CA1066107A - Paper support with sealing layer and layer containing diazonium compound, polyvinyl alcohol and starch particles - Google Patents
Paper support with sealing layer and layer containing diazonium compound, polyvinyl alcohol and starch particlesInfo
- Publication number
- CA1066107A CA1066107A CA227,895A CA227895A CA1066107A CA 1066107 A CA1066107 A CA 1066107A CA 227895 A CA227895 A CA 227895A CA 1066107 A CA1066107 A CA 1066107A
- Authority
- CA
- Canada
- Prior art keywords
- diazotype material
- sealing layer
- light
- polyvinyl alcohol
- material according
- 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
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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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
- G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
-
- 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
- G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Diazotype material comprising a paper support, the same side of which is coated successively with a sealing layer containing as a film-forming binder polyvinyl acetate, or a copolymer of styrene with butadiene, and a light-sensitive layer having a dry weight of at most 8 g/m2 and comprising a diazonium compound, polyvinyl alcohol with a degree of hydrolysis over 75% and starch particles, whereby the weight ratio starch particles to polyvinyl alcohol is from 5 - 20:1. The diazotype material can be developed quickly and completely giving strong copies which feel immediately dry and show no appreciable curl.
Diazotype material comprising a paper support, the same side of which is coated successively with a sealing layer containing as a film-forming binder polyvinyl acetate, or a copolymer of styrene with butadiene, and a light-sensitive layer having a dry weight of at most 8 g/m2 and comprising a diazonium compound, polyvinyl alcohol with a degree of hydrolysis over 75% and starch particles, whereby the weight ratio starch particles to polyvinyl alcohol is from 5 - 20:1. The diazotype material can be developed quickly and completely giving strong copies which feel immediately dry and show no appreciable curl.
Description
)7 The invention relates to diazotype material, more particularly to - a one-component diazotype material that can be developed by applying a small amount of developing liquid c6l /llo~ve~nber ~P, Iq73 The Dutch Patent Application 72 07 099~ describes a process for mak-ing diazotype copies, in which one-component diazotype material is developed after imagewise exposure by spreading a buffered, aqueous solution of an azo-coupling component over the light-sensitive layer, in an amount between 1.,5 and 4.5 cm3 per square metre.
The diazotype paper used in the process according to the patent application mentioned above consists, in a simple embodiment, of a paper support that, after a so-called precoat layer has been applied for smoothing its surface, has been sensitized in such a way that, after drying, the diazon-ium compound has penetrated into the precoat layer to an average depth of at most 8 micrometres. The sensitization of the material is accomplished by applying an adapted concentrated diazo-solution over the precoat layer in an amount of 2-8 cm3 per square metre.
Due to the fact that, upon development only one side of the diazo-type paper is wetted with developing liquid and the developing liquid pene-trates through the precoat layer into the paper support, the diazotype copies will show a strong curl, in particular immediately after development. To avoid curling of the copy, the paper support may be provided with a sealing layer preventing the developing liquid from penetrating into the paper fibres.
Preferably, the sealing layer is applied on either side of the paper support, because otherwise curling may occur as a consequence of water penetrating into the paper fibres of the reverse side of the copy. For instance, unless the reverse side of the diazotype paper is coated with a sealing layer, the just developed copies will curl during piling, as a consequence of moisture pene-trating from the image side of one copy into the reverse side of the overlying copy.
The manufacture of non-curling or almost non-curling diazotype -1- ~F
106611~i7 paper by providing either side of a paper support with a sealing layer, then coating one side with a precoat layer and, finally, sensitizing the precoat layer by applying a small amount of concentrated diazo-solution, is cumber-some and requires a complex coating machine with long drying paths, when it is desired to manufacture the material in one machining operation and at high speed. Due to the fact that the front side of the paper is subjected to three coating operations and, on the other hand, the reverse side to one oper-ation only, it may frequently occur that the paper does not remain flat in the coating machine, in consequence of which an additional treatment of the reverse side is necessary, thus complicating the manufacture of the diazotype paper even more.
