EP0074950B1 - Materiaux diazotypes thermodeveloppables contenant un precurseur d'activateur liberant lors du chauffage une base forte - Google Patents

Materiaux diazotypes thermodeveloppables contenant un precurseur d'activateur liberant lors du chauffage une base forte Download PDF

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Publication number
EP0074950B1
EP0074950B1 EP81903099A EP81903099A EP0074950B1 EP 0074950 B1 EP0074950 B1 EP 0074950B1 EP 81903099 A EP81903099 A EP 81903099A EP 81903099 A EP81903099 A EP 81903099A EP 0074950 B1 EP0074950 B1 EP 0074950B1
Authority
EP
European Patent Office
Prior art keywords
group
groups
radical
carbon atoms
acid
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
EP81903099A
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German (de)
English (en)
French (fr)
Other versions
EP0074950A1 (fr
Inventor
Claude Ceintrey
Michel Crochemore
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.)
Rhone Poulenc Systemes SA
Original Assignee
Rhone Poulenc Systemes SA
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 Rhone Poulenc Systemes SA filed Critical Rhone Poulenc Systemes SA
Priority to AT81903099T priority Critical patent/ATE18814T1/de
Publication of EP0074950A1 publication Critical patent/EP0074950A1/fr
Application granted granted Critical
Publication of EP0074950B1 publication Critical patent/EP0074950B1/fr
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
    • 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
    • G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives
    • G03C1/615—Substances generating bases
    • 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
    • G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives

Definitions

  • the present invention relates, by way of new industrial products, to diazotype products capable of being developed by heat and the sensitive layer of which comprises a precursor of activator of the coupling reaction.
  • the present invention also relates to a thermal diazo reproduction process characterized by the use of the diazotype products of the invention.
  • Diazotype products which can be developed by heat and whose sensitive layer which is generally bi-component and which therefore comprises a diazonium salt and a coupler, contains a precursor of activator of the reaction of copulation, the activator precursor also being commonly called basic generator. Indeed in general the activator precursor releases under the action of heat a basic compound such as ammonia or an organic nitrogenous base.
  • thermolabile salt consists of a nitrogenous organic base trihaloacetate such as piperidinium trichloroacetate which liberates on heating carbon dioxide, a haloform (chloroform) and an organic nitrogenous base (piperidine).
  • a diazotype material is described, the sensitive layer of which contains an aryl diazonium salt carrying a free carboxylic group ortho to the diazonium group, a coupler and a basic generator. which releases under the action of heat a base which initiates and completes the coupling reaction.
  • the activator precursor also called base generator can be urea, thiourea or their derivatives, guanidine or its derivatives, amides or alternatively salts of trichloroacetic acid and basic compound such as ammonia, a amine, a guanidine or even a mineral base.
  • activator precursors comprising an acid part and a basic part, the acid part being an ⁇ -sulfonyl-acetate group.
  • the problem therefore arose of developing new diazotype heat-developable materials having a set of qualities capable of ensuring them a good commercial development and having in particular a good resistance to storage, a good sensitivity to the source of exposure, a speed sufficient development at not too high temperature without release of volatile products and ensuring at the same time a good intensity of the color of the image, a good definition of the image (no appearance of holes or bubbles) and a good resistance to aging after exposure and development.
  • the present invention meets precisely this goal. It has been found, and this is what constitutes the object of the present invention, new heat-developable diazotype materials, the sensitive layer of which contains a basic generator as an activator precursor of the coupling reaction generating a colored trace from of a diazonium salt and of a coupler, the basic generator comprising a basic part and an acid part, the acid part being a 2-carboxy-carboxamide group, the diazotype materials being characterized in that the basic part of the generator base consists of an alkali or alkaline earth cation or a quaternary tetraalkylammonium cation.
  • the diazotype materials according to the invention had, after exposure and development, a much better resistance to aging than the diazotype materials comprising, as activator precursors, a compound comprising a basic part and an acid part, the acid part being a 2-carboxy carboxamide group, the basic part being constituted by a basic protonated nitrogen group.
  • the activator precursor according to the invention releases a strong base, therefore having a high pKa and which is not volatile during the development heat treatment and whose presence could only be perceived as detrimental to good aging conservation.
  • the existence of this excellent resistance to aging appeared unpredictable in view of the prior art and in particular of French patent 2,056,231.
  • the basic generator can be a derivative of a phthalamic acid, a maleamic acid, or a succinamic acid or a polyhydrophthalamic acid.
  • these various basic generators which can be mixed together may moreover comprise any substituent which does not have an unfavorable effect on the sensitometric characteristics or the other properties of the heat-developable diazotype material.
  • These various substituents may be carried by the groups (L) or (R).
  • the basic generators according to the invention are derivatives of phthalamic acids, or polynydrophthalamic, succinamic or maleamic acids. These various compounds can also be represented by one of the following formulas, depending on the valence of R, and the valence of the cation M,
  • ammonia butylamine, cyclohexylamine, hydrazine, aniline, chloroaniline, trifluoromethylaniline, toluidine, xylidine, 4,4-diamino diphenylmethane, diamino-4,4 'diphenyl ether, ethylene diamine, hexamethylene diamine, cyclohexylene diamine ...
  • the diazotype materials according to the invention can be of varied nature and find their application in any field where the use of a basic generator can be recommended and where the process of developing the colored image puts at least one step into action of heating. It is thus generally a dry thermal process and according to which the sensitive layer contains, in addition to the binder, at the same time a diazonium salt, a coupling agent, a basic generator and possibly the annexed compounds and various well known those skilled in the art (acid stabilizer, reducing agent, anti-UV, humectant, contrast modifying agent, etc.); this process thus leads directly to a positive.
  • Positive images can also be obtained from diazotype products according to the invention and the sensitive layer of which comprises a diazonium salt and a basic generator, the development after exposure being ensured by a semi-wet process, by wetting the diazotype paper hot with a solution of a coupling agent.
  • diazotype materials which can be used to reproduce opaque originals by a reflex process and according to which the insolation is first carried out using infrared radiation, then destroyed in a second stage the residual diazonium salt, for example by exposure to intense ultraviolet radiation.
  • At least one of the main constituents of the diazotype material of the invention can be introduced encapsulated by any material which can be used for this purpose.
  • radicals Z By way of illustration, mention may be made, among the radicals Z, of the radicals having one of the following formulas:
  • the coupling agent can itself be very varied in nature. To this end, reference may be made to the work by J. KOSAR previously cited or even to the work by Kirk-Othmer “Encyclopedia of chemical technology edition 1978 volume 3 - Azodyes - p. 387 and following.
