EP0118846B1 - Zweikomponenten-Diazotypiematerial - Google Patents

Zweikomponenten-Diazotypiematerial Download PDF

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Publication number
EP0118846B1
EP0118846B1 EP84102210A EP84102210A EP0118846B1 EP 0118846 B1 EP0118846 B1 EP 0118846B1 EP 84102210 A EP84102210 A EP 84102210A EP 84102210 A EP84102210 A EP 84102210A EP 0118846 B1 EP0118846 B1 EP 0118846B1
Authority
EP
European Patent Office
Prior art keywords
diazonium
toluenesulfonate
morpholino
benzenediazonium
dibutoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84102210A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0118846A3 (en
EP0118846A2 (de
Inventor
Siegfried Dr. Scheler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT84102210T priority Critical patent/ATE43923T1/de
Publication of EP0118846A2 publication Critical patent/EP0118846A2/de
Publication of EP0118846A3 publication Critical patent/EP0118846A3/de
Application granted granted Critical
Publication of EP0118846B1 publication Critical patent/EP0118846B1/de
Expired legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

  • the invention relates to a two-component diazotype material consisting of a support and a light-sensitive layer of at least one diazonium compound which is derived from p-phenylenediamine and carries a basic, heterocyclic radical in the 4-position and ether groups in the 2- and 5-position, coupling component and acidic stabilizer.
  • Two-component diazotype materials made from a support with a light-sensitive layer made from a diazonium compound, coupling component and acid stabilizer are known.
  • the diazonium compound When exposed to actinic radiation, the diazonium compound is decomposed into colorless, non-couplable compounds at the points hit by the light.
  • the development of the two-component diazo material is usually accomplished with dry or wet ammonia gas.
  • the acidic stabilizer is neutralized and, at the same time, the coupling reaction is initiated by changing the pH in the light-sensitive layer at the points not hit by the light between the diazonium compound remaining there and the coupling component.
  • diazonium compounds which are derived from p-phenylenediamine and are substituted in the 2- and 5-position by ether groups, in addition to their high photosensitivity in the spectral range around 400 nm, are particularly notable for their good stability and their coupling activity sufficient for many applications award.
  • these diazonium salts couple with many coupling components to form strong and brilliant azo dyes with high optical density.
  • Particularly suitable are those compounds which are substituted in the 4-position relative to the diazonium group by a heterocyclic radical, for example a morpholine radical, and in the 2- and 5-positions by alkoxy radicals having 1 to 6 carbon atoms. These connections are easily accessible.
  • Such compounds are, for example, 4-N-morpholino-benzene diazonium salts which are in the 2- and 5-position by an alkoxy group with longer alkyl radicals, e.g. B. an n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, n-pentyloxy, iso-pentyloxy, hexyloxy and cyclohexyloxy group, are substituted.
  • These compounds are also distinguished from the 2,5-disubstituted dimethoxy and diethoxy compounds by a higher thermal stability and a higher coupling activity.
  • the hues of the blue coupling dyes are shifted from reddish to greenish blue with increasing number of carbon atoms in the alkoxy radical.
  • Greenish blue azo dyes in combination with orange and brown azo dyes give neutral black tints and are therefore particularly suitable for black settings.
  • the stability and coupling activity of a diazonium compound are influenced not only by the diazonium salt cation, but also by the diazonium salt anion.
  • the diazonium compounds are salts of inorganic acids, e.g. B. hydrochloric acid, sulfuric acid, phosphoric acid, borofluorohydric acid, hexafluorophosphoric acid, or as diazonium chloride double salts with zinc chloride, cadmium chloride and tin tetrachloride before. Because of their good water solubility, the sulfuric acid salts and the zinc chloride double salts are particularly suitable for aqueous sensitizing preparations.
  • Organic sensitization preparations are used in particular in the case of diazonium tetrafluoroborates and the diazonium hexafluorophosphates.
  • a disadvantage of the most commonly used diazonium chlorides, hydrogen sulfates, tetrafluoroborates and the diazonium chloride double salts with zinc chloride and cadmium chloride is their relatively low thermal stability and their excessive coupling activity.
  • Two-component diazotype material which contains these diazonium salts in the light-sensitive layer, develops sufficiently quickly in most commercially available duplicating devices, but shows a significantly reduced shelf life.
  • the diazonium hexafluorophosphates are thermally considerably more stable than the aforementioned diazonium salts and diazonium chloride double salts, but show considerable disadvantages in their coupling activity.
  • Two-component diazotype material with these diazonium hexafluorophosphates can be stored very well, but develops only slowly, so that the maximum achievable optical density of such a diazotype material is only achieved after repeated development. However, a low willingness to develop is not acceptable for the usual duplication.