The manufacture of the diazotype paper is considerably simplified, if it would be possible to apply the light-sensitive diazonium compound as well as the further solid components of the sensitizing liquid simultaneously with the precoat over the sealing layer. However, the choice of the compon-ents for such a diazotype material is no simple matter, because a lot of demands, partly contrary to each other, must be met. For instance, the paper support must be coated with a more or less hydrophobic sealing layer on which it must be possible, without the aid of an adhesive layer, to apply a very smooth, more or less hydrophilic light-sensitive layer having sufficient adhesion both in dry and in moist condition. It should be possible to apply the components of the light-sensitive layer with sufficient adhesion to the sealing layer, using a coating liquid that contains no solvents penetrating deeply into the sealing layer, or swelling it, because the diazonium compound would otherwise be partly trapped in the sealing layer and be inaccessible to the developing liquid.
The light-sensitive layer itself may not be too thick, because the developing liquid, in order to obtain complete development of the diazotype material, must be able to penetrate through the whole thickness of the layer but, on the other hand, it must fully absorb the amount of developing liquid ~L066~7 applied, in order to obtain copies feeling dry. Further, substances reducing the durability of the diazotype material, or the quality or durability of the diazotype copy to an unacceptable level may, of course, not be incorporated in the sealing layer and the light-sensitive layer.
The invention provides for a diazotype material of the desired composition which meets the requirements with respect to durability and quality of the copy, and which, according to the developing method described in the Dutch Patent Application 72 07 099, can be developed fast and compl,ete-ly, whereby copies feeling immediately dry are obtained. The diazotype material according to the invention comprises a paper support, the same side of which is coated successively with a sealing layer containing as a film-forming binder polyvinyl acetate, or a copolymer of styrene with butadiene, and a light-sensitive layer having a dry weight of at most 8 g/m2 and com-prising a diazonium compound, polyvinyl alcohol with a degree of hydrolysis over 75% and starch particles, whereby the weight ratio starch particles to polyvinyl alcohol is from 5 - 20:1. Upon development in the process accord-ing to the Dutch Patent Application 72 07 099 the diazotype material accord-ing to the invention produces strong copies, feeling dry to the touch almost immediately and showing no or no appreciable curl.
In another aspect, the invention provides a process for the manufacture of copies, in which a diazotype material is imagewise exposed and then developed by spreading 1.5 to 4.5 cm3 per square metre of developing liquid over the light-sensitive side of the diazotype material, character-ized in that the diazotype material comprises a paper support, the same side of which is coated successively with a sealing layer containing as a film-forming binder polyvinyl acetate, or a copolymer of styrene with butadiene, and a light-sensitive layer having a dry weight of at most 8 g per square metre and comprising a diazonium compound, polyvinyl alcohol with a degree of hydrolysis of at least 75% and starch particles, whereby the weight ratio;polyvinyl alcohol to starch particles is from 1 : 5 to 20.
~ _ 3 _ 1066~07 The paper support is coated with a sealing layer containing as a binder polyvinyl acetate or a copolymer of styrene with butadiene.
The sealing layer can be applied to the support using a solution of the film-forming binder but, preferably, it is formed by means of a dispersion of the binder in water, or in a mixture of water with one or more water-miscible organic solvents, for example alcohols, ketones, glycol, and glycol esters. To sized papers the sealing layer is preferably applied from an aqueous dispersion, whereas on well-milled papers, such as natural~
transparent paper,the sealing layer is often advantageously formed from a dispersion of the binder in a mixture(of water and an organic solvent. The mixtures of water with organic solvent may contain up to 75% by volume of 1~66107 organic solvent but, in general, mixtures containing no more than 50% by volume of organic solvent are used. To form a dense coating, the dispersion layer applied is dried at increased temperature.
For the formation of the sealing layer, suitable aqueous dispersions of polyvinyl acetate and copolymers of styrene with butadiene are commercially available. If the sealing layer on the support material is formed using a polyvinyl acetate dispersion, a cross-linking agent is preferably added to the dispersion, and the polyvinyl acetate coating is cross-linked by heating it at 130-180C for some time. It has appeared that this cross-linking improves the adhesive properties of the polyvinyl acetate coating for the light-sensitive layer subsequently to be applied. Moreover, the penetration of the sensitizing liquid into the polyvinyl acetate coating is reduced to a minimum. The familiar products can be used as cross-linking agent, such as paraformaldehyde, glyoxal, and water-soluble, optionally modified, condensat-ion products of urea and melamine with formaldehyde, for example dimethylol-urea, dimethylolmelamine, hexamethylolmelamine, dimethyloltetramethoxymethyl-melamine and hexamethoxymethylmelamine. A very suitable cross-linking agent is hexamethoxymethylmelamine.
