of the formula Ia are cyclised directly, i.e. without intermediate isolation, to the bis-imides of the formula Ib.
The compounds according to the invention, of the formula Ib, may be used for the preparation of pho-tocur-able (photo-crosslinkable) mixtures for photomechanical applications. Such mixtures contain at least one polymeric compound and at least one compound of the formula Ib, the weight ratio of the former to the latter advantageously being about 9:1 to 1:4 and preferably about 9:1 to l:l Polymeric compounds ~hich can be crosslinked or cured wi-th the bis-azidophthalimidyl com-pounds of the formula Ib under the action of light, es-pecially of W light, can in principle be any kno~m syn-thetic or natural polyMers, for exarnple polyesters, ~oly-... . ~
~, _ 10 --ester-amides, polyamides, polyamidoacids, poly~mide-amidoacids, polyimides, polyamidoimides, polyethers, polyamines, polyimines, polyurethanes, polyureas, poly-urethane-ureas, polycarbonates, polycondensates based on phenol-formaldehyde, polysaccharides, gelatin and polymers which are o~tained by homopolymerisation or copolymer-isation of monomers containing reactive C=C double bonds Preferred polymers are polyethers, especially those which contain recurring structural units of the formula VI
t o - ~ CH ~ O - CH2 ~ CH - CH ~ (VI);
phenol-formaldehyde condensation products (novolacs) which contain recurring structural uni-ts of the formula VII
-CH (VII);
~ CH2 - C~ ~ H2 homopolymers or copolymers of ethylenically unsaturated monomers, which contain identical or different recurring structural units of the formula VIII
2 ~ (VIII);
L Z3 ~4 ~
and cyclised isoprene polymers.
In the formula VIII, Zl and Z~ are each hydrogcn, Z2 is hydrogen, chlorine or methyl and Z~ is hydrogen, , .. .
.
methyl, chlorine, -CN, -COOH, -CO~H2, phenyl, methylphenyl, methoxyphenyl, cyclohexy], pyridyl, imidazolyl, pyrrolid-onyl, ~COO-alkyl having 1-12 C atoms in -the alkyl moiety, -COO-phenyl, -COOCH2CH - ~ E~2, ~COO-alkyl having 1;3 C
atoms in the alkyl moiety, -COOR7-(OC-C=CH2)~ (in which R7 is a straight-chain or branched saturated aliphatic radical having 1-10 C atoms, R5 is hydrogen or methyl and z is an integer from 1 to ~), -OCO-alkyl having 1-4 C
atoms in the alkyl moiety, -OCO-phenyl, -CO-alkyl having 1-3 C atoms in the alkyl moiety, alkoxy having 1-6 C atoms phenoxy, -CH~CH2 or ~ -CH-CH2 ~ or Zl and Z2 are each hydrogen and Z3 and Z4 together are the O C~O ~ ~O
group or are each -COOH or -COO-alkyl having 1-6 C atoms in the alkyl moiety.
` Particularly preferred polymers are polyvinyl chloride, polystyrene, poly(alkyl acrylates) and poly-(alkyl methacrylates) having 1-8 C atoms in the alkyl moie-ty, cyclised isoprene polyme~s, copolymers of maleic anhydride and vinyl ethers or a-olefins, such as methyl vinyl ether or ethylene, as well as polyethers having re-curring structural units of the formula YI
Such mixtures may be used, for example, for the manufacture of printing plates for the offset printing process, for -the manufacture of photo-offset lacquers, for unconventional photography, ~or example for the pro-duction of so-called vesicular images, or for colouring polymer images, which after exposure and development are not easily visible, by means of suitable dyes, such as oil-soluble dyes or, if the polymer contains acid groups, such as carboxylic acid or sulphonic:acid groups, with cationic dyes The Mixturss mentioned are used in particular as so called pho-toresists for the manufacture of printed circuits by methods known per se.
In these, the s.ide of the conductive plate provided with , the photosensitive layer .is exposed through a negative transparency carrying the conductor image and is then developed, after which the unexposed areas of the layer are removed with developer .fluid Exposure can be effected by means of sunlight, carbon arcs or xenon lamps, but is preferably carried out with mercury high pressure lamps Example 1 . -CH2-~H-~H2- f CH2 c~2 / ~ C~3 /
¦ 2 1_CH2_1H_CH2_CH2_ N3 l C~3 CH3 N3 20 3 g (0 04 mol) of an isomer mixture of 1,6-bis-(3-nitrophthalimidyl)-2-methyl-4-dimethylhexane and 1,6-bis-(3-nitrophthalimidyl)-2-dimethyl-4-methylhexane are stirred with 7.78 g (0.104 mol) of NaN3 in 100 ml of N,N-dimethylformamide for 20 hours at 80C. The reaction mixture is evaporated in vacuo at 80C, the oily residue is suspended in 200 ml of water and the suspension is stirred vigorously for 60 hours. The suspension, in which the suspended phase gradually solidifies, is fil-tered with suction and the filter residue is washed with water and dried for 6 days at 25C over phosphorus pent-oxide. 17.6 g (88% of theory) of an isomer mixture of 1,6-bis-(~-azidophthalimidyl)-2-methyl-4-dimethylhexane and 1,6-bis-(3-azidophthalimidyl)-2-dimethyl-4-methyl-hexane are obtained. The product is in the form of a finely divided glassy mass, which melts on heating and decomposes, with frothing, at 1~0C.
IR spectrum (KBr): 1780 crn 1 and 17~5 cm 1 (C0--N-C0~;
2120 cm~l (N3).
The isomer mixture of 1,6-bis-(3-nitrophthalimi-dyl)-2-methyl-4-dimethylhexane and 17 6-bis-(3-nitro-phthalimidyl)-2-dimethyl-4-methylhe~ane, used in the above example, can be prepared as follows:
8.1 g (0.042 mol) of 3-nitrophthalic anhydride~
3.12 g (0.02 mol) of Montamin (an isomer mix-ture of 1,6 diamino-2-methyl-4-dimethylhexane and 1,5-diarnino 2-dimethyl-4-methylhexane) and 30 ml of acetic acid are heated for 12 hours at 130C in an autoclave. The reaction mixture is then concentra-ted to dryness in vacuo at 80C, the residue is dissolved in 200 ml of methylene chloride and this solution is extracted with saturated sodium bicar~onate solution. The methylene chloride solution is dried with anhydrous sodium sulphate and is finally evaporated. 8.7 g (86% of theory) of an isomer mixture of 1,6-bis-(3-nitrophthalimidyl)-2-methyl-L~-dimethylhexane and -2-dimethyl-4-methylhexane are obtained in the form of a yellow oil which cannot be dis- ;
tilled.
- - IR spectrum (CH2C12): 1785 cm 1 and 1725 cm 1 (C0-N-C0);
1550 cm 1 and 1360 cm 1 (N02).
E~ample 2 9.5 g (0.017 mol) of 4,4'-bis-(3-nitrophthalimi-dyl)-diphenylmethane and 2.8 g (0.044 mol) of sodium azide are dissolved in 80 ml of dimethylsulphoxide and the solu-tion is stirred for 14 hours at ~0C. The reaction mixture is then concentrated in vacuo at 80C, the residue is stirred with 100 ml of water, the mixture is filtered ~ith suction and the filter residue is washed with 10 ml of water. 8.8 g (81.5% of theory) of 4,4'-bis-(3-azidophthalimidyl)-diphenylmethane are obtained. Melt-ing point 182C (with decomposition).
