EP0001617B1 - Matériau pour diazotypie - Google Patents

Matériau pour diazotypie Download PDF

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Publication number
EP0001617B1
EP0001617B1 EP78101128A EP78101128A EP0001617B1 EP 0001617 B1 EP0001617 B1 EP 0001617B1 EP 78101128 A EP78101128 A EP 78101128A EP 78101128 A EP78101128 A EP 78101128A EP 0001617 B1 EP0001617 B1 EP 0001617B1
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EP
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Prior art keywords
coupler
blue
diazo
hydroxy
molar ratio
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Expired
Application number
EP78101128A
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German (de)
English (en)
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EP0001617A1 (fr
Inventor
Siegfried Dr. Scheler
Heinz Schäfer
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Hoechst AG
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Hoechst AG
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    • 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
    • G03C1/58—Coupling substances therefor

Definitions

  • the invention relates to a diazo material with a diazo component and a coupling component that provides a black color image in the light-sensitive layer.
  • Diazotype materials consist of a layer support and a photosensitive layer applied thereon, comprising essentially a diazo component and a coupling component, which can be coupled together to form an azo dye. If such a material is exposed through an original, the diazo component is destroyed at the points hit by the radiation. Subsequent treatment of the latent copy obtained with a basic medium such as moist ammonia gas, dry ammonia gas or alkaline solution results in the coupling reaction of the undestroyed diazo with the coupling component, the azo dye being produced in the unexposed areas in accordance with the template.
  • a basic medium such as moist ammonia gas, dry ammonia gas or alkaline solution
  • DE-B-19 23 115 discloses a two-component diazo material that provides a black color image during wet development.
  • the material contains two coupling components in the photosensitive layer, one of which couples to a blue dye when used alone and the other to a yellow dye when used alone.
  • 4-Diazo-2,5-dialkoxy-phenylmorpholine is used as the diazo component and a substituted 2-hydroxy-3-naphthoic acid - N ".”
  • An acetoacetamide is used as the yellow coupler.
  • the known black copying diazo materials can generally be used to produce copies with satisfactory sensitometric and application properties.
  • these materials according to the different processes used today in blueprint technology, such as development with moist ammonia gas, development with dry ammonia gas under pressure and development with alkaline solutions at different temperatures, there are sometimes considerable color differences when developing the same material. So you get e.g. in conventional development with moist ammonia gas at elevated temperature, copies with black tones, while in development with dry ammonia gas under pressure, copies with sepia tones are obtained. Similar hue differences can occur if such a diazo material is developed with moist ammonia gas at different temperatures.
  • black-line copying diazotype materials Another disadvantage of these black-line copying diazotype materials is that copies of different colors are often obtained from originals of different densities, in particular from halftone originals. Such two-tone copies are unsuitable for many applications due to their different spectral properties. This is especially the case if there is a transparent diazo copy, i.e. H. of an intermediate diazo original, one or more generation copies are to be made with the same diazo type material. If the information on the intermediate diazo copy is very small, for example in the case of a diazo microfilm copy, then there may be significant loss of detail either during the first generation of diazo, but mostly determined during the subsequent second and third generation of diazo, either through amplification or through weakening.
  • a process for the development of diazotype materials is also known (DE-A-23 25 999), in which the diazotype material is substituted as a 2,5-dialkoxy-4-morpholino-benzene diazonium salt as the diazo component and a combination of one substituted on the aryl radical of the carbonamide group as the coupling component Contains 2-hydroxy-3-naphthoamide and one or two yellow couplers.
  • Substituted tetrahydroxydiphenyl sulfides or substituted tetrahydroxy-diphenyl sulfones and hydroxylphenyl derivatives of urea or thiourea are used as yellow couplers.
  • black color tones With the imagewise exposure of originals of different densities and the subsequent development with moist ammonia gas, black color tones can be achieved within a large density range. When developing with dry ammonia gas under pressure, however, violet to sepia-colored tones are produced.
  • the object of the invention is to provide a diazo material with which copies can be made Have a black shade produced, which, under different development conditions, delivers copies with the same black shades as possible and with good color stability.
  • the molar ratio of diazo component to coupling component is preferably in the range of 1: (1, 1-1.4).
  • a molar ratio of 1: 1.3 has proven to be particularly favorable.