Paraformaldehyde and glyoxal are not preferably used, because they generally have an adverse effect on the durability of the diazotype material.
Used as cross-linking catalysts are acids or acid salts, for example hydrochloric acid, sulphuric acid, formic acid, acetic acid, benzenesulphonic acids such as p-toluene sulphonic acid, ammonium chloride, ammonium sulphate and aluminium sulphate.
In addition to the film-forming binder, the sealing layer may con-tain one or more fillers, in order to make it more susceptible to the sensit-izing liquid to be applied, and to improve the adherence of the light-sensit-ive layer. The filler content may not be so high that the sealing layer be-comes water-permeable. In general the weight ratio filler to binder in the sealing layer lies under 1 : 1 and preferably it is from 0.25 - 0.75 : 1.
10~6107 The familiar products can be used as fillers, such as clay, kaolin, diatoma-ceous earth, talcum, silica, barium sulphate~ titanium dioxide, zinc oxide and aluminium oxide. A preferred filler is silica with a particle size under 10 micrometres. The use of this filler in the sealing layer proves to have a favourable effect on the complete development of the diazotype material and the brilliancy of the azo-dyestuff. The sealing layer must fully cover the paper surface. The weight of the sealing layer to be applied depends largely on the surface roughness of the paper.
For papers with a smooth surface the application of a sealing layer having a dry weight of 2-5 g per square metre will mostly suffice. Papers with a rough surface require the application of a thicker layer but, in most cases, the layer need not be thicker than equivalent to a dry weight from 8 to 10 g per square metre.
Highly suitable sealing layers according to the invention are filler-free polyvinyl acetate layers applied from an aqueous dispersion, which have been cross-linked, preferably with hexamethoxymethylmelamine, as well as filler-containing layers from a copolymer of styrene with butadiene, which copolymer contains 50-75% by weight of styrene and 50-25% by weight of buta-diene, whereby the weight ratio filler to binder is from 0.25 - 0.75 : 1, and the filler preferably is silica with a particle size under 10 micrometres.
The sealing layer is coated with a light-sensitive layer which con-tains at least a light-sensitive diazonium compound and, moreover, polyvinyl alcohol and starch particles in the weight ratio of 1 to 5-20. The degree of hydrolysis of the polyvinyl alcohol must at least amount to 75% and, prefer-ably, it amounts to at least 98%. Further, high-molecular polyvinyl alcohols are preferred to low-molecular products, because they possess a higher bind-ing capacity. Particularly preferred are high-molecular polyvinyl alcohols with a degree of hydrolysis of at least 98%, of which a 4 per cent aqueous solution of 20C has a viscosity of at least 25 centipoises. The light-sensitive layer contains as a filler starch particles, whereby the weight ~6.610~7.
ratio starch particles to polyvinyl alcohol is from 5-20 : 1. If the weight ratio starch to polyvinyl alcohol is higher than 20 : 1 the adherence of the light-sensitive layer to the sealing layer will be insufficient, especially in moist condition, immediately after development of the diazotype material.
If the weight ratio starch to polyvinyl alcohol is smaller than 5 : 1 the ability of the light-sensitive layer to absorb the developer, and the velocity with which the developer penetrates into the light-sensitive' layer become too low, as a result of which the developing speed of the diazo-type material decreases too much and copies that do not immediately feel dry are obtained. The starch particles may consist of wheat starch, maize starch and rice starch, e.g. rice starch is preferably used, because this product has an intenser whiteness than other starch products, and because, thanks to a relatively low spread in particle size, smoother layers can be obtained with it.
The light-sensitive diazonium compound is selected from the diazon-ium compounds known for application in the diazotype process. In general, these are benzene diazonium compounds carrying, in 4-position, a tertiary amino group, a secondary acylamino group, a phenyl group or an etherified mercapto group and, in one or two of the other positions, a halogen atom, an alkyl, alkoxy, phenoxy or tertiary acylamino group or a combination of these substituents. Preferably, a diazonium compound having such a high coupling activity that the diazotype material can be developed with a neutral to weakly acid buffered phloro-glucinol solution, is used. Suitable activity coupling diazonium compounds are described, inter alia, in the British Patent Specifi-cations 919,037, 919,812, 1,045,242, 1,064,128 and 1,064,129, as well as in the Belgian Patent Specifications 657,907, 665,368 and 661,008.
