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Patent US4555469 - Process of preparing light-sensitive naphthoquinonediazidesulfonic acid ester - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA light-sensitive mixture comprising a water-insoluble binder soluble in aqueous alkaline solutions, and the reaction product of a naphthoquinonediazidesulfonyl halide with a mixture composed of a low molecular weight compound having a definite structure and molecular size containing at least one phenolic...http://www.google.com/patents/US4555469?utm_source=gb-gplus-sharePatent US4555469 - Process of preparing light-sensitive naphthoquinonediazidesulfonic acid esterAdvanced Patent SearchPublication numberUS4555469 APublication typeGrantApplication numberUS 06/542,173Publication dateNov 26, 1985Filing dateOct 14, 1983Priority dateJan 3, 1981Fee statusLapsedAlso published asCA1186439A, CA1186439A1, DE3100077A1, EP0055814A2, EP0055814A3, EP0055814B1, EP0055814B2, US4424270Publication number06542173, 542173, US 4555469 A, US 4555469A, US-A-4555469, US4555469 A, US4555469AInventorsFritz Erdmann, Ulrich SimonOriginal AssigneeHoechst AktiengesellschaftExport CitationBiBTeX, EndNote, RefManPatent Citations (9), Referenced by (55), Classifications (15), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetProcess of preparing light-sensitive naphthoquinonediazidesulfonic acid ester
US 4555469 AAbstract
1. A process for preparing a light-sensitive naphthoquinonediazide-sulfonic acid ester which is non-explosive, comprising the steps of (I) reacting a naphthoquinonediazidesulfonyl halide in the presence of a base and a solvent with a mixture comprising:A. a polymeric compound having recurring units, each of said recurring units containing at least one phenolic hydroxyl group, and B. a low molecular weight compound corresponding to the formula ##STR2## wherein (1a) R denotes a single bond or one from the group consisting of CO, S, O, SO2 and CR6 R7 ;(b) R1, R2, R3, and R5 represent hydrogen, halogen, hydroxyl groups, alkyl groups having 1 to 4 carbon atoms or alkoxy groups having 1 to 4 carbon atoms; and (c) R6 and R7 represent hydrogen or alkyl groups having 1 to 4 carbon atoms; or wherein (2a) two of the radicals R3, R4, and R5 and the radicals R1 and R2 in each case jointly form a fused aromatic ring; and (b) at least one of the radicals R1, R2, R3, R4, and R5 represents a hydroxyl group, wherein (i) said polymeric compound and said low molecular weight compound are present in a ratio in the range of 0.1-20:1 and (ii) said ester has a diazo nitrogen content of between about 2% and about 9%; and (II) isolating the reaction product of step (I). 2. A process according to claim 1, wherein said naphthoquinonediazidesulfonyl halide is formed from a monosulfonic acid compound.
3. A process according to claim 1, wherein said naphthoquinonediazidesulfonyl halide is formed from a disulfonic acid compound.
4. A process according to claim 1, wherein said low molecular weight compound containing at least one phenolic hydroxyl group is selected from the group consisting of 2,4-dihydroxybenzophenone; 2,3,4-trihydroxybenzophenone; 2,4,2',4'-tetrahydroxydiphenyl sulfide; 2,2'-dihydroxydinaphthylmethane; 4,4'dihydroxy-2,2'-dimethyl-5,5-di-tert-butyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulfide; 4,6-bis-(2,4-dihydroxyphenylthio)-resorcinol; 2,3,2',4'-tetrahydroxy-3,5,5'-tetrabromodiphenyl sulfone; 2,3,2',4'-tetrahydroxy-3,5,3',5'-tetrabromobiphyenyl, and 2,4-dihydroxy-3,5-dibromobenzophenone.
5. A process according to claim 1, wherein said polymeric compound having recurring units comprises a phenolic resin.
6. A process according to claim 5, wherein said polymeric compound having recurring units comprises a resin selected from the group consisting of phenol-formaldehyde novolac resins and cresol-formaldehyde novolac resins.
7. A process according to claim 1, wherein the weight ratio of polymeric compound having recurring units to said low molecular weight compound lies in the range from 0.1 to 20 parts by weight of said polymeric compound per 1 part by weight of said low molecular weight compound.
8. A process according to claim 7, wherein the weight ratio of polymeric compound having recurring units to said low molecular weight compound lies in the range from 0.3 to 12 parts by weight of said polymeric compound per 1 part by weight of said low molecular weight compound.
9. A process according to claim 1, wherein the proportion of naphthoquinonediazidesulfonyl halide reacted with said reaction mixture is sufficient to completely esterify all of the phenolic hydroxyl groups of said low molecular weight compound.
10. A process according to claim 1, wherein said esterified reaction product has a diazo nitrogen content from about 2 to about 9 weight percent.
11. A process according to claim 10, wherein said esterified reaction product has a diazo nitrogen content from 3 to 8 weight percent.