  • a disadvantage of many high-light-sensitive two-component diazo materials currently used in practice is that these materials cannot be stored sufficiently or cannot be developed sufficiently quickly in the high-performance duplicating devices. Shelf life and willingness to develop are in opposite directions, so that a two-component diazo material with good shelf life is generally more difficult to develop than one with low shelf life. A good shelf life is particularly required where there is only a small copy requirement or where the storage takes place in extreme climatic conditions, for example in a humid tropical climate.
  • the willingness to develop and the shelf life of a two-component Diaztype materials are determined by the acidic stabilizer in the light-sensitive layer and by the development conditions and especially by the coupling activity of the diazonium compound and the coupling component.
  • the coupling rate of a diazonium compound is in turn determined by the chemical constitution of the diazonium salt cation and the diazonium salt anion.
  • the solution to this problem is based on a two-component diazotype material mentioned at the outset, consisting of a layer support and a light-sensitive layer of at least one diazonium compound which is derived from p-phenylenediamine and a basic, heterocyclic radical in the 4-position and in 2- and 5 Position carries ether groups, coupling component and acid stabilizer, and it is characterized in that the diazonium compound is present as benzene or toluenesulfonate.
  • the p-toluenesulfonate is particularly suitable as the toluenesulfonate.
  • the diazonium salts of the same diazonium cation with naphthalene sulfonic acid, sulfosalicylic acid and chlorinated benzenesulfonic acid are not sufficiently soluble in aqueous sensitizing preparations.
  • naphthalene sulfonates are used in two-component diazotype materials, discoloration of the exposed base is observed even with increasing storage time.
  • diazonium salts of sulfonic acids of aromatic mono- and dicarboxylic acids are known, which are characterized by high heat resistance, low flammability and better storage stability of the diazotype materials prepared with these compounds.
  • the solubility of these diazonium salts in the customary aqueous and organic sensitizing preparations is not entirely sufficient, despite the use of solvent additives. It is therefore only possible to produce sensitization preparations with a low diazo concentration. This disadvantage leads to considerable problems in terms of coating technology.
  • the diazonium salts are obtained as reaction products of benzene, p-toluenesulfonic acid or o-toluenesulfonic acid or their alkali metal salts and a diazonium compound.
  • the reaction is usually carried out in a weakly acidic, aqueous solution and the resulting precipitate of the diazonium sulfonate is isolated by filtration and washed neutral with a saturated saline solution.
  • the diazonium compounds used for the reaction with the aromatic sulfonic acid the readily water-soluble diazonium chlorides, diazonium hydrogen sulfates or diazonium zincates known for sensitizing preparations can be used. It is not necessary to isolate the diazonium salt as chloride, hydrogen sulfate or zincate during production.
  • Mixtures of diazonium compounds, at least one of which is a benzene or toluenesulfonate, can also be used according to the invention. In these cases, at least 75 percent by weight of the benzene or toluenesulfonate, based on the diazonium compounds present, is present.
  • the aqueous diazonium salt solution after the diazotization of the corresponding amine salt is sufficient as the reaction medium. Since zinc and zinc salts can be dispensed with in the production of the diazonium sulfonates, the costly isolation and removal of zinc salts from the production waste water in the case of previous conventional diazo production processes is eliminated.
  • the diazonium salts according to the invention are sensitive to high light and, like the known diazonium salts, are photolytically decomposed. They dissolve equally well in water and organic solvents and are therefore suitable for both aqueous and organic or aqueous / organic sensitizing preparations. Their stability is better than that of the known diazonium chlorides, hydrogen sulfates, tetrafluoroborates and diazonium chloride double salts with zinc chloride, cadmium chloride and tin tetrachloride and reaches that of the known diazonium hexafluorophosphates. Their coupling speed is sometimes greater than that of the known diazonium salts and diazonium chloride double salts and considerably higher than that of the tetrafluoroborates and hexafluorophosphates.
  • the two-component diazo materials according to the invention can also be stored very well, especially under warm, humid climatic conditions. They develop strong, brilliant color tones and show no undesirable discoloration of the exposed and developed diazo material background due to photolysis.
  • the diazonium sulfonates or the two-component diazotype materials produced therewith according to Invention differ in the sum of their properties: solubility, durability, willingness to develop and diazotype material background - advantageously from the commercially available diazonium salts of the same cation and the two-component diazotype materials produced therewith.
  • Sensitization preparations that are used for the production of two-component diazo material are easy to produce.
  • the coupling component and the acid stabilizers they also contain other additives customary in diazo coating preparations.