If for the development of the diazotype material an alkaline develop-ing liquid is used, more slowly coupling diazonium compounds, for instance the diazonium compounds described in the British Patent Specifications 867,630, 875,307, 888,598, 919,037; the French Patent Specifica~ions 1,269,874, 1,269,875, 1,269,876; the Belgian Patent Specification 574,785; the Dutch Patent Application 69 12 554, published February 22, 1971 and the German Patent Application 2,003,508 published July 9, 1970 may also be used for the sensitization of the diazotype material.
The auxiliary agents usually applied in diazotype materials such as acid stabilizers~ for example citric acid, tartaric acid, boric acid, benzene and naphthalene sulphonic acid, anti-yellowing agents and developing accelerators, may be used in the light-sensitive layer.
The light-sensitive layer is applied over the sealing layer by means of an aqueous liquid, preferably containing a wetting agent. To prevent the diazonium compound from being trapped in the sealing layer no or no essential amounts of substances, for example organic solvents or swelling agents, caus-ing strong penetration of the sensitizing liquid into the sealing layer, are incorporated in the sensitizing liquid.
The light-sensitive layer applied has a dry weight of at most 8 g per square metre, which corresponds with a layer thickness not exceeding approximately 8 micrometres. Preferably, the dry weight of the light-sensitive layer is from 3 to 6 g per square metre, This layer, notwithstanding its slight thickness, is able to fully absorb 1.5 - 4.5 cm3 per square metre of developing liquid, so that upon development of the diazotype material according to the process referred to before, copies feeling dry are obtained almost immediately. Preferably, also the reverse side of the diazotype material according to the invention is provided with a sealing layer. Also this layer is preferably applied to the paper support from an aqueous liquid. The composition of this sealing layer may be equal to that of the front layer. However, the reverse layer can also be formed with th0 aid of other, more or less hydrophobic, film-forming sub-stances, such as for example polyacrylates, polymethacrylates, polyvinyl chloride, copolymers of acrylates with methacrylates, of vinyl chloride with vinyl acetate, of styrene with acrylonitrile and, optionally, butadiene, and of acrylonitrile with butadiene.
~066~07 A filler can also be incorporated in the reverse layer, e.g. to improve the drafting characteristics of the layer. Besides ordinary opaque paper, the support of the diazotype material according to the invention may be natural transparent paper or transparentized paper. As a sealing layer is applied between the support and the light-sensitive layer, extremely high demands, for example with respect to the degree of sizing and pH of the sur-face, need not be made upon the support.
The diazotype material according to the invention can, of course, als-o be developed in the conventional way, whereby the developing liquid is applied onto the light-sensitive side or on either side of the diazotype material, and the amount of liquid applied is 6 cm3 or more per square metre per side.
In addition to the diazonium compound, an azo-coupling component or a mixture of azo-coupling components may be incorporated in the light-sensitive layer of the diazotype material according to the invention. The two-component diazotype material thus obtained can be developed by spreading a small amount of alkaline developing liquid, which need not contain any azo-coupling component now, over the light-sensitive side of the diazotype mater-ial. The two-component diazotype material is suitable, e.g., for being developed according to the process described in the United States Patent Specification 3,446,620, whereby concentrated amine solution is spread to an amount of approximately 3 cm3 per square metre over the light-sensitive layer.
It stands to reason that this two-component diazotype material can also be developed in the conventional way, by the action of ammonia vapour or other alkaline vapours.
Example 1 White base paper for the diazotype process of 80 g/m2 was provided on either side with a sealing layer having a dry weight of 4 - 4.5 g per square metre, using a liquid of the following composition:
60 ml of a 50 per cent aqueous dispersion of polyvinyl acetate ~ ~6:~Q7
The diazotype paper used in the process according to the patent application mentioned above consists, in a simple embodiment, of a paper support that, after a so-called precoat layer has been applied for smoothing its surface, has been sensitized in such a way that, after drying, the diazon-ium compound has penetrated into the precoat layer to an average depth of at most 8 micrometres. The sensitization of the material is accomplished by applying an adapted concentrated diazo-solution over the precoat layer in an amount of 2-8 cm3 per square metre.
Due to the fact that, upon development only one side of the diazo-type paper is wetted with developing liquid and the developing liquid pene-trates through the precoat layer into the paper support, the diazotype copies will show a strong curl, in particular immediately after development. To avoid curling of the copy, the paper support may be provided with a sealing layer preventing the developing liquid from penetrating into the paper fibres.