  • diazotype material which is balanced in its components can be made available which, regardless of its type of development, can be copied with dark violet to bluish black, i.e. with moist or dry ammonia gas or with the aid of alkaline solution at different pressure and temperature conditions. in all black shades.
  • the copies also have high visual contrast, a medium to flat gradation and good generation ability.
  • the diazo material according to the invention has an excellent shelf life and can be used universally.
  • the diazo component additionally contains a 4 - (dialkylamino) benzenediazonium salt, the d-os molar ratio of 2.5 - dialkoxy - 4 - morpholinobenzene diazonium salt to 4 - (dialkylamino) benzenediazonium salt being in the range from (5 to 7): 1 .
  • a molar ratio of about 6.5: 1 is particularly favorable.
  • the molar ratio of blue to yellow coupler is reduced below the specified limit, the coupling is given a more yellow-greenish dark shade. The same applies if the molar ratio of blue to red-brown couplers is outside the specified limit range. Exceeding the coupling leads to greenish-blue shades, falling below violet-blue shades. Higher coupler concentrations lead e.g. to an unnecessary excess of unreacted coupling components and are therefore not appropriate.
  • the molar ratio of diazo component to coupling component is therefore preferably in the range given above.
  • a compound of the structural formula given, where R is n-butoxy and X as the fluoborate anion, can be used particularly advantageously.
  • a compound with R equal to n-propyl and X as fluoborate anion is very particularly advantageous.
  • the diazotype material according to the invention contains 2,5 - di - butoxy - 4 - morpholino - benzenediazonium fluoroborate and 4 - (di - propylamino) - benzenediazonium fluoroborate, 6 - methoxy - 2 - hydroxy - 3 - naphthoic acid - N (3 - morpholinopropyl) - amide, 2 - methyl - 1,3 - dihydroxy - benzene and 2,2 ', 4,4' - tetrahydroxy diphenyl sulfide.
  • a diazonium salt mixture By using a diazonium salt mixture, it is possible to control the hue from the diazo component as well.
  • a diazotype material In addition to almost the same sensitivity to light, such a diazotype material is characterized by its insensitivity to different development processes and development conditions. Copies made with this material develop into practically the same color, completely neutral black shades.
  • the diazonium salts and coupling components used are known, customary compounds.
  • the diazo composition is usually applied to the support in the form of a solution of the individual components in a solvent or a solvent mixture. After drying, the photosensitive obtained can then Layer are exposed imagewise in a known manner and developed.
  • the diazotype constituents are preferably applied to the layer support from organic medium which contains a film-forming binder.
  • concentration of the azo dye-forming constituents in the binder can vary between approximately 15 and 30 parts by weight per 100 parts by weight of binder.
  • Suitable binders are cellulose ethers, such as ethyl cellulose, cellulose esters, such as cellulose acetate, triacetate, acetopropionate, butyrate and acetobutyrate, vinyl polymers, such as polyvinyl acetate, polyvinylidene chloride, vinyl chloride / vinyl acetate copolymers, poly (methyl methacrylate) and alkylactic methyl acrylate Acrylic acid or polyphenylene oxides or ethylene glycol / isophthalic acid RE erephthalic acid terpolymers.
  • cellulose ethers such as ethyl cellulose
  • cellulose esters such as cellulose acetate, triacetate, acetopropionate, butyrate and acetobutyrate
  • vinyl polymers such as polyvinyl acetate, polyvinylidene chloride, vinyl chloride / vinyl acetate copolymers, poly (methyl methacrylate) and alkylactic methyl acrylate
  • the light-sensitive layer can also contain acidic stabilizers and other diazotype auxiliaries.
  • Suitable acidic stabilizers which prevent the diazonium salts from coupling too early with the coupling components are organic acids such as 5-sulfosalicylic acid. Such organic acids used for stabilization are preferably used in concentrations of about 4-8 parts by weight per 100 parts by weight of binder.
  • metal salts e.g. Zinc chloride, which, in addition to their stabilizing effect, contribute in particular to improving the contrast of the developed copy.
  • substances that accelerate development are added to the light-sensitive layer.
  • Such substances are e.g. Carboxylic acid esters from aliphatic and aromatic mono- or dicarboxylic acids and monohydric low-aliphatic alcohols, and esters from carboxylic acids and polyhydric aliphatic alcohols.
  • the glycerol esters of lower aliphatic acids e.g. Glycerol and glycerol triacetate used.
  • hygroscopic agents such as glycol, glycerin etc. can be used to regulate the moisture balance in the light-sensitive layer and to improve the exposed areas of the copy, suitable dyes in a low concentration, e.g. Methyl violet can be added.
  • anti-yellowing agents e.g. Thiourea or thiourea derivatives can be added.
  • inorganic fine-particle pigments are used as so-called “slip agents", e.g. Silicic acid, aluminum oxide etc. added.
  • Suitable supports for the light-sensitive layers are all customary support materials, e.g. coated or uncoated opaque and transparent paper, textiles, cellulose esters such as cellulose 2 1/2 and cellulose triacetate, polyesters such as polyethylene terephthalate, vinyl polymers such as polyvinyl acetate or polystyrene.
  • the light-sensitive layer can also be a self-supporting layer, i.e. it is not absolutely necessary for the coating composition to be adhered to a layer support.
  • a visual optical density of about 1-2.5 is achieved after the development of the light-sensitive layer. If the visual optical density is less than 1.0, the diazo material produced in this way generally provides copies with only a low contrast, which is insufficient for practical use. On the other hand, if the visual optical density is above 2.5, such a diazotype material is usually too light-insensitive and, after image-wise exposure and development, also provides copies with too high a contrast, so that if the support is transparent, the generation capacity of these diazocopies is very limited is.
  • a basecoat (BL) of 7.5% cellulose acetopropionate in a mixture of acetone, methanol, butanol and glycol monomethyl ether is used for the diazotype materials produced in the examples.
  • the diazo materials produced according to the examples are developed using three different development processes (EV 1-EV 3) and the color shades obtained are assessed visually for comparison.
  • EV 1 is the development with moist ammonia gas at 60-70 ° C
  • EV 2 is the development with dry ammonia gas under pressure at 20-25 ° C
  • EV 3 is the development with an alkaline developer solution at 40-45 ° C (bath development) is displayed.
  • the alkaline developer solution (EL) consists of ethanolamine, water and an alkylphenol polyglycol ether as a wetting agent.
  • Each of the solutions is then applied to a polyethylene terephthalate support provided with an adhesive layer in such a way that, after drying, the diazotype materials obtained can develop to an optical solid density of approximately 1.8-2.0, measured using a green filter (Kodak Wratten NR 93) .
  • the solids content of the individual solutions is between 8.5 and 9.0 percent by weight.
  • a first section is developed according to the development process EV 1
  • a second section according to the development process EV 2
  • a third section according to the development process EV 3.
  • the color tones achieved are assessed visually in transmitted light.
  • the blue couplers of type BK 1, 2 or 6 are obtained in a known manner by aminolysis of methyl 2-hydroxy-3-naphthoate or 6-methoxy- or 6-bromo-2-hydroxy-3-naphthoic acid methyl ester with the corresponding N, N- disubstituted alkylene diamines.
  • the blue couplers of type BK 3, 4 or 5 are obtained by known processes by aminolysis of 2-hydroxy-3-naphthoic acid chloride with the corresponding nucleus-substituted aniline derivatives.
  • the solids content is 10 percent by weight.
  • Example 2 As described in Example 1, the solution is applied to a polyethylene terephthalate film provided with an adhesive layer and dried. Subsequently, 3 pieces of approximately 10 cm 2 of equal size are cut off from the diazo material obtained in this way and each section is exposed under a silver image template until the exposed background has a visual optical density of 0.07. Sections 1, 2 and 3, each exposed in an image, are developed according to the respective development processes EV 1, EV 2 and EV 3.
  • the diazo film copies produced are viewed in transmitted light for visual assessment of the color tone. It can be seen that the unexposed areas of the three diazo film sections were developed into neutral black dyes with only very slight color fluctuations.
  • Neutral black shades are also achieved in the result if, instead of 2,5 - dibutoxy - 4 - morpholino - benzenediazonium fluoroborate, 2,5 - diethoxy - 4 - morpholino - benzenediazonium fluoroborate and instead of 4 - (dipropylamino) - benzenediazonium fluoroborate 4 - (diethylamino) - uses benzenediazonium fluoroborate.
  • the solids content of the solution is 10 percent by weight.
  • the molar ratio of blue coupler 6 - methoxy - 2 - hydroxy - 3 - naphthoic acid - N (3 - morpholinopropyl) - amide and yellow coupler 2-methylresorcinol is 0.8: 1.
  • the solution is applied to a polyethylene terephthalate film provided with an adhesive layer and dried.
  • the solids content of the solution is 10 percent by weight.
  • the molar ratio of 6 - methoxy - 2 - hydroxy - 3 - naphthoic acid - N (3 - morpholinopropyl) amide and 2,2 ', 4,4' - tetrahydroxydiphenyl sulfide is 8: 1.
  • Example 2 As described in Example 1, the solution is applied to a polyethylene terephthalate film provided with an adhesive layer, then dried and then, as described in Example 2. exposed and developed imagewise.
  • a natural transparent paper used in the diazo type is coated on one side with the following solution and dried: The solids content of the solution is 10 percent by weight.
  • the solution is applied to the transparent paper support in such a way that after drying and development of the diazo layer with moist ammonia gas, a maximum visual optical density of 1.70 is achieved.
  • the diazo material produced in this way is exposed and developed imagewise in a commercially available blueprint device under a template.
  • a standard blueprint base paper with a primer made of colloidal silica and polyvinyl acetate was coated on the pretreated surface with a filtered solution of the following composition:
  • the sensitized paper was exposed imagewise under a transparent template and developed in a commercially available blueprint device with moist ammonia gas. Neutral black dye images were obtained.

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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)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (4)

1. Matériel pour diazotypie comprenant dans la couche photosensible comme composé diazoïque un sel de 2,5 - dialcoxy - 4 - morpholinobenzènediazonium et une combinaison donnant une image colorée en noir, d'un amide de l'acide 2 - hydroxy - 3 - naphtoîque en tant que copulant bleu, d'un copulant jaune et d'un copulant rouge-brun, caractérisé en ce que le copulant bleu est un N - (ω-aminoalkyl) amide de l'acide 6 - méthoxy - 2 - hydroxy - 3 - naphtoïque, le copulant jaune est le 2-alkyl- ou le 2-aryl-1,3-dihydroxybenzène ou un cyanacétamide et le copulant rouge-brun est un composé de formule:
Figure imgb0015
dans laquelle X est =S, =SO, =S02 ou rien du tout, le rapport molaire entre les copulants bleu et jaune étant compris entre (0,7 et 0,9):1 et celui entre les copulants bleu et rouge-brun entre (6 et 12):1.
2. Matériel de diazotypie selon la revendication 1, caractérisè en ce que le rapport molaire entre le composé diazoïque et les copulants est compris entre 1:(1,1 et 1,4).
3. Matériel de diazotypie selon les revendications 1 et 2, caractérisé en ce que le composé diazoïque contient en outre un sel de 4 - (dialkylamino) benzènediazonium, le rapport molaire entre le sel de 2,5 - dialcoxy - 4 - morpholinobenzènediazonium et le sel de 4 - (dialkylamino)benzènediazonium étant compris entre (5 et 7):1.
4. Matériel de diazotypie selon les revendications 1 à 3, caractérisé en ce qu'il contient dans la couche photosensible du fluoborate de 2,5 - di - butoxy - 4 - morpholinobenzènediazonium, le fluoborate de 4 - (dipropylamino)benzènediazonium, le N-(3-morpholinopropyl)amide de l'acide 6 - méthoxy - 2 - hydroxy - 3 - naphtoïque, le'2 - méthyl - 1,3 - dihydroxybenzène et le sulfure de 2,2',4,4'-tetrahydroxydiphényle.
EP78101128A 1977-10-17 1978-10-12 Matériau pour diazotypie Expired EP0001617B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2746551 1977-10-17
DE19772746551 DE2746551A1 (de) 1977-10-17 1977-10-17 Diazotypiematerial

Publications (2)

Publication Number Publication Date
EP0001617A1 EP0001617A1 (fr) 1979-05-02
EP0001617B1 true EP0001617B1 (fr) 1981-07-22

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EP78101128A Expired EP0001617B1 (fr) 1977-10-17 1978-10-12 Matériau pour diazotypie

Country Status (13)

Country Link
US (1) US4207110A (fr)
EP (1) EP0001617B1 (fr)
JP (1) JPS5465522A (fr)
AT (1) AT382727B (fr)
BR (1) BR7806805A (fr)
CA (1) CA1122048A (fr)
DE (2) DE2746551A1 (fr)
DK (1) DK460578A (fr)
ES (1) ES474208A1 (fr)
IT (1) IT1109283B (fr)
MX (1) MX149653A (fr)
PT (1) PT68663A (fr)
ZA (1) ZA785798B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3340829A1 (de) * 1983-11-11 1985-05-23 Henkel KGaA, 4000 Düsseldorf Haarfaerbemittel
JPH0290259U (fr) * 1988-12-28 1990-07-17

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL52177C (fr) * 1938-11-17
US2545057A (en) * 1946-06-12 1951-03-13 Gen Aniline & Film Corp Diazotypes containing resorcinol sulfonic acids as coupling components
US2537001A (en) * 1947-08-06 1951-01-02 Gen Aniline & Film Corp Diazotype layers having cyan acetyl amides as azo components
US2542560A (en) * 1949-11-10 1951-02-20 Gen Aniline & Film Corp Diazotypes on plastic surfaced carrier containing 5,5' diresorcinol
BE539176A (fr) * 1954-09-08
DE1246401B (de) * 1964-11-06 1967-08-03 Kalle Ag Diazotypieverfahren, bei dem als Azokomponente ein 2-Hydroxy-3-naphthoesaeureamid verwendet wird
USB417241I5 (fr) * 1964-12-09
DE1572159C3 (de) * 1967-02-24 1975-01-16 Renker Gmbh, 5161 Lendersdorfkrauthausen Zweikomponenten· Diazotypiematerial
ZA6804932B (fr) * 1967-07-31
US3573051A (en) * 1967-07-31 1971-03-30 Eastman Kodak Co Two-component diazotype composition
US3585033A (en) * 1967-09-13 1971-06-15 Tecnifax Corp The Diazotype composition employing 3'-substituted 2-hydroxy-3-naphthanilides as couplers
GB1259849A (en) * 1968-05-06 1972-01-12 Ricoh Kk Improvements in and relating to two-component diazotype materials
JPS5213741B2 (fr) * 1972-05-22 1977-04-16
US3971663A (en) * 1974-04-11 1976-07-27 Bialczak Edward C Light-sensitive diazotype with yellow diazo couplers
US3976491A (en) * 1974-11-26 1976-08-24 Scott Paper Company Diazo compositions and diazotype materials prepared from same

Also Published As

Publication number Publication date
JPS6148145B2 (fr) 1986-10-22
US4207110A (en) 1980-06-10
EP0001617A1 (fr) 1979-05-02
PT68663A (de) 1978-11-01
IT7851488A0 (it) 1978-10-13
ATA742478A (de) 1986-08-15
DE2746551A1 (de) 1979-04-26
DK460578A (da) 1979-04-18
DE2860867D1 (de) 1981-10-29
ZA785798B (en) 1979-09-26
AT382727B (de) 1987-04-10
IT1109283B (it) 1985-12-16
MX149653A (es) 1983-12-08
CA1122048A (fr) 1982-04-20
BR7806805A (pt) 1979-05-15
ES474208A1 (es) 1979-11-01
JPS5465522A (en) 1979-05-26

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