12. A process according to claim 11, wherein said esterified reaction product has a diazo nitrogen content from 4.5 to 7.5 weight percent.
13. A process according to claim 1, wherein a solvent solution of said naphthoquinonediazidesulfonyl halide is added to a solvent solution of said mixture of phenolic compounds.
14. A process according to claim 1, wherein said reaction is effected in the presence of a base.
15. A process according to claim 1, wherein said low molecular weight compound contains at least two phenolic hydroxyl groups.
16. A process according to claim 1, wherein said naphthoquinonediazidesulfonyl halide is a 1,2-naphthoquinone-2-diazide-sulfonyl chloride.
17. A process according to claim 1, wherein said diazo nitrogen content is between about 3% and about 8%.
18. A process according to claim 17, wherein said nitrogen content is between about 4.5% and about 7%.
19. A process according to claim 1, wherein said reaction product is isolated by precipitation.
20. A process according to claim 1, wherein said reaction product is isolated by evaporating said solvent.
This is a division of application Ser. No. 333,338 filed on Dec. 22, 1981, Pat. No. 4,424,270.
On the other hand, it is known to prepare and use high molecular weight o-quinone diazides to solve other problems. German Pat. No. 850,860 describes the reaction of o-quinonediazidesulfonyl halides with phenolic resins and the use of the reaction products for coating printing plates, it being necessary to prevent the quinone diazides from crystallizing in the layer. However, the light-sensitivity and other technical properties of these compounds are insufficient for present-day copying and printing requirements.
A further object of the present invention is to produce a light-sensitive mixture comprising a naphthoquinonediazidesulfonic acid ester which exhibits a high light-sensitivity and good developer resistance.
Additionally, it is an object of the present invention to provide a process for producing a nonexplosive naphthoquinonediazidesulfonic acid ester material.
The esterification products obtained by the process of the invention can be isolated from the reaction mixture, purified, dried, stored and transported without risk and without exhibiting any tendency to explode. On the other hand, as a result of their content of low molecular weight constitutents, the esters of the invention have essentially the same advantageous properties as the known low molecular weight compounds.
R denotes a single bond or one of the groups CO, S, O, SO2 and CR6 R7, peferably CO or CR6 R7,
Suitable low molecular weight phenolic compounds include 2,4-dihydroxybenzophenone; 2,3,4-trihydroxybenzophenone; 2,4,2',4'-tetrahydroxydiphenyl sulfide; 2,2'-dihydroxydinaphthylmethane; 4,4'-dihydroxy-2,2'-dimethyl-5,5'-di-tert.-butyldiphenyl sulfide; 4,4'-dihydroxydiphenyl sulfide; 4,6-bis-(2,4-dihydroxyphenylthio)-resorcinol; 2,4,2',4'-tetrahydroxy-3,5,3',5'-tetrabromodiphenyl sulfone; 2,4,2',4'-tetrahydroxy-3,5,3',5'-tetrabromobiphenyl or 2,4-dihydroxy-3,5-dibromobenzophenone.
The polymeric compounds containing phenolic hydroxyl groups are primarily condensation resins of phenols with carbonyl compounds. Preferred reactants in this connection are the known condensation products which are customarily used as constituents of o-naphthoquinone diazide layers. Phenol-formaldehyde novolacds or cresol-formaldehyde novolacs are particularly preferred for this reason. Use of the esterification products of these resins has the advantage that the presence of unesterified phenolic compound causes no problems, since such material is present in the mixture in any event. Additional useful phenolic resins include the condensation products of pyrogallol and acetone described in British Pat. No. 1,113,759. The polycondensation products of polyhydroxybenzophenones and formaldehyde described in German Offenlegungsschrift No. 2,847,878 can also be utilized.
It is supposed that, in the esterification of the mixture of low molecular weight phenol and polymeric phenol with the sulfonyl halide, the low molecular weight constituent reacts preferentially. This belief is based on the fact that, even at relatively low proportions of low molecular weight phenol, the technical properties of the mixed esterification product in copying and printing are predominantly determined by this low molecular weight proportion and differ markedly from the esterification products formed from pure phenolic resin and naphthoquinonediazidesulfonic acid described in German Pat. No. 865,890.
The proportion of naphthoquinonediazidesulfonic acid ester relative to the non-volatile constituents in the whole light-sensitive mixture can be of the same order of magnitude as in known naphthoquinone diazides. However, the proportion of ester can also be considerably higher, particularly if the esterification product still contains some unesterified phenolic resin. In general, said proportion is from about 5 to about 50 weight percent, preferably from about 10 to about 30 weight percent.