Preferably, the sealing layer is applied on either side of the paper support, because otherwise curling may occur as a consequence of water penetrating into the paper fibres of the reverse side of the copy. For instance, unless the reverse side of the diazotype paper is coated with a sealing layer, the just developed copies will curl during piling, as a consequence of moisture pene-trating from the image side of one copy into the reverse side of the overlying copy.
The manufacture of non-curling or almost non-curling diazotype -1- ~F
106611~i7 paper by providing either side of a paper support with a sealing layer, then coating one side with a precoat layer and, finally, sensitizing the precoat layer by applying a small amount of concentrated diazo-solution, is cumber-some and requires a complex coating machine with long drying paths, when it is desired to manufacture the material in one machining operation and at high speed. Due to the fact that the front side of the paper is subjected to three coating operations and, on the other hand, the reverse side to one oper-ation only, it may frequently occur that the paper does not remain flat in the coating machine, in consequence of which an additional treatment of the reverse side is necessary, thus complicating the manufacture of the diazotype paper even more.
The manufacture of the diazotype paper is considerably simplified, if it would be possible to apply the light-sensitive diazonium compound as well as the further solid components of the sensitizing liquid simultaneously with the precoat over the sealing layer. However, the choice of the compon-ents for such a diazotype material is no simple matter, because a lot of demands, partly contrary to each other, must be met. For instance, the paper support must be coated with a more or less hydrophobic sealing layer on which it must be possible, without the aid of an adhesive layer, to apply a very smooth, more or less hydrophilic light-sensitive layer having sufficient adhesion both in dry and in moist condition. It should be possible to apply the components of the light-sensitive layer with sufficient adhesion to the sealing layer, using a coating liquid that contains no solvents penetrating deeply into the sealing layer, or swelling it, because the diazonium compound would otherwise be partly trapped in the sealing layer and be inaccessible to the developing liquid.
The light-sensitive layer itself may not be too thick, because the developing liquid, in order to obtain complete development of the diazotype material, must be able to penetrate through the whole thickness of the layer but, on the other hand, it must fully absorb the amount of developing liquid ~L066~7 applied, in order to obtain copies feeling dry. Further, substances reducing the durability of the diazotype material, or the quality or durability of the diazotype copy to an unacceptable level may, of course, not be incorporated in the sealing layer and the light-sensitive layer.
The invention provides for a diazotype material of the desired composition which meets the requirements with respect to durability and quality of the copy, and which, according to the developing method described in the Dutch Patent Application 72 07 099, can be developed fast and compl,ete-ly, whereby copies feeling immediately dry are obtained. The diazotype material according to the invention comprises a paper support, the same side of which is coated successively with a sealing layer containing as a film-forming binder polyvinyl acetate, or a copolymer of styrene with butadiene, and a light-sensitive layer having a dry weight of at most 8 g/m2 and com-prising a diazonium compound, polyvinyl alcohol with a degree of hydrolysis over 75% and starch particles, whereby the weight ratio starch particles to polyvinyl alcohol is from 5 - 20:1. Upon development in the process accord-ing to the Dutch Patent Application 72 07 099 the diazotype material accord-ing to the invention produces strong copies, feeling dry to the touch almost immediately and showing no or no appreciable curl.
In another aspect, the invention provides a process for the manufacture of copies, in which a diazotype material is imagewise exposed and then developed by spreading 1.5 to 4.5 cm3 per square metre of developing liquid over the light-sensitive side of the diazotype material, character-ized in that the diazotype material comprises a paper support, the same side of which is coated successively with a sealing layer containing as a film-forming binder polyvinyl acetate, or a copolymer of styrene with butadiene, and a light-sensitive layer having a dry weight of at most 8 g per square metre and comprising a diazonium compound, polyvinyl alcohol with a degree of hydrolysis of at least 75% and starch particles, whereby the weight ratio;polyvinyl alcohol to starch particles is from 1 : 5 to 20.
~ _ 3 _ 1066~07 The paper support is coated with a sealing layer containing as a binder polyvinyl acetate or a copolymer of styrene with butadiene.