  • the coupling agent is generally a phenolic compound which can be a monophenol optionally substituted by various groups such as halogen atoms, alkyl, alkoxy, hydroxyalkyl, hydroxyalkoxyl, amino, sulfamido, sulfonic, carboxylic groups and / or may include urea and thiourea groups; it is known that such couplers generally give yellow or brown compounds.
  • the coupling agent can be a polyphenol or its derivatives derived from pyrocatechin, resorcin, aminoresorcinol, resorcylic acid and hydroquinone and comprising substituents such as those which have been previously defined in the context of monophenols.
  • the coupler can also be a trihydroxybenzene or one of these derivatives such as phloroglucin or its derivatives.
  • the coupler can also be a phenolic derivative of the biphenyl or naphthalene series: we can in this context cite trihydroxydiphenyl or even tetrahydroxydiphenyl, naphthols, hydroxynaphthoic acids and their derivatives, naphthalene diol, these various compounds being optionally substituted by the various groups as previously defined or used in the form of derivatives of their functional groups.
  • couplers various non-phenolic compounds such as ⁇ -diketone, acetonitrile, cyanacetylamide, sulfonamide, derivatives of acetoacetic acid, alkylmalonamate, pyronone, hydroxypyridone, oxyquinolone can be mentioned. , pyrazolone, thiophene derivatives ...
  • diazotypy it may be necessary to use a mixture of various couplers and / or diazonium salts.
  • the proportions between the diazonium salt and the coupler are according to the usual limits well known to those skilled in the art, that is to say between 0.3 and 3.
  • the quantity of base generator this latter is usually such that there is per m 2 of sensitive layer from 0.1 to 5 g and preferably from 0.5 to 3 g of base generator.
  • acid stabilizer such as organic or inorganic acids such as oxalic, citric, tartaric, para-toluenesulfonic, phosphoric acids, etc.
  • diazotype materials according to the invention can be manufactured according to the usual techniques! Es in mono or possibly in multilayers by using any suitable support such as paper, paper provided with a barrier layer to solvents, polyester, varnish layer, cellulose acetate.
  • the base generator can be laid on the same side as the other main reactive constituents of the sensitive layer.
  • the diazotype materials according to the invention are exposed using a UV source through a transparent or semi-transparent original or according to the reflex process. Thermal development is ensured by heating to a temperature between 80 ° and 160 ° C and preferably between 100 ° and 140 ° C.
  • an object of the present invention also consists of a diazo reproduction method according to which a colored image is created by selective reaction of a diazonium salt and of coupler, the method being characterized in that materials are used dyazotypes the diazotype materials according to the invention.
  • This dispersion is coated using an air knife, at a rate of 12 g / m 2 , on a heliographic paper and dried.
  • the sheet After exposure to a positive original, the sheet is developed in a thermal development machine, the heating roller of which reaches 140 ° C.
  • Example 1 Same example as Example 1 in which the Na salt of NN 'ethylene bis phthalamic acid is replaced in the pre-coating by the tetrabutyl ammonium salt.
  • Example 1 Same example as Example 1 in which the Na salt of NN 'ethylene bisphthalamic acid is replaced in the precoating with the Na salt of NN' ethylene bis succinamic acid.
  • Example 1 Same example as Example 1 in which the Na salt of NN 'ethylene bisphthalamic acid is replaced in the precoating with the Na salt of NN' ethylene bis maleamic acid.
  • This dispersion is coated using an air knife on a support for diazotypy and then dried.
  • the sheet After exposure to a positive original, the sheet is developed in a thermal development machine at 140 ° C. We get a positive blue image of the original.
  • the background whiteness (designated by B) and the optical density (designated by DO) are measured. These measurements are made immediately after development (time 0) and then after 30 days of aging in a black polyethylene pouch.
  • the starting paper has a background whiteness at most equal to 90. Furthermore, images whose background whiteness is less than 75 and where the optical density is less than or equal to 0.75 are not considered acceptable. .
  • Example 6 The same test is carried out as in Example 6, using as a base generator a calcium or magnesium salt of an -N, N 'ethylene bis phthalamic acid. A colored image is obtained whose optical density is greater than 0.75.
  • Example 6 The procedure is as in Example 6 from 100 g / l of the sodium salt of -N, N 'ethylene bis phthalamic acid, and citric acid is replaced by 10 g / l of p-toluene sulfonic acid. Furthermore, no glycerin is added. A colored image is obtained, the background whiteness is 84 while the optical density is 1.30. After an aging of 30 days the background whiteness is 80 while the optical density remains of 1.30.
  • the sheet After exposure to a positive original, the sheet is developed in a thermal machine, the roller of which is at 130 ° C.
  • the copy After exposure to a positive original, the copy is developed in a thermal machine, the roller of which reaches a temperature of 130 ° C.
  • This mixture is coated on a paper support, equalized with an air knife and then dried.
  • a sepia counter-plate After drying at 70 ° C and UV exposure under an original, a sepia counter-plate is obtained by passing through a heat machine at 120 ° C having good opacity to ultraviolet radiation.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Saccharide Compounds (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP81903099A 1980-12-02 1981-11-19 Materiaux diazotypes thermodeveloppables contenant un precurseur d'activateur liberant lors du chauffage une base forte Expired EP0074950B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81903099T ATE18814T1 (de) 1980-12-02 1981-11-19 Thermisch entwickelbare diazotypiematerialien, die einen aktivatorvorlaeufer enthalten, der beim erhitzen eine starke base abspaltet.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8025958 1980-12-02
FR8025958A FR2495343B1 (fr) 1980-12-02 1980-12-02 Materiaux diazotypes thermodeveloppables contenant un precurseur d'activateur liberant lors du chauffage une base forte. procede de diazotypie mettant en oeuvre ces materiaux

Publications (2)

Publication Number Publication Date
EP0074950A1 EP0074950A1 (fr) 1983-03-30
EP0074950B1 true EP0074950B1 (fr) 1986-03-26

Family

ID=9248760

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81903099A Expired EP0074950B1 (fr) 1980-12-02 1981-11-19 Materiaux diazotypes thermodeveloppables contenant un precurseur d'activateur liberant lors du chauffage une base forte

Country Status (21)

Country Link
US (1) US4584256A (enExample)
EP (1) EP0074950B1 (enExample)
JP (1) JPS57501931A (enExample)
KR (1) KR830007766A (enExample)
AT (1) ATE18814T1 (enExample)
AU (1) AU547595B2 (enExample)
BR (1) BR8109006A (enExample)
CA (1) CA1158474A (enExample)
DE (1) DE3174209D1 (enExample)
DK (1) DK345582A (enExample)
FI (1) FI67763C (enExample)
FR (1) FR2495343B1 (enExample)
GR (1) GR75039B (enExample)
HU (1) HU185996B (enExample)
IE (1) IE52254B1 (enExample)
IL (1) IL64419A (enExample)
NO (1) NO822624L (enExample)
PT (1) PT74055B (enExample)
RO (1) RO86617B (enExample)
WO (1) WO1982001944A1 (enExample)
ZA (1) ZA818285B (enExample)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59195237A (ja) * 1983-04-20 1984-11-06 Fuji Photo Film Co Ltd 熱現像感光材料
EP0555749B1 (en) * 1992-02-14 1999-05-19 Shipley Company Inc. Radiation sensitive compositions and processes
US6080521A (en) * 1998-06-15 2000-06-27 Andrews Paper & Chemical Co., Inc. Universal diazotype precoat for application to base papers with acidic or alkaline sizing
WO2009030887A2 (en) * 2007-09-04 2009-03-12 Biolipox Ab Bis-aromatic compounds useful in the treatment of inflammation
CN116535333B (zh) * 2023-04-06 2025-02-11 华南理工大学 一种酰胺类β晶型成核剂及其制备方法和应用

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL258232A (enExample) * 1959-11-23
US3220846A (en) * 1960-06-27 1965-11-30 Eastman Kodak Co Use of salts of readily decarboxylated acids in thermography, photography, photothermography and thermophotography
NL288596A (enExample) * 1962-02-06
US3367776A (en) * 1964-04-17 1968-02-06 Addressograph Multigraph Heat sensitive diazotype materials
FR1452286A (fr) * 1964-08-17 1966-02-25 Ibm Compositions et éléments photosensibles thermodéveloppables
US3420666A (en) * 1964-10-15 1969-01-07 Gaf Corp Two-component heat developing diazotypes
US3389996A (en) * 1964-10-15 1968-06-25 Gen Aniline & Film Corp Two-component heat developable diazotypes
DE1572048C3 (de) * 1965-09-10 1978-10-26 Hoechst Ag, 6000 Frankfurt Wärmeentwickelbares Diazotypiematerial
NL136527C (enExample) * 1966-11-07
US3625693A (en) * 1966-11-09 1971-12-07 Ricoh Kk Thermally developable diazotype copying materials
NL6905657A (enExample) * 1968-04-22 1969-10-24
GB1292607A (en) * 1968-12-28 1972-10-11 Ricoh Kk Improvements in and relating to heat-developable light-sensitive material
GB1307314A (en) * 1969-06-07 1973-02-21 Ricoh Kk Heat developable diazotype copying materials
JPS5140455A (ja) * 1974-10-03 1976-04-05 Unitika Ltd Taidenboshiseisenishugotai no seizohoho
FR2340567A1 (fr) * 1976-02-05 1977-09-02 Ozalid Group Holdings Ltd Materiau diazotype developpable par la chaleur
JPS538486A (en) * 1976-07-10 1978-01-25 Okura Denki Co Ltd Interruption backup system
US4060420A (en) * 1976-08-06 1977-11-29 Eastman Kodak Company Sulfonylacetate activator-stabilizer precursor
JPS5330322A (en) * 1976-09-02 1978-03-22 Ricoh Co Ltd Heat-type diazo copying material
US4088496A (en) * 1976-12-22 1978-05-09 Eastman Kodak Company Heat developable photographic materials and process

Also Published As

Publication number Publication date
PT74055A (fr) 1981-12-01
ZA818285B (en) 1982-11-24
FI824503A0 (fi) 1982-12-29
JPS57501931A (enExample) 1982-10-28
IL64419A (en) 1984-11-30
FI67763B (fi) 1985-01-31
FI67763C (fi) 1985-05-10
RO86617B (ro) 1985-05-01
IL64419A0 (en) 1982-03-31
CA1158474A (fr) 1983-12-13
EP0074950A1 (fr) 1983-03-30
ATE18814T1 (de) 1986-04-15
IE52254B1 (en) 1987-08-19
PT74055B (fr) 1983-04-26
IE812798L (en) 1982-06-02
FR2495343A1 (fr) 1982-06-04
FR2495343B1 (fr) 1987-02-20
DK345582A (da) 1982-08-02
BR8109006A (pt) 1983-04-12
FI824503L (fi) 1982-12-29
KR830007766A (ko) 1983-11-07
DE3174209D1 (en) 1986-04-30
RO86617A (ro) 1985-04-17
AU7807681A (en) 1982-06-17
NO822624L (no) 1982-07-30
WO1982001944A1 (fr) 1982-06-10
GR75039B (enExample) 1984-07-12
AU547595B2 (en) 1985-10-24
HU185996B (en) 1985-04-28
US4584256A (en) 1986-04-22

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