IR spectrum (KBr): 1790 cm 1 and 1725 cm 1 (C0-N-C0);
2130 cm 1 (N3),
Examples of cycloalkyl and aralkyl substituents ~or alkylene groups R are cyclo~entyl,cyclohexyl, cyclooctyl or benzyl groups.
Examples of such alkylene groups R are ~he 1,2-ethylene, 1,3- or 1,2-propylene, 1,4- or 1,3-butylene, pentamethylene, hexamethylene, Z-methyl-4-dimethylhexane, ~-dlmethyl-4~methylhe~an~, l,lO~dicyclohaxyldecan~, 1,10 dicyclooctyldecane, l,10-di-isopropyldecane, l,l,lO,10-tetramethyldecane, l,10-diethyl-1/lO-dimethyldecane, octa-methylene, decamethylene and dodecamethylene group~.
Unsubstituted straight-chain or branched alkylene groups having 2-12, and especlally 2-10, C atom~ are pre-erred.
Alkyl groups Xl, X2 and X3 may be straight-chaln or branched. Preferably, they are straight-chain alkyl groups havlng 1-4 C atoms. Suitable alkyl substituents are, ln particular, methyl and ethyl. I~ M is a HN\Xl group, Xl and X2 are preferably alkyl groups havlng l-4 C atom~
and X3 is preferably an alkyl group having 1-4 C atoms, or the benzyl group.
Preferred substi~uents -C00 M or -S03 M are those in which R is a hydrogen ion, an alkali metal cation, a benzyldialkylammonium ca~ion or a trialkylammonium cation, with l 4 C atoms in each alkyl moiety. Part-icularly preferred meanings of ~ are a hydrogen ion, a sodium .., ~i cation or a potassium ca-tion, Phenylene, naphthylene, biphenylene, cyclohexylene and dicyclohexylrnethane groups and ~ z ~
groups, are preferably unsubsti-tuted. Preferred bridge members Z are -0~, -S02- and -CH2-, The N3 groups are preferably in each case 30ined to the benzene ring in the ortho-position to a carbonyl, carboxyl or carboxamide group.
Preferred compounds are those of the formula Ia, and especially those of the formula Ib, in which R is un~
substituted straight-chain or branched alkylene having 2-12, and especially 2-10, C atoms, unsubstituted phenyl-ene, biphenylene or an unsubstituted diphenyl ether, diphenylmethane or diphenylsulphone radical, or the 3,3'-dimethyl-dicyclohexylmethane radical.
~ Particularly preferred compounds according -to the invention are the compound cf the formula VI
C0 0 ~ ~ ~ ~ (VI) the compound of the formula VII
CO . ~CO
\ ~ ` ~ \CO~
"--- 5 ~
and the compound of the formula VIII
CO CH . CH CO
\ ~ C~2 N ~ ~VIII) I CO CO I
The compounds of the formula Ia and Ib can be pre-pared by reacting a compound of the formula II
~ CO (II) in a molar ratio of at least 1:2 with a diamine of the formula III
H2N-R-NH2 (I~I) to give a compound o~ the formula Ia 0 - NH - R - NH - OC ~ ~Ia) . ~ COOH HOOC ~
R being as de~ined under ~ormula Ia or Ib, and, if desired, subsequently cyclising the compound of the ~ormula Ia.
The reaction of the anhydride of the formula II
with the diamine of the ~ormula III is advantageously carried out in an organic medium, at temperatures between about 0C and 120C depending on the nature of the re-actants.
Advantageously, the anhydride o~ the ormula II
is employed in stoichiometric amount or in slight excess over the diamine of the formula III, for example in up to about 20% molar excess.
Suitable organic solvents are, in par~icular, .
aprotic solvents Examples of suitable aprotic orgar~c sol-vents are aliphatic or aromatic hydrocarbons which may or may not be chlorinated, such as benzene, toluene, methyl-ene chloride, chloroform, carbon tetrachloride, 1,1,~-trichloroethane, 1,2-dichloroethylene and chlorobenzene;
aliphatic and cycloalipha-tic ke-tones, such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone;
cyclic ethers, such as tetrahydrofuran, tetrahydropyran and dioxane; cyclic amides, such as N-methyl-2-pyrroli-done, N-acetyl~2-pyrrolidone and N-methyl-~-caprolac-tam;
N,N-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, such as N,N-dimethyl-formamide, N,N~dimethylacetamide, N,N-diethylamide and N,N-dimethylmethoxyacetamide; alkyl esters of aliphatic mono-carboxylic acids, having a total of 2-6 carbon atoms, such as methyl, ethyl and n-butyl formate or acetate; hexa-methylphosphoric acid triamide (hexametapol); N,N,N',N'-tetrame-thylurea; tetrahydrothiophene dioxide (sulpholan);
and dialkylsulphoxides, such as dimethylsulphoxide or diethylsulphoxide. Mixtures of such solvents can also be employed.
The cyclisation of the compounds of the formula Ia can be carried out in a manner known per se, by chemical means,i.e. with addition of dehydrating agents known per se. Depending on the nature of the reactants, the re-action conditions and the solvent employed, the cyclisation can, especially at elevated temperatures, also be carried out without adding a dehydrating agent, the water formed advantageously being removed azeotropically.
The cyclisation is in general carried out at temperatures be-tween about 40 and 120C, preferably at 70-90C, in the presence of a dehydrating agent and in -the presence or absence o~ an aprotic organic solven-t.
Suitable dehydrating agents are, in particular, anhydrides of aliphatic monocarboxylic acids, having ~-5 C a-toms, which are unsubstitu-ted or substituted by halogen atoms or alkyl group,s, such as acetic anhydride, propionic anhydride, .
butyric anhydride, valeric anhydrlde, trichloroacetic anhydride and trlmethylacetic anhydride, The pre-~erred dehydrating agent is acetic anhydride, According to a preferredprocess, the compoun~s of the formula Ib can also be prepared directly, in a par-ticularly simple manner, by reacting a compound of the formula IV
~ R - N \ ~ (IV) Ql Ql in which R is as defined under formula Ia or Ib and Ql is a halogen atom, such as chlorine, fluorine or bromine, or is a nitro group, in an inert organic solvent, at a temperature between about 0 and 120C, preferably between about 70 and 100C, with an azide of the formula V
Mnl+ (N3 )n~ ~V) in which n is 1 or 2 and Ml is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation.
The literature [Tetrahedron Letters, 12, 1305 -1309 (1966)] discloses that 3-nitrophthalic anhydride can be converted to 3-azidophthalic anhydride by means of sodium azide in the presence of an inert organic solvent at a temperature of 110C, However, 4-nitrophthalic anhydride and 3-chlorophthalic anhydride cannot be con-verted to the corresponding azide by this method, It is therefore surprising that, according to the invention, both the bis-(3-nitrophthalimides) and the bis-(4-nitro-phthalimides) of the formula IV, and the corresponding 3-and 4-halogen compounds can be converted to the corres-ponding azides with good to very good yields and in some cases even at lower temperatures, A prior expensive , , ,.. . . , . , , , . . ~,.. ..