The sealing layer can be applied to the support using a solution of the film-forming binder but, preferably, it is formed by means of a dispersion of the binder in water, or in a mixture of water with one or more water-miscible organic solvents, for example alcohols, ketones, glycol, and glycol esters. To sized papers the sealing layer is preferably applied from an aqueous dispersion, whereas on well-milled papers, such as natural~
transparent paper,the sealing layer is often advantageously formed from a dispersion of the binder in a mixture(of water and an organic solvent. The mixtures of water with organic solvent may contain up to 75% by volume of 1~66107 organic solvent but, in general, mixtures containing no more than 50% by volume of organic solvent are used. To form a dense coating, the dispersion layer applied is dried at increased temperature.
For the formation of the sealing layer, suitable aqueous dispersions of polyvinyl acetate and copolymers of styrene with butadiene are commercially available. If the sealing layer on the support material is formed using a polyvinyl acetate dispersion, a cross-linking agent is preferably added to the dispersion, and the polyvinyl acetate coating is cross-linked by heating it at 130-180C for some time. It has appeared that this cross-linking improves the adhesive properties of the polyvinyl acetate coating for the light-sensitive layer subsequently to be applied. Moreover, the penetration of the sensitizing liquid into the polyvinyl acetate coating is reduced to a minimum. The familiar products can be used as cross-linking agent, such as paraformaldehyde, glyoxal, and water-soluble, optionally modified, condensat-ion products of urea and melamine with formaldehyde, for example dimethylol-urea, dimethylolmelamine, hexamethylolmelamine, dimethyloltetramethoxymethyl-melamine and hexamethoxymethylmelamine. A very suitable cross-linking agent is hexamethoxymethylmelamine.
Paraformaldehyde and glyoxal are not preferably used, because they generally have an adverse effect on the durability of the diazotype material.
Used as cross-linking catalysts are acids or acid salts, for example hydrochloric acid, sulphuric acid, formic acid, acetic acid, benzenesulphonic acids such as p-toluene sulphonic acid, ammonium chloride, ammonium sulphate and aluminium sulphate.
In addition to the film-forming binder, the sealing layer may con-tain one or more fillers, in order to make it more susceptible to the sensit-izing liquid to be applied, and to improve the adherence of the light-sensit-ive layer. The filler content may not be so high that the sealing layer be-comes water-permeable. In general the weight ratio filler to binder in the sealing layer lies under 1 : 1 and preferably it is from 0.25 - 0.75 : 1.
10~6107 The familiar products can be used as fillers, such as clay, kaolin, diatoma-ceous earth, talcum, silica, barium sulphate~ titanium dioxide, zinc oxide and aluminium oxide. A preferred filler is silica with a particle size under 10 micrometres. The use of this filler in the sealing layer proves to have a favourable effect on the complete development of the diazotype material and the brilliancy of the azo-dyestuff. The sealing layer must fully cover the paper surface. The weight of the sealing layer to be applied depends largely on the surface roughness of the paper.
For papers with a smooth surface the application of a sealing layer having a dry weight of 2-5 g per square metre will mostly suffice. Papers with a rough surface require the application of a thicker layer but, in most cases, the layer need not be thicker than equivalent to a dry weight from 8 to 10 g per square metre.
Highly suitable sealing layers according to the invention are filler-free polyvinyl acetate layers applied from an aqueous dispersion, which have been cross-linked, preferably with hexamethoxymethylmelamine, as well as filler-containing layers from a copolymer of styrene with butadiene, which copolymer contains 50-75% by weight of styrene and 50-25% by weight of buta-diene, whereby the weight ratio filler to binder is from 0.25 - 0.75 : 1, and the filler preferably is silica with a particle size under 10 micrometres.
The sealing layer is coated with a light-sensitive layer which con-tains at least a light-sensitive diazonium compound and, moreover, polyvinyl alcohol and starch particles in the weight ratio of 1 to 5-20. The degree of hydrolysis of the polyvinyl alcohol must at least amount to 75% and, prefer-ably, it amounts to at least 98%. Further, high-molecular polyvinyl alcohols are preferred to low-molecular products, because they possess a higher bind-ing capacity. Particularly preferred are high-molecular polyvinyl alcohols with a degree of hydrolysis of at least 98%, of which a 4 per cent aqueous solution of 20C has a viscosity of at least 25 centipoises. The light-sensitive layer contains as a filler starch particles, whereby the weight ~6.610~7.
ratio starch particles to polyvinyl alcohol is from 5-20 : 1. If the weight ratio starch to polyvinyl alcohol is higher than 20 : 1 the adherence of the light-sensitive layer to the sealing layer will be insufficient, especially in moist condition, immediately after development of the diazotype material.