The ight-stable, water-insoluble, alkali-soluble, film-forming phenolic resins present in the mixture of the invention have a molecular weight of about 300 to about 5,000 and are prepared by subjecting phenol or a substituted phenol to a condensation reaction with formaldehyde. Suitable substituted phenols include cresol, xylenol, butylphenol and the like. Particularly preferred alkali-soluble, film-forming phenolic resins include phenol-formaldehyde novolacs, cresol-formaldehyde novolacs and phenol-modified xylenol-formaldehyde novolacs. The proportion of phenolic resin ranges from about 50 to about 90 weight percent of the non-volatile constituents of the total mixture. Preferably, the phenolic resin comprises from about 65 to about 85 weight percent of the non-volatile content of the mixture.
The invention makes it possible to handle without risk all constituents of the light-sensitive mixture without the necessity of accepting at the same time any significant disadvantages in the copying or printing performance, i.e, a reduction in light-sensitivity, a decrease in the resistance of the copying layer to developer, a loss of gradation, a reduction in image contrast, or a decrease in the length of a printing run.
An electrolytically roughened and anodically oxidized aluminum plate having an oxide layer weighing about 3 g/m2, was immersed briefly in a 0.1% aqueous solution of polyvinylphosphonic acid at 80� C. and dried. A filtered solution of
1.82 parts naphthoquinonediazidesulfonic acid ester described below,
0.215 part 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride,
0.07 part 2,3,4-trihydroxybenzophenone,
6.621 parts cresol/formaldehyde novolac having a melting range of 105�-120� C. according to DIN 53,181 and
0.079 part Crystal Violet in
91.195 parts of a solvent mixture comprising 5 parts by volume tetrahydrofuran, 4 parts by volume ethylene glycol monomethyl ether and 1 part by volume butyl acetate was applied to the pretreated support and dried. The resulting light-sensitive material was exposed imagewise under a half-tone positive original and was then developed with the following solution:
5.3 parts sodium metasilicate.9H2 O
3.4 parts trisodium phosphate.12H2 O and
0.3 part anhydrous sodium dihydrogen phosphate in
91.0 parts water.
The resulting printing plate provided a large number of copies on an offset printing machine. The printing and copying properties of the plate were essentially the same as those of a corresponding plate containing an equivalent quantity of 2,3,4-tris-[1,2-naphthoquinone-2-diazide-5-sulfonyloxy]-benzophenone instead of the napththoquinonediazidesulfonic acid ester mixture described below.
A solution of 25.5 parts 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride in 442 parts acetone was clarified with active charcoal. 26.3 parts of the above-mentioned cresol-formaldehyde novolac and 4.4 parts 2,3,4-trihydroxybenzophenone were dissolved in the solution and a solution of 11.9 parts NaHCO3 in 124 parts water and 160 parts saturated sodium chloride solution were added to the mixture. The mixture was stirred for 10 minutes and allowed to stand. The lower phase was then discarded and the acetone solution was allowed to run, in the course of a few minutes, into a solution of 6 parts HCl (30%) and 1,500 parts water. The yellow, flocculant, precipitated reaction product was vacuum filtered, washed with water and dried. The yield amounted to 48 parts by weight. The product had a diazo nitrogen content of 4.7 percent and a water content of 1.8 percent.
The following ingredients were reacted analogously to the procedure described in Example 1:
25 parts 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride
1 part 2,2',4,4'-tetrahydroxydiphenyl sulfide
2.6 parts 2,3,4-trihydroxybenzophenone and
25 parts of the novolac described in Example 1.
40 parts of the novolac described in Example 1,
8.35 parts of the condensation product of 2 moles 2,3,4-trihydroxybenzophenone and 1 mole formaldehyde (described in German Offenlegungsschrift No. 2,847,878, Example 1) and
48.2 parts 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.
The following reactants were reacted as in Example 1:
13.4 parts of the above-described condensation product of 2,3,4-trihydroxybenzophenone and formaldehyde, and
53.9 parts 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.
3.83 parts naphthoquinonediazidesulfonic acid ester described below,
0.21 part 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride,
4.31 parts of the novolac described in Example 1, and
0.08 part Crystal Violet in
91.50 parts of a solvent mixture comprising 5 parts by volume tetrahydrofuran, 4 parts by volume ethylene glycol monomethyl ether and 1 parts by volume butyl acetate,
and was dried. The light-sensitive material was exposed and developed as in Example 1 and gave a planographic printing plate which produced long printing runs. The technical properties of the plate in copying and printing were substantially the same as those of the comparison plate described in Example 1 containing a low molecular weight naphthoquinonediazidesulfonic acid ester.
Similar results were obtained if an equal quantity of the reaction product formed from 37 parts 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride, 18.6 parts of a polycondensation product formed from pyrogallol and acetone and 2.3 parts 2,3,4-trihydroxybenzophenone were used instead of the above-described naphthoquinonediazidesulfonic acid ester.
7 parts naphthoquinonediazidesulfonic acid ester described in Example 1 and
23 parts of a cresol/formaldehyde novolac having a softening range of 105�-120� C., measured by the capillary method of DIN 53,181, in
83 parts of a solvent mixture composed of
82 percent ethylene glycol ethyl ether-acetate
9 percent butyl acetate and
9 percent xylene,
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