--separa-tion of the starting rna-terials into the 3- and 4-isomers is therefore not necessary in the process accord-ing to the invention.
Preferably, Q1 is the nitro group A quaternary ammonium cation Ml is, for exarnple, a tetraalkylammonium cation or benzyltrialkyla~monium cation with each alkyl moiety having 1-12 and especially-1-4 C atoms~in partiaular the te-tramethylamtnonium cation and the trimethylbenzylammonium cation.
~ xamples of suitable alkali metal azides and alkaline earth metal azides are lithium, sodium, potass-ium, calcium, magnesium and barium azide. . The use of alkali metal azides, in particular of sodium azide, is preferred.
The azide of the formula V is advantageously em-ployed in excess, for example in a molar excess o~ about 5-50% and preferably of about 10-30%.
Sui-table inert organic solvents are, in particular, polar solvents, for exarnple lower aliphatic alcohols, for instance those having upto 6 C atoms, such as methanl, ethanol, propanol, isopropanol, butanols and pentanols;
dibenzyl ethers and dialkyl ethers with each alkyl moi-ety having 1-4 C atoms, such as diethyl ether, di-n-propyl ether and di-isopropyl ether; cyclic ethers, such as tetrahydrofuran, tetrahydropyran and dioxane; diethylene glycol dialkyl ethers and triethylene glycol dialkyl ethers with each alkyl moiety having 1-4 C atoms, such as diethylene glycol diethyl ether and di-n-butyl ether, and triethylene glycol dimethyl ether; aliphatic and aromatic nitriles, such as alkylnitriles having 2-5 C atoms in the alkyl moiety, for example acetonitrile, propionitrile, butyronitrile and benzonitrile; and also aprotic polar organic solvents of the abovementioned type, such as cyclic amides, N,N-dialkylamides of aliphatic monocarboxylic acids having 1-3 C atoms in the acid moiety, dialkylsulphoxides, hexame-thylphosphoric acid triamide (hexametapol) and -tetra-hydrothiophene dioxide (sulpholan) , . :, . , .
~, _ g~
Mixtures of such solvents can also be used Preferred solvents are dialkylsulphoxides, es-pecially dimethylsulphoxide, and N,N dialkylarnides of aliphatic monocarboxylic acids having 1-3 C atoms in.the acid moiety, especially N,N-dimethylformarnide and N,N-dimethylacetamide.
The starting materials of the formula II to V are known or can be prepared by methods known per se. Com-pounds of the f`ormula IV can, for example, be obtained in accordance with known methods by reacting 3- or 4-nitro-phthalic anhydride or the corresponding halogen compounds with a diamine of the formula III and then cyclisin~ the resulting amidocarboxylic acid.
The azidophthalic a-nhydrides of the formula II
are described in U.S Patent Specification 3,002,00~, The compounds of the formula Ia and Ib can be isolated, with or without purification, by conventional means, for example by stripping off the solvent or con-centrating the reaction solution or suspension in vacuo and then washing the reaction product with water or a suitable inert organic solvent, such as methanol, ethanol 7 dioxane, diethyl ether, methylene chloride or chloroform.
In general, the amidocarboxylic acids of the formula Ia are cyclised directly, i.e. without intermediate isolation, to the bis-imides of the formula Ib.
The compounds according to the invention, of the formula Ib, may be used for the preparation of pho-tocur-able (photo-crosslinkable) mixtures for photomechanical applications. Such mixtures contain at least one polymeric compound and at least one compound of the formula Ib, the weight ratio of the former to the latter advantageously being about 9:1 to 1:4 and preferably about 9:1 to l:l Polymeric compounds ~hich can be crosslinked or cured wi-th the bis-azidophthalimidyl com-pounds of the formula Ib under the action of light, es-pecially of W light, can in principle be any kno~m syn-thetic or natural polyMers, for exarnple polyesters, ~oly-... . ~
~, _ 10 --ester-amides, polyamides, polyamidoacids, poly~mide-amidoacids, polyimides, polyamidoimides, polyethers, polyamines, polyimines, polyurethanes, polyureas, poly-urethane-ureas, polycarbonates, polycondensates based on phenol-formaldehyde, polysaccharides, gelatin and polymers which are o~tained by homopolymerisation or copolymer-isation of monomers containing reactive C=C double bonds Preferred polymers are polyethers, especially those which contain recurring structural units of the formula VI
t o - ~ CH ~ O - CH2 ~ CH - CH ~ (VI);
phenol-formaldehyde condensation products (novolacs) which contain recurring structural uni-ts of the formula VII
-CH (VII);
~ CH2 - C~ ~ H2 homopolymers or copolymers of ethylenically unsaturated monomers, which contain identical or different recurring structural units of the formula VIII
2 ~ (VIII);
L Z3 ~4 ~
and cyclised isoprene polymers.
In the formula VIII, Zl and Z~ are each hydrogcn, Z2 is hydrogen, chlorine or methyl and Z~ is hydrogen, , .. .
.
methyl, chlorine, -CN, -COOH, -CO~H2, phenyl, methylphenyl, methoxyphenyl, cyclohexy], pyridyl, imidazolyl, pyrrolid-onyl, ~COO-alkyl having 1-12 C atoms in -the alkyl moiety, -COO-phenyl, -COOCH2CH - ~ E~2, ~COO-alkyl having 1;3 C
atoms in the alkyl moiety, -COOR7-(OC-C=CH2)~ (in which R7 is a straight-chain or branched saturated aliphatic radical having 1-10 C atoms, R5 is hydrogen or methyl and z is an integer from 1 to ~), -OCO-alkyl having 1-4 C
atoms in the alkyl moiety, -OCO-phenyl, -CO-alkyl having 1-3 C atoms in the alkyl moiety, alkoxy having 1-6 C atoms phenoxy, -CH~CH2 or ~ -CH-CH2 ~ or Zl and Z2 are each hydrogen and Z3 and Z4 together are the O C~O ~ ~O
group or are each -COOH or -COO-alkyl having 1-6 C atoms in the alkyl moiety.
` Particularly preferred polymers are polyvinyl chloride, polystyrene, poly(alkyl acrylates) and poly-(alkyl methacrylates) having 1-8 C atoms in the alkyl moie-ty, cyclised isoprene polyme~s, copolymers of maleic anhydride and vinyl ethers or a-olefins, such as methyl vinyl ether or ethylene, as well as polyethers having re-curring structural units of the formula YI
Such mixtures may be used, for example, for the manufacture of printing plates for the offset printing process, for -the manufacture of photo-offset lacquers, for unconventional photography, ~or example for the pro-duction of so-called vesicular images, or for colouring polymer images, which after exposure and development are not easily visible, by means of suitable dyes, such as oil-soluble dyes or, if the polymer contains acid groups, such as carboxylic acid or sulphonic:acid groups, with cationic dyes The Mixturss mentioned are used in particular as so called pho-toresists for the manufacture of printed circuits by methods known per se.
In these, the s.ide of the conductive plate provided with , the photosensitive layer .is exposed through a negative transparency carrying the conductor image and is then developed, after which the unexposed areas of the layer are removed with developer .fluid Exposure can be effected by means of sunlight, carbon arcs or xenon lamps, but is preferably carried out with mercury high pressure lamps Example 1 . -CH2-~H-~H2- f CH2 c~2 / ~ C~3 /
¦ 2 1_CH2_1H_CH2_CH2_ N3 l C~3 CH3 N3 20 3 g (0 04 mol) of an isomer mixture of 1,6-bis-(3-nitrophthalimidyl)-2-methyl-4-dimethylhexane and 1,6-bis-(3-nitrophthalimidyl)-2-dimethyl-4-methylhexane are stirred with 7.78 g (0.104 mol) of NaN3 in 100 ml of N,N-dimethylformamide for 20 hours at 80C. The reaction mixture is evaporated in vacuo at 80C, the oily residue is suspended in 200 ml of water and the suspension is stirred vigorously for 60 hours. The suspension, in which the suspended phase gradually solidifies, is fil-tered with suction and the filter residue is washed with water and dried for 6 days at 25C over phosphorus pent-oxide. 17.6 g (88% of theory) of an isomer mixture of 1,6-bis-(~-azidophthalimidyl)-2-methyl-4-dimethylhexane and 1,6-bis-(3-azidophthalimidyl)-2-dimethyl-4-methyl-hexane are obtained. The product is in the form of a finely divided glassy mass, which melts on heating and decomposes, with frothing, at 1~0C.
IR spectrum (KBr): 1780 crn 1 and 17~5 cm 1 (C0--N-C0~;
2120 cm~l (N3).
The isomer mixture of 1,6-bis-(3-nitrophthalimi-dyl)-2-methyl-4-dimethylhexane and 17 6-bis-(3-nitro-phthalimidyl)-2-dimethyl-4-methylhe~ane, used in the above example, can be prepared as follows:
8.1 g (0.042 mol) of 3-nitrophthalic anhydride~
3.12 g (0.02 mol) of Montamin (an isomer mix-ture of 1,6 diamino-2-methyl-4-dimethylhexane and 1,5-diarnino 2-dimethyl-4-methylhexane) and 30 ml of acetic acid are heated for 12 hours at 130C in an autoclave. The reaction mixture is then concentra-ted to dryness in vacuo at 80C, the residue is dissolved in 200 ml of methylene chloride and this solution is extracted with saturated sodium bicar~onate solution. The methylene chloride solution is dried with anhydrous sodium sulphate and is finally evaporated. 8.7 g (86% of theory) of an isomer mixture of 1,6-bis-(3-nitrophthalimidyl)-2-methyl-L~-dimethylhexane and -2-dimethyl-4-methylhexane are obtained in the form of a yellow oil which cannot be dis- ;
tilled.
- - IR spectrum (CH2C12): 1785 cm 1 and 1725 cm 1 (C0-N-C0);
1550 cm 1 and 1360 cm 1 (N02).
E~ample 2 9.5 g (0.017 mol) of 4,4'-bis-(3-nitrophthalimi-dyl)-diphenylmethane and 2.8 g (0.044 mol) of sodium azide are dissolved in 80 ml of dimethylsulphoxide and the solu-tion is stirred for 14 hours at ~0C. The reaction mixture is then concentrated in vacuo at 80C, the residue is stirred with 100 ml of water, the mixture is filtered ~ith suction and the filter residue is washed with 10 ml of water. 8.8 g (81.5% of theory) of 4,4'-bis-(3-azidophthalimidyl)-diphenylmethane are obtained. Melt-ing point 182C (with decomposition).
IR spectrum (KBr): 1790 cm 1 and 1725 cm 1 (C0-N-C0);
2130 cm 1 (N3),
4,4'-Bis-(3-nitrophthalimid~Jl)-diphenylMethane, used in the above example, can be prepared as follows , :
- 14 _ 44.36 g (O.23 mol) of 3-ni-trophthalic anhydride and 21.61 g (0,109 mol) of 4,4'-diaminodiphenylmethane in 300 ml of acetic acid are refluxed ~or 5 hours, the mixture is then concentra-ted in vacuo and the residue is stirred with 400 ml of water.
The resulting yellow crystalline precipitate is filtered off with suction, then stirred with 20% aqueous NaOH solution at 40C, again filtered off, washed with water and again filtered off with suction. After stirring the material, whilst still moist, with 200 rnl of methyl alcohol, the product is filtered off wi-th suction-and dried for 24 hours at 120C/100 mm Hg 54 g (90% of theory) o~ 4,4'-bis-(3-nitrophthalimidyl)-diphenylmethane are obtained.
Melting point 260-262C (with decomposition).
IR spectrum (KBr): 1790 cm 1 and 17~0 cm 1 (CO-N-CO);
1550 cm 1 and 1360 cm 1 (N02) Exarnp e ~
22 g (0.04 mol) of 4,4'-bis-(3-nitrophthalimidyl)-diphenyl ether are dissolved in 100 ml of dimethylsulphox-ide at 100C and 7.78 g (0~104 mol) of sodium azide are added The reaction mixture is stirred for 16 hours at 100C and is then concentrated in vacuo at 100C
The residue is stirred with 200 ml of water, filtered off with suction and dried for 24 hours in a drying cabinet at 100C 19.2 g (88.5% of theory) of 4,4'-(3-azido-phthalimidyl)~diphenyl ether are obtained~ Melting point 185C (with decomposition).
IR spectrum (KBr): 1790 cm 1 and 1725 cm 1 (CO-N-CO);
21~0 cm 1 (N3) 4,4'-Bis-(3-nitrophthalimidyl)-diphenyl ether, used in the above example, can be prepared as follows:
21 86 g (0 113 mol) of 3-nitrophthalic anhydride are dissolved in 50 ml of N,N-dimethylformamide, after which a solution of 10 8 g (0,054 mol) of 4,4'-di~nino-diphenyl ether in 50 ml of N,N-dimethylformamide is added dropwise 200 ml of toluene are then added, the re-action mixture is heated to the boil and the water formed ,: .
. .
%~
is distilled off azeotropically, Thè reaction rnix-ture is then evaporated to dryness and the residue is stirred with wa-ter, filtered off with suction and dried at 100C, 29.5 g (98% of theory) of 4,4'-(3-ni~ro-phthalimidyl)-diphenyl ether are obtained as a pale yellow powder; melting point 296C (with decomposition), IR spectrum (KBr): 1790 cm 1 and 1730 cm~l (C0-N-C0);
1550 cm 1 and 1360 cm 1 (N02), '~:
. A mixture of 21,3 g (o,048 mol) of 1,4-bis-(3-nitrophthalimidyl)-butane and 7,2 g (0.11 mol) of sodium azide in 225 ml of N,N-dimethylformamide is heated for 18 hours at 80C and is then evaporated in vacuo at the same temperature. The resîdue is stirred with 200 ml of water and the mixture is acidified with 1 ml of ;~
concentrated hydrochloric acid, The resulting sus-pension of the product is filtered with suction and the filter residue is washed with 20 ml of water and dried for 24 hours at 80C in a drying cabinet, 20.4 g (98.8%
of theory) of 1,4-bis-(3-azidophthalimidyl)-butane are obtained; melting point 162C (with decomposition), IR spectrum (KBr): 1775 cm 1 and 1720 cm 1 (C0 N-C0);
2120 cm 1 (N3).
1,4-Bis-(3-nitrophthalimidyl)-butane, used in the above example~can be prepared as follows:
8.1 g (0.042 mol) of 3-nitrophthalic anhydride are suspended in 15 ml of acetic acid in an autoclave 9 1.76 g (0.02 mol) of 1,4-diaminobutane in 15 ml of toluene are added and the mixture is stirred for 6 hours at 120C.
The resulting thick precipitate is filtered off with suction and dried for 24 hours at 120C/100 mm Hg.
7.8 g (90% of theory) of 1,4-bis-(3-nitrophthalimidyl)-butane are obtained; melting point 245C.
IR spectrum (KBr): 1780 cm 1 and 1725 cm 1 (C0-N-C0);
1550 cm 1 and 1350 cm 1 (N02).
Example 5 A solution of 3,78 g (0,02 molj of 3-a~ido-, phthalic anhydride in 50 rnl of methylene chloride is mixed with a solution of 1 98 g (0.01 mol) of 4,4'-diaminodi-phenylmethane in 50 ml of methylene chloride. After a short time, the corresponding amidoacid crystallises out. The latter is filtered off with suction and then suspended in 100 ml of dioxan, 5 ml of acetic anhydride are added and the mixture is heated to 85C for 1 hour.
The solution is then concentrated to dryness and the resi-due is stirred with water, washed with ethanol and dried at 60C~ 4~ g (80% of theory) of 4,4'-bis-(3-azido-phthalimidyl)-diphenylmethane are obtained; melting point 180C (with decomposition).
Examples 6_and 7 Following a method analogous to that described in Examples 1 to 4, 1,6-bis-(3-azidophthalimidyl)-hexane and l,lO-bis-(3-azidophthalimidyl)-l,10-dimethyldecane are prepared respectively from:
20 g (0.043 mol) of 1,6-bis-(3-nitroph-thalimidyl)-hexane and 7.2 g (0 111 mol) of sodium azide; yield 78%
of theory, melting point 147C (with decomposition), and 8 g (0.014 mol) of 1,10-bis-(3-nitrophthalimidyl)-l,lO-dimethyldecane and 2.~6 g (0.035 mol) of sodium azide;
yield 80% of theory, viscous oil.
Example 8 An aluminium plate is coated with a solution of 3 g of 1,4-bis-(3-azidophthalimidyl)-butane and 5 g of a copolymer of maleic anhydride and ethylene ("EMA 21", a commercial product from Monsanto) in 72 ml of N,N-dimetnylformamide, using a coating centrifuge (300 revolutions per minute) After drying the coating, the coated plate is exposed for 1 minute, through a line negative, to W light (mercury high pressure lamp with a Pyrex~filter in front of the lamp, wavelength greater than 320 nm). The exposed plate is then developed in 5-10% aqueous sodium bicarbonate solution, resulting in a relief image, corresponding to the line negative; if desired, the image can be dyed with a ca-tionic dye.
,~ .............. . .
I ra~lem~ rk ExamE~
1 35 g of 4,4'-bis-(3-azidophthalirnidyl)-diphenyl ether are dissolved in 100 ml of cyclohexanone and -the solution is then mixed, with exclusion of light, with 100 g of a 2 5% solution of a synthetic isoprene polyrner ("Cariflex IR 309", a comrnercial product from Shell) in chlorobenzene.
A copper-laminated epoxy plate is coa-ted with this solution and the coating is dried in vacuo a-t 40C and -then exposed, through a negative, to UV light (~ greater than 320 nm). After developrnent with 1,1,1-tri-chloroethane, an image corresponding to the negative appears.
~ ~ . r N ~ -A mix-ture of 9.16 g (0.02 mol) of 1,4-bis-(3-nitrophthalimidyl)-benzene, 2.84 g (0.044 mol) of sodium azide and 180 ml of dimethylsulphoxide is stirred for 24 hours at 80C. The reaction mixture is evaporated in vacuo and the residue is stirred with 200 ml of water.
The crystals ~hich have precipitated are filtered off with suction, washed with 100 ml of water and dried for 12 hours at 80/lOO ~m Hg 8.8 g (98% of theory) of 1,4-bis-(3-azidophthalimidyl)-benzene are obtained; melting point 189C (with decomposition) IR spectrum (KBr): 1780 cm 1 and 1725 cm 1 ~C0-N-C0) 2130 cm 1 (-N3) 1,4-Bis-(3-ni-trophthalimidyl)~benzene, used in the above example, can be prepared a~ follows: a mixture of 21.2 g (0.11 rnol) of 3-nitrophthalic anhydride, 5.4 g z~
~ ~8 -(0.05 mol) of p-phenylenediamine, 100 ml of dimethyl-formarnide and 200 ml of -toluene is boiled, the water formed during the reaction being removed azeotropically.
The reaction mixture is then evaporated to dryness and the residue is stirred with 1,000 rnl of water, filtered off wi-th suction and dried for 24 hours at 100/100 mm Hg.
16.8 g (73% of theory) of 1,4-bis-(3-nitrophthalimidyl)-benzene are obtained; melting point: above 250C
Example 11 ~CO ,CO
N~ N3 A mixture of 10.7 g (0.02 mol) of 4,4'-bis-(3--- nitrophthalimidyl)-diphenyl, 2.84 g (0.044 mol) of sodium azide and 20 ml of dimethylsulphoxide is stirred for 24 hours at 80. The reaction mixture is then e~apora-ted to dryness and the residue is stirred with 100 ml of water. The resulting crystals are washed with twice 50 ml of water and dried for 24 hours at 80/100 mm Hg.
9.8 g (92.8% of theory) of 4,4'--bis-(3-azido-phthalimidyl)-diphenyl are obtained. Melting point:
above 250.
IR spectrum (KBr): 1775 cm 1 and 1725 cm 1 (C0-N-C0) 2130 cm~~ 3) - 4,4'-Eis-(3-nitrophthalimidyl)-diphenyl, used in the above exarnple, can be prepared as follows. A mix-ture of 21.2 g (0.11 mol) of 3-nitrophthalic anhydride, 8.7 g (0.05 mol) of benzidine, 100 ml of dimethylformamide and 200 ml of toluene is boiled, the water formed during the reaction being removed azeotropically. The re-action mixture is then evaporated to dryness and the residue is stirred wi-th 1,000 ml of wa-ter and fil-tered off wi-th suction. The product, whilst still moist, is stirred with 500 rnl of 10% sodiurn carbonate solution, filtered off wi-th suction, washed thoroughly wi-th water (the water must have a final pH of 7) and dried at 80/100 mm Hg for 24 hours 20,2 g (75 6% of theory) of 4,4'~bis-(3-nitrophthalimidyl)-diphenyl are obtained.
Melting point: above 250C.
Example 12 CH3 ~H3 N ~} CH2 ~ ~
A mixture of 11.74 g (0 02 mol) of 3,3'-dimethyl-4,4'-bis-(3-nitrophthalimidyl)-dicyclohexylmethane, 3.64 g (0.056 mol) of sodium azide and 180 ml of dimethylsulphox-ide was stirred for 24 hours at 80C. The reaction mixture is evaporated to dryness and the residue is stirred with 100 ml of water, filtered off with suction, washed with three times 50 ml of water and dried over phosphorus pentoxide for 24 hours at 40/0.1 mm Hg.
9.9 g (85 3% of theory) of 3,3'-dimethyl-4,4'-bis-(3-azidophthalimidyl)-dicyclohexylmethane are obtained;
melting point 95-100 (with decomposition) IR spectrum (KBr): 1780 and 1725 cm 1 (C0-N-C0) 2130 cm 1 (N3) - 3,3'~Dimethyl-4,4'-bis-(3-nitroph-thalimidyl)-di-cyclohexylme-thane, used in the above example, can be pre-pared as follows:
A mixture of 21.2 g (0.11 mol) of 3-nitrophthalic anhydride, 11.9 g (0.05 mol) of 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 100 ml of dimethylformamide and 200 ml o~ tcluene is boiled, the water formed during the re-action being removed azeotropically. The reaction mixture is then concen-tra-ted to dryness and the residue is stirred with three times 100 ml of water and filtered off with suction. The produc-t, whilst still moist, is ..... , ' . ~ , ............ . .
. ' .
stirred with 250 ml of 10% sodium carbonate solu-tion, filtered off with suction, washed with water until the latter reacts neutral and dri.ed at 80/100 mm Hg for 24 hours 29 g (98.60/o of theory) of 3,3'-dimethyl-4,4'-bis-(3~nitrophthalimidyl)-dicyclohexylmethane are ob-tained;
rnelting point: 125.
- 14 _ 44.36 g (O.23 mol) of 3-ni-trophthalic anhydride and 21.61 g (0,109 mol) of 4,4'-diaminodiphenylmethane in 300 ml of acetic acid are refluxed ~or 5 hours, the mixture is then concentra-ted in vacuo and the residue is stirred with 400 ml of water.
The resulting yellow crystalline precipitate is filtered off with suction, then stirred with 20% aqueous NaOH solution at 40C, again filtered off, washed with water and again filtered off with suction. After stirring the material, whilst still moist, with 200 rnl of methyl alcohol, the product is filtered off wi-th suction-and dried for 24 hours at 120C/100 mm Hg 54 g (90% of theory) o~ 4,4'-bis-(3-nitrophthalimidyl)-diphenylmethane are obtained.
Melting point 260-262C (with decomposition).
IR spectrum (KBr): 1790 cm 1 and 17~0 cm 1 (CO-N-CO);
1550 cm 1 and 1360 cm 1 (N02) Exarnp e ~
22 g (0.04 mol) of 4,4'-bis-(3-nitrophthalimidyl)-diphenyl ether are dissolved in 100 ml of dimethylsulphox-ide at 100C and 7.78 g (0~104 mol) of sodium azide are added The reaction mixture is stirred for 16 hours at 100C and is then concentrated in vacuo at 100C
The residue is stirred with 200 ml of water, filtered off with suction and dried for 24 hours in a drying cabinet at 100C 19.2 g (88.5% of theory) of 4,4'-(3-azido-phthalimidyl)~diphenyl ether are obtained~ Melting point 185C (with decomposition).
IR spectrum (KBr): 1790 cm 1 and 1725 cm 1 (CO-N-CO);
21~0 cm 1 (N3) 4,4'-Bis-(3-nitrophthalimidyl)-diphenyl ether, used in the above example, can be prepared as follows:
21 86 g (0 113 mol) of 3-nitrophthalic anhydride are dissolved in 50 ml of N,N-dimethylformamide, after which a solution of 10 8 g (0,054 mol) of 4,4'-di~nino-diphenyl ether in 50 ml of N,N-dimethylformamide is added dropwise 200 ml of toluene are then added, the re-action mixture is heated to the boil and the water formed ,: .
. .
%~
is distilled off azeotropically, Thè reaction rnix-ture is then evaporated to dryness and the residue is stirred with wa-ter, filtered off with suction and dried at 100C, 29.5 g (98% of theory) of 4,4'-(3-ni~ro-phthalimidyl)-diphenyl ether are obtained as a pale yellow powder; melting point 296C (with decomposition), IR spectrum (KBr): 1790 cm 1 and 1730 cm~l (C0-N-C0);
1550 cm 1 and 1360 cm 1 (N02), '~:
. A mixture of 21,3 g (o,048 mol) of 1,4-bis-(3-nitrophthalimidyl)-butane and 7,2 g (0.11 mol) of sodium azide in 225 ml of N,N-dimethylformamide is heated for 18 hours at 80C and is then evaporated in vacuo at the same temperature. The resîdue is stirred with 200 ml of water and the mixture is acidified with 1 ml of ;~
concentrated hydrochloric acid, The resulting sus-pension of the product is filtered with suction and the filter residue is washed with 20 ml of water and dried for 24 hours at 80C in a drying cabinet, 20.4 g (98.8%
of theory) of 1,4-bis-(3-azidophthalimidyl)-butane are obtained; melting point 162C (with decomposition), IR spectrum (KBr): 1775 cm 1 and 1720 cm 1 (C0 N-C0);
2120 cm 1 (N3).
1,4-Bis-(3-nitrophthalimidyl)-butane, used in the above example~can be prepared as follows:
8.1 g (0.042 mol) of 3-nitrophthalic anhydride are suspended in 15 ml of acetic acid in an autoclave 9 1.76 g (0.02 mol) of 1,4-diaminobutane in 15 ml of toluene are added and the mixture is stirred for 6 hours at 120C.
The resulting thick precipitate is filtered off with suction and dried for 24 hours at 120C/100 mm Hg.
7.8 g (90% of theory) of 1,4-bis-(3-nitrophthalimidyl)-butane are obtained; melting point 245C.
IR spectrum (KBr): 1780 cm 1 and 1725 cm 1 (C0-N-C0);
1550 cm 1 and 1350 cm 1 (N02).
Example 5 A solution of 3,78 g (0,02 molj of 3-a~ido-, phthalic anhydride in 50 rnl of methylene chloride is mixed with a solution of 1 98 g (0.01 mol) of 4,4'-diaminodi-phenylmethane in 50 ml of methylene chloride. After a short time, the corresponding amidoacid crystallises out. The latter is filtered off with suction and then suspended in 100 ml of dioxan, 5 ml of acetic anhydride are added and the mixture is heated to 85C for 1 hour.
The solution is then concentrated to dryness and the resi-due is stirred with water, washed with ethanol and dried at 60C~ 4~ g (80% of theory) of 4,4'-bis-(3-azido-phthalimidyl)-diphenylmethane are obtained; melting point 180C (with decomposition).
Examples 6_and 7 Following a method analogous to that described in Examples 1 to 4, 1,6-bis-(3-azidophthalimidyl)-hexane and l,lO-bis-(3-azidophthalimidyl)-l,10-dimethyldecane are prepared respectively from:
20 g (0.043 mol) of 1,6-bis-(3-nitroph-thalimidyl)-hexane and 7.2 g (0 111 mol) of sodium azide; yield 78%
of theory, melting point 147C (with decomposition), and 8 g (0.014 mol) of 1,10-bis-(3-nitrophthalimidyl)-l,lO-dimethyldecane and 2.~6 g (0.035 mol) of sodium azide;
yield 80% of theory, viscous oil.
Example 8 An aluminium plate is coated with a solution of 3 g of 1,4-bis-(3-azidophthalimidyl)-butane and 5 g of a copolymer of maleic anhydride and ethylene ("EMA 21", a commercial product from Monsanto) in 72 ml of N,N-dimetnylformamide, using a coating centrifuge (300 revolutions per minute) After drying the coating, the coated plate is exposed for 1 minute, through a line negative, to W light (mercury high pressure lamp with a Pyrex~filter in front of the lamp, wavelength greater than 320 nm). The exposed plate is then developed in 5-10% aqueous sodium bicarbonate solution, resulting in a relief image, corresponding to the line negative; if desired, the image can be dyed with a ca-tionic dye.
,~ .............. . .
I ra~lem~ rk ExamE~
1 35 g of 4,4'-bis-(3-azidophthalirnidyl)-diphenyl ether are dissolved in 100 ml of cyclohexanone and -the solution is then mixed, with exclusion of light, with 100 g of a 2 5% solution of a synthetic isoprene polyrner ("Cariflex IR 309", a comrnercial product from Shell) in chlorobenzene.
A copper-laminated epoxy plate is coa-ted with this solution and the coating is dried in vacuo a-t 40C and -then exposed, through a negative, to UV light (~ greater than 320 nm). After developrnent with 1,1,1-tri-chloroethane, an image corresponding to the negative appears.
~ ~ . r N ~ -A mix-ture of 9.16 g (0.02 mol) of 1,4-bis-(3-nitrophthalimidyl)-benzene, 2.84 g (0.044 mol) of sodium azide and 180 ml of dimethylsulphoxide is stirred for 24 hours at 80C. The reaction mixture is evaporated in vacuo and the residue is stirred with 200 ml of water.
The crystals ~hich have precipitated are filtered off with suction, washed with 100 ml of water and dried for 12 hours at 80/lOO ~m Hg 8.8 g (98% of theory) of 1,4-bis-(3-azidophthalimidyl)-benzene are obtained; melting point 189C (with decomposition) IR spectrum (KBr): 1780 cm 1 and 1725 cm 1 ~C0-N-C0) 2130 cm 1 (-N3) 1,4-Bis-(3-ni-trophthalimidyl)~benzene, used in the above example, can be prepared a~ follows: a mixture of 21.2 g (0.11 rnol) of 3-nitrophthalic anhydride, 5.4 g z~
~ ~8 -(0.05 mol) of p-phenylenediamine, 100 ml of dimethyl-formarnide and 200 ml of -toluene is boiled, the water formed during the reaction being removed azeotropically.
The reaction mixture is then evaporated to dryness and the residue is stirred with 1,000 rnl of water, filtered off wi-th suction and dried for 24 hours at 100/100 mm Hg.
16.8 g (73% of theory) of 1,4-bis-(3-nitrophthalimidyl)-benzene are obtained; melting point: above 250C
Example 11 ~CO ,CO
N~ N3 A mixture of 10.7 g (0.02 mol) of 4,4'-bis-(3--- nitrophthalimidyl)-diphenyl, 2.84 g (0.044 mol) of sodium azide and 20 ml of dimethylsulphoxide is stirred for 24 hours at 80. The reaction mixture is then e~apora-ted to dryness and the residue is stirred with 100 ml of water. The resulting crystals are washed with twice 50 ml of water and dried for 24 hours at 80/100 mm Hg.
9.8 g (92.8% of theory) of 4,4'--bis-(3-azido-phthalimidyl)-diphenyl are obtained. Melting point:
above 250.
IR spectrum (KBr): 1775 cm 1 and 1725 cm 1 (C0-N-C0) 2130 cm~~ 3) - 4,4'-Eis-(3-nitrophthalimidyl)-diphenyl, used in the above exarnple, can be prepared as follows. A mix-ture of 21.2 g (0.11 mol) of 3-nitrophthalic anhydride, 8.7 g (0.05 mol) of benzidine, 100 ml of dimethylformamide and 200 ml of toluene is boiled, the water formed during the reaction being removed azeotropically. The re-action mixture is then evaporated to dryness and the residue is stirred wi-th 1,000 ml of wa-ter and fil-tered off wi-th suction. The product, whilst still moist, is stirred with 500 rnl of 10% sodiurn carbonate solution, filtered off wi-th suction, washed thoroughly wi-th water (the water must have a final pH of 7) and dried at 80/100 mm Hg for 24 hours 20,2 g (75 6% of theory) of 4,4'~bis-(3-nitrophthalimidyl)-diphenyl are obtained.
Melting point: above 250C.
Example 12 CH3 ~H3 N ~} CH2 ~ ~
A mixture of 11.74 g (0 02 mol) of 3,3'-dimethyl-4,4'-bis-(3-nitrophthalimidyl)-dicyclohexylmethane, 3.64 g (0.056 mol) of sodium azide and 180 ml of dimethylsulphox-ide was stirred for 24 hours at 80C. The reaction mixture is evaporated to dryness and the residue is stirred with 100 ml of water, filtered off with suction, washed with three times 50 ml of water and dried over phosphorus pentoxide for 24 hours at 40/0.1 mm Hg.
9.9 g (85 3% of theory) of 3,3'-dimethyl-4,4'-bis-(3-azidophthalimidyl)-dicyclohexylmethane are obtained;
melting point 95-100 (with decomposition) IR spectrum (KBr): 1780 and 1725 cm 1 (C0-N-C0) 2130 cm 1 (N3) - 3,3'~Dimethyl-4,4'-bis-(3-nitroph-thalimidyl)-di-cyclohexylme-thane, used in the above example, can be pre-pared as follows:
A mixture of 21.2 g (0.11 mol) of 3-nitrophthalic anhydride, 11.9 g (0.05 mol) of 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 100 ml of dimethylformamide and 200 ml o~ tcluene is boiled, the water formed during the re-action being removed azeotropically. The reaction mixture is then concen-tra-ted to dryness and the residue is stirred with three times 100 ml of water and filtered off with suction. The produc-t, whilst still moist, is ..... , ' . ~ , ............ . .
. ' .
stirred with 250 ml of 10% sodium carbonate solu-tion, filtered off with suction, washed with water until the latter reacts neutral and dri.ed at 80/100 mm Hg for 24 hours 29 g (98.60/o of theory) of 3,3'-dimethyl-4,4'-bis-(3~nitrophthalimidyl)-dicyclohexylmethane are ob-tained;
rnelting point: 125.
Claims (12)
l. A compound of the formula Ia or Ib (Ia) or (Ib) in which R is alkylene having 2-12 C atoms,which is unsubstituted or substituted by one or two phenyl groups, cycloalkyl groups having 5-8 C atoms or aralkyl groups having 7 or 8 C atoms, or is phenylene, naphthylene, biphenylene, cyclohexylene, dicyclohexylmethane or which are unsubstituted or substituted by one alKyl group having 1-4 C-atoms or one -OH, -COO-M+
or -SO3-M+ group per ring, Z is -O-, -S-, -SO2-, -CH2-, -CO-, or , M+ is a hydrogen ion, an alkali metal cation, the pyridinium cation or , X1 and X2 independently of one another are hydrogen or alkyl having
1-12 C atoms and X3 is hydrogen, alkyl having 1-12 C atoms or benzyl.
2. A compound of the formula Ia or Ib according to claim 1, in which the N3 groups are each linked to the benzene ring in the ortho-position to a carbonyl, carboxyl or carboxamide group.
3. A compound of the formula Ia or Ib according to claim 1, in which R is unsubstituted straight-chain or branched alkylene having 2-12 C-atoms, unsubstituted phenylene,bi-phenylene,an unsubstituted diphenyl ether,diphenylmethane or diphenylsulphone radical or the 3,3'-dimethyl-dicyclohexyl-methane radical.
4. A compound according to claim 1, of the formula VI
(VI)
(VI)
5. A compound to claim 1, of the formula VII
(VII)
(VII)
6. A compound according to claim 1 of the formula VIII
(VIII)
(VIII)
7. A process for the preparation of a compound of the formula Ia or Ib according to claim 1, which comprises A. reacting a compound of the formula II
(II) with a diamine of the formula III
H2N-R-NH2 (III) to give a compound of the formula Ia (Ia) R being defined as under formula Ia or Ib, and, if desired, subsequently cyclising the compound of the formula Ia to a compound of the formula Ib, or B. reacting a compound of the formula IV
(IV) in which R is as defined under formula Ia or Ib and Q1 is a halogen atom or the nitro group, in an inert organic solvent, at a temperature between about 0°C and 120°C, with an azide of the formula V
M1n+ (N3-)n (V) in which n is 1 or 2 and M1 is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation, to give a compound of formula Ib.
(II) with a diamine of the formula III
H2N-R-NH2 (III) to give a compound of the formula Ia (Ia) R being defined as under formula Ia or Ib, and, if desired, subsequently cyclising the compound of the formula Ia to a compound of the formula Ib, or B. reacting a compound of the formula IV
(IV) in which R is as defined under formula Ia or Ib and Q1 is a halogen atom or the nitro group, in an inert organic solvent, at a temperature between about 0°C and 120°C, with an azide of the formula V
M1n+ (N3-)n (V) in which n is 1 or 2 and M1 is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation, to give a compound of formula Ib.
8. A process for the preparation of a compound of the formula Ia or Ib according to claim 7, which comprises reacting a compound of the formula II
(II) with a diamine of the formula III
H2N-R-NH2 (III) to give a compound of the formula Ia (Ia) R being defined as under formula Ia or Ib, and, if desired, subsequently cyclising the compound of the formula Ia to a compound of the formula Ib.
(II) with a diamine of the formula III
H2N-R-NH2 (III) to give a compound of the formula Ia (Ia) R being defined as under formula Ia or Ib, and, if desired, subsequently cyclising the compound of the formula Ia to a compound of the formula Ib.
9. A process for the preparation of a compound of the formula Ib according to claim 7, which comprises reacting a compound of the formula IV
(IV) in which R is as defined under formula Ia or Ib and Q1 is a halogen atom or the nitro group, in an inert organic solvent, at a temperature between about 0°C and 120°C,with an azide of the formula V
M1n+ (N3-)n (V) in which n is 1 or 2 and M1 is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation.
(IV) in which R is as defined under formula Ia or Ib and Q1 is a halogen atom or the nitro group, in an inert organic solvent, at a temperature between about 0°C and 120°C,with an azide of the formula V
M1n+ (N3-)n (V) in which n is 1 or 2 and M1 is an alkali metal cation, alkaline earth metal cation or quaternary ammonium cation.
10. A process according to claim 7, wherein a compound of the formula IV, in which Q1 is a nitro group, is used.
11. A process according to claim 7, wherein an alkali metal azide is used as the compound of the formula V.
12. A process according to claim 7, wherein the reaction between a compound of formula IV and a compound of formula V is carried out at a temperature between about 70 and 100°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH12579/77 | 1977-10-14 | ||
| CH1257977 | 1977-10-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1112246A true CA1112246A (en) | 1981-11-10 |
Family
ID=4384365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA313,230A Expired CA1112246A (en) | 1977-10-14 | 1978-10-12 | Bis-azidophthalic acid derivatives |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0002182B1 (en) |
| JP (1) | JPS5470239A (en) |
| CA (1) | CA1112246A (en) |
| DE (1) | DE2860609D1 (en) |
| ES (1) | ES474175A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0353666A2 (en) * | 1988-08-03 | 1990-02-07 | Toyo Gosei Kogyo Co., Ltd. | Photosensitive agent,photosensitive resin composition containing same, and method of image formation using the composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3372550D1 (en) * | 1982-11-04 | 1987-08-20 | Ciba Geigy Ag | Compositions photocurable in the presence of sensitizers, and their use |
| US4615968A (en) * | 1982-11-04 | 1986-10-07 | Ciba-Geigy Corporation | Compositions of matter which crosslink under the action of light in the presence of sensitizers |
| JPS62127735A (en) * | 1985-11-29 | 1987-06-10 | Toshiba Corp | Photosensitive resin composition and preparation of color filter by using it |
| JPH04182466A (en) * | 1990-11-19 | 1992-06-30 | Mitsubishi Gas Chem Co Inc | Production of bistrimellitic imides |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2852379A (en) * | 1955-05-04 | 1958-09-16 | Eastman Kodak Co | Azide resin photolithographic composition |
| DE2000623C3 (en) * | 1970-01-08 | 1979-06-28 | Agfa-Gevaert Ag, 5090 Leverkusen | Photographic process for the production of images |
-
1978
- 1978-10-06 DE DE7878101084T patent/DE2860609D1/en not_active Expired
- 1978-10-06 EP EP19780101084 patent/EP0002182B1/en not_active Expired
- 1978-10-12 CA CA313,230A patent/CA1112246A/en not_active Expired
- 1978-10-13 ES ES474175A patent/ES474175A1/en not_active Expired
- 1978-10-14 JP JP12676478A patent/JPS5470239A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0353666A2 (en) * | 1988-08-03 | 1990-02-07 | Toyo Gosei Kogyo Co., Ltd. | Photosensitive agent,photosensitive resin composition containing same, and method of image formation using the composition |
| EP0353666A3 (en) * | 1988-08-03 | 1990-05-23 | Toyo Gosei Kogyo Co., Ltd. | Photosensitive agent,photosensitive resin composition containing same, and method of image formation using the composition |
Also Published As
| Publication number | Publication date |
|---|---|
| ES474175A1 (en) | 1979-09-01 |
| DE2860609D1 (en) | 1981-04-30 |
| EP0002182A3 (en) | 1979-07-11 |
| EP0002182B1 (en) | 1981-04-08 |
| JPS5470239A (en) | 1979-06-05 |
| EP0002182A2 (en) | 1979-06-13 |
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