If the weight ratio starch to polyvinyl alcohol is smaller than 5 : 1 the ability of the light-sensitive layer to absorb the developer, and the velocity with which the developer penetrates into the light-sensitive' layer become too low, as a result of which the developing speed of the diazo-type material decreases too much and copies that do not immediately feel dry are obtained. The starch particles may consist of wheat starch, maize starch and rice starch, e.g. rice starch is preferably used, because this product has an intenser whiteness than other starch products, and because, thanks to a relatively low spread in particle size, smoother layers can be obtained with it.
The light-sensitive diazonium compound is selected from the diazon-ium compounds known for application in the diazotype process. In general, these are benzene diazonium compounds carrying, in 4-position, a tertiary amino group, a secondary acylamino group, a phenyl group or an etherified mercapto group and, in one or two of the other positions, a halogen atom, an alkyl, alkoxy, phenoxy or tertiary acylamino group or a combination of these substituents. Preferably, a diazonium compound having such a high coupling activity that the diazotype material can be developed with a neutral to weakly acid buffered phloro-glucinol solution, is used. Suitable activity coupling diazonium compounds are described, inter alia, in the British Patent Specifi-cations 919,037, 919,812, 1,045,242, 1,064,128 and 1,064,129, as well as in the Belgian Patent Specifications 657,907, 665,368 and 661,008.
If for the development of the diazotype material an alkaline develop-ing liquid is used, more slowly coupling diazonium compounds, for instance the diazonium compounds described in the British Patent Specifications 867,630, 875,307, 888,598, 919,037; the French Patent Specifica~ions 1,269,874, 1,269,875, 1,269,876; the Belgian Patent Specification 574,785; the Dutch Patent Application 69 12 554, published February 22, 1971 and the German Patent Application 2,003,508 published July 9, 1970 may also be used for the sensitization of the diazotype material.
The auxiliary agents usually applied in diazotype materials such as acid stabilizers~ for example citric acid, tartaric acid, boric acid, benzene and naphthalene sulphonic acid, anti-yellowing agents and developing accelerators, may be used in the light-sensitive layer.
The light-sensitive layer is applied over the sealing layer by means of an aqueous liquid, preferably containing a wetting agent. To prevent the diazonium compound from being trapped in the sealing layer no or no essential amounts of substances, for example organic solvents or swelling agents, caus-ing strong penetration of the sensitizing liquid into the sealing layer, are incorporated in the sensitizing liquid.
The light-sensitive layer applied has a dry weight of at most 8 g per square metre, which corresponds with a layer thickness not exceeding approximately 8 micrometres. Preferably, the dry weight of the light-sensitive layer is from 3 to 6 g per square metre, This layer, notwithstanding its slight thickness, is able to fully absorb 1.5 - 4.5 cm3 per square metre of developing liquid, so that upon development of the diazotype material according to the process referred to before, copies feeling dry are obtained almost immediately. Preferably, also the reverse side of the diazotype material according to the invention is provided with a sealing layer. Also this layer is preferably applied to the paper support from an aqueous liquid. The composition of this sealing layer may be equal to that of the front layer. However, the reverse layer can also be formed with th0 aid of other, more or less hydrophobic, film-forming sub-stances, such as for example polyacrylates, polymethacrylates, polyvinyl chloride, copolymers of acrylates with methacrylates, of vinyl chloride with vinyl acetate, of styrene with acrylonitrile and, optionally, butadiene, and of acrylonitrile with butadiene.
~066~07 A filler can also be incorporated in the reverse layer, e.g. to improve the drafting characteristics of the layer. Besides ordinary opaque paper, the support of the diazotype material according to the invention may be natural transparent paper or transparentized paper. As a sealing layer is applied between the support and the light-sensitive layer, extremely high demands, for example with respect to the degree of sizing and pH of the sur-face, need not be made upon the support.
The diazotype material according to the invention can, of course, als-o be developed in the conventional way, whereby the developing liquid is applied onto the light-sensitive side or on either side of the diazotype material, and the amount of liquid applied is 6 cm3 or more per square metre per side.
In addition to the diazonium compound, an azo-coupling component or a mixture of azo-coupling components may be incorporated in the light-sensitive layer of the diazotype material according to the invention. The two-component diazotype material thus obtained can be developed by spreading a small amount of alkaline developing liquid, which need not contain any azo-coupling component now, over the light-sensitive side of the diazotype mater-ial. The two-component diazotype material is suitable, e.g., for being developed according to the process described in the United States Patent Specification 3,446,620, whereby concentrated amine solution is spread to an amount of approximately 3 cm3 per square metre over the light-sensitive layer.