  • Examples of coupling components which can be used are: dihydroxynaphthalenes, dihydroxynaphthalene mono- and disulfonic acids and their amides and substituted amides, ⁇ - and ⁇ -hydroxynaphthoic acid amides and correspondingly substituted amides, resorcinol and its halogenated and alkyl or alkoxylated derivatives, resorcylic acids, optionally with halogen substituted, resorcylic acid amides and substituted amides, compounds with active methylene groups, such as acetoacetyl and cyanoacetyl derivatives, mono- and polyhydroxy-diphenyls, polyhydroxy-diphenyl sulfides, aminophenol derivatives, pyrazolone derivatives and the like. a.
  • Known compounds such as acid stabilizers such as citric acid, tartaric acid, boric acid, sulfosalicylic acid, p-toluenesulfonic acid and the like can be used as an additive to the diazo coating compositions.
  • acid stabilizers such as citric acid, tartaric acid, boric acid, sulfosalicylic acid, p-toluenesulfonic acid and the like
  • compounds for increasing contrast such as zinc chloride, aluminum sulfate or nickel sulfate, antioxidants such as thiourea or thiourea derivatives and dyes in small concentrations, such as methyl violet, alizarinirisol and the like.
  • development accelerators such as glycerol, glycerol mono-, di- and triacetate, urea and alkyl-substituted ureas u. a., finely divided or colloidal silicon dioxide or aluminum oxide and / or aqueous dispersions or colloidal solutions of organic film-forming binders, such as polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose and the like. a. or latex-like dispersions of polyvinyl acetate, polyvinyl chloride, polyvinyl chloride acetate, polyvinylidene chloride, polyacrylonitrile or polymethyl methyl acrylate.
  • Suitable film-forming binders are cellulose ethers, such as ethyl cellulose, cellulose esters, such as cellulose acetate, acetopropionate, butyrate, acetobutyrate, vinyl polymers, such as polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride. Vinyl acetate copolymers, poly (methyl methacrylate) copolymers of alkyl acrylates and acrylic acid or polyphenylene oxides or ethylene glycol / isophthalic acid / terephthalic acid terpolymers.
  • All conventional opaque and transparent materials are suitable as a layer support for the two-component diazo layer.
  • a film made of polyethylene terephthalate is preferably used as the support.
  • the two-component diazo material according to the invention is processed, as is customary, by imagewise exposure under a transparent template with a light source rich in ultraviolet and short-wave visible radiation, for example with a high-pressure mercury lamp or a fluorescent fluorescent lamp and subsequent development with moist or dry ammonia gas in the case of normal or elevated temperature.
  • a light source rich in ultraviolet and short-wave visible radiation for example with a high-pressure mercury lamp or a fluorescent fluorescent lamp and subsequent development with moist or dry ammonia gas in the case of normal or elevated temperature.
  • a coating solution of the composition given below is divided into 6 portions of 100 g each (paint samples 1 to 6).
  • Each lacquer sample is applied with the aid of a 10 cm wide die coater with a 0.16 mm gap width to a glass-clear polyethylene terephthalate film 125 ⁇ m thick provided with a conventional adhesive layer, dried in a forced-air drying cabinet at 90 ° C for 1 minute and the diazo film samples obtained in this way correspond to the lacquer samples with 1 numbered to 6.
  • the layer weight of each film sample is 6.8 g / m 2.
  • 4-N-Morpholino-2,5-dibutoxy-benzenediazonium sulfonates were prepared with the following aromatic sulfonic acids (Table 3). The solubility of the 4-N-morpholino-2,5-dibutoxy-benzenediazonium sulfonates was determined in water at 23 ° C.
  • the water solubility of the diazonium sulfonates 1 and 2 according to the invention is better by a factor of about 10 to 20 than that of the diazonium sulfonates 3 to 9.
  • the diazonium sulfonates 1 to 8 are good in organic solvents and the diazonium sulfonate 9 is significantly less soluble.
  • the diazoniumbenzene sulfonates and toluenesulfonates according to the invention can be used both for the production of aqueous and organic sensitization preparations and provide highly light-sensitive two-component diazotype materials which, despite good shelf life, can be developed very quickly.
  • a 125 ⁇ m thick polyethylene terephthalate film provided with a conventional adhesive layer is coated on the subbed surface with a solution of the following composition:
  • the solids content is 9.7 percent by weight.
  • Coating was carried out using a 10 cm wide die-caster with a 0.16 mm gap width and then dried in a forced-air drying cabinet at 90 ° C. Layer weight: 7.1 g / m 2 . A portion of the film pattern produced in this way is exposed, as described in Example 1, under a grid template, then developed and the visual contrast is determined (pattern).
  • a second section of the unprocessed film sample was stored for 7 days at 50 ° C and 60% relative humidity and then also exposed under a grid, developed and the contrast determined.
  • the contrast loss of the stored film sample is only very small compared to the comparison film sample and can hardly be determined practically.
  • the pattern with the diazonium o-toluenesulfonate according to the invention advantageously differs from that with the commercial diazonium tetrafluoroborate.
  • a base paper customary in the diazo type which is coated on one side with a primer of silica and polyvinyl acetate, is coated on the precoated surface with an aqueous solution of the following composition:

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Pyrane Compounds (AREA)
EP84102210A 1983-03-09 1984-03-02 Zweikomponenten-Diazotypiematerial Expired EP0118846B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84102210T ATE43923T1 (de) 1983-03-09 1984-03-02 Zweikomponenten-diazotypiematerial.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3308395 1983-03-09
DE19833308395 DE3308395A1 (de) 1983-03-09 1983-03-09 Zweikomponenten-diazotypiematerial

Publications (3)

Publication Number Publication Date
EP0118846A2 EP0118846A2 (de) 1984-09-19
EP0118846A3 EP0118846A3 (en) 1987-05-27
EP0118846B1 true EP0118846B1 (de) 1989-06-07

Family

ID=6192985

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84102210A Expired EP0118846B1 (de) 1983-03-09 1984-03-02 Zweikomponenten-Diazotypiematerial

Country Status (12)

Country Link
US (1) US4590143A (enrdf_load_stackoverflow)
EP (1) EP0118846B1 (enrdf_load_stackoverflow)
JP (1) JPS59168437A (enrdf_load_stackoverflow)
AT (1) ATE43923T1 (enrdf_load_stackoverflow)
BR (1) BR8401009A (enrdf_load_stackoverflow)
CA (1) CA1220065A (enrdf_load_stackoverflow)
DE (2) DE3308395A1 (enrdf_load_stackoverflow)
DK (1) DK105584A (enrdf_load_stackoverflow)
ES (1) ES529991A0 (enrdf_load_stackoverflow)
FI (1) FI74155C (enrdf_load_stackoverflow)
NO (1) NO840851L (enrdf_load_stackoverflow)
ZA (1) ZA841583B (enrdf_load_stackoverflow)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2732328B2 (ja) * 1992-03-06 1998-03-30 富士写真フイルム株式会社 赤外レーザー用感熱記録材料
DE69708795T2 (de) * 1996-08-26 2002-08-08 Fuji Photo Film Co., Ltd. Thermisches Aufzeichnungsmaterial

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2809189A (en) * 1957-10-08 Method of producing stabilized
BE580370A (enrdf_load_stackoverflow) * 1958-07-16
NL132291C (enrdf_load_stackoverflow) * 1961-01-25
US3153592A (en) * 1962-05-15 1964-10-20 Dietzgen Co Eugene Complex salt diazotype photoprinting materials
US3522048A (en) * 1965-12-09 1970-07-28 Gaf Corp Two-component heat developing diazotypes
US3719491A (en) * 1968-06-18 1973-03-06 Gaf Corp Diazo-type reproduction process
CH647229A5 (de) * 1981-01-26 1985-01-15 Andrews Paper & Chem Co Inc Lichtempfindliche diazoniumsalze, verfahren zu deren herstellung und diazotypiematerialien.
DD156740A1 (de) * 1981-03-04 1982-09-15 Rainer Haessner Diazotypiematerial
DE3472472D1 (en) * 1983-04-13 1988-08-04 Fuji Photo Film Co Ltd Heat sensitive recording materials

Also Published As

Publication number Publication date
ZA841583B (en) 1984-10-31
FI840917A0 (fi) 1984-03-07
ES8505118A1 (es) 1985-05-01
DE3478647D1 (en) 1989-07-13
EP0118846A3 (en) 1987-05-27
NO840851L (no) 1984-09-10
ES529991A0 (es) 1985-05-01
EP0118846A2 (de) 1984-09-19
JPH0361180B2 (enrdf_load_stackoverflow) 1991-09-19
DK105584D0 (da) 1984-02-27
DE3308395A1 (de) 1984-09-13
DK105584A (da) 1984-09-10
FI74155B (fi) 1987-08-31
FI840917L (fi) 1984-09-10
ATE43923T1 (de) 1989-06-15
FI74155C (fi) 1987-12-10
JPS59168437A (ja) 1984-09-22
US4590143A (en) 1986-05-20
BR8401009A (pt) 1984-10-16
CA1220065A (en) 1987-04-07

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