It stands to reason that this two-component diazotype material can also be developed in the conventional way, by the action of ammonia vapour or other alkaline vapours.
Example 1 White base paper for the diazotype process of 80 g/m2 was provided on either side with a sealing layer having a dry weight of 4 - 4.5 g per square metre, using a liquid of the following composition:
60 ml of a 50 per cent aqueous dispersion of polyvinyl acetate ~ ~6:~Q7
2.5 ml of hexamcthoxyllletllylmelamine 0.2 g of p-toluene sulphonic acid water up to 100 ml.
The layers were dried and cross-linked by heating thom at 150-lS0C
for 30 seconds.
One side of the coated support was then provided with a light-sensi-tive layer, using a liquid of the following composition:
2 g of 4-dimethylamino-3-(4'-chlorophenoxy)-6-chlorobenzene diazonium hydrogen-sulphate 2 g of high-molecular polyvinyl alcohol with a degree of hydrolysis of 98% (Elvanol 72-60*of Du Pont de Nemours and Co., U.S.A.) g of rich starch ml of n-propanol water up to 100 ml.
The light-sensitive layer had a dry weight of approximately 4 g/m2.
The diazotype material thus obtained was exposed under a line original until all the diazonium compound underneath the white areas of the original had been bleached out.
The exposed material was then developed in a developing device as described in the Dutch Patent Application 72 07 099, whereby developing liquid to an amount of approximately 3.5 cm3 per square metre was applied to the light-sensitive side.
The developing liquid contained per litre:
29 g of phloroglucinol 89 g of succinic acid, potassium hydroxide to bring the pH of the liquid on 6.0, and water.
A copy with a strong, blac~ imagc on a clear background was obtain-ed. The copy showcd no curl and folt dry to the touch almost immediately.
Example 2 Baso paper or the diazotype process of 80 g/m was providcd on cither side wi~h a sealing laycr having a dry weigllt of approxima~cly 2 g * Trade Mark _9_ 1066107.
per square metre, using a liquid of the following composition:
ml of a 50 per cent aqueous dispersion of a copolymer of 60% by weight of styrene witll 40% by weight of butadiene ml of water.
One side of the support was then coated with a light-sensitive layer having a dry weight of 5 g per square metre, using the sensitizing liquid described in Example 1, with the proviso that it now contained 7.5 ml of n-propanol. The diazotype material obtained was exposed imagewise and developed in the way described in Example 1.
The development of the material proceeded quickly. The copy showed no curl, it immediately felt dry to the touch, and yielded a strong, black image on a clear background.
Example 3 Base paper for the diazotype process of 65 g/m2 was provided on either side with a sealing layer having a dry weight of approximately 7 g per square metre, using a liquid of the following composition:
60 ml of a 50 per cent aqueous dispersion of polyvinyl acetate 40 ml of water.
One side of the support was coated with a light-sensitive layer having a dry weight of approximately 4 g per square metre, by means of a liquid containing:
The layers were dried and cross-linked by heating thom at 150-lS0C
for 30 seconds.
One side of the coated support was then provided with a light-sensi-tive layer, using a liquid of the following composition:
2 g of 4-dimethylamino-3-(4'-chlorophenoxy)-6-chlorobenzene diazonium hydrogen-sulphate 2 g of high-molecular polyvinyl alcohol with a degree of hydrolysis of 98% (Elvanol 72-60*of Du Pont de Nemours and Co., U.S.A.) g of rich starch ml of n-propanol water up to 100 ml.
The light-sensitive layer had a dry weight of approximately 4 g/m2.
The diazotype material thus obtained was exposed under a line original until all the diazonium compound underneath the white areas of the original had been bleached out.
The exposed material was then developed in a developing device as described in the Dutch Patent Application 72 07 099, whereby developing liquid to an amount of approximately 3.5 cm3 per square metre was applied to the light-sensitive side.
The developing liquid contained per litre:
29 g of phloroglucinol 89 g of succinic acid, potassium hydroxide to bring the pH of the liquid on 6.0, and water.
A copy with a strong, blac~ imagc on a clear background was obtain-ed. The copy showcd no curl and folt dry to the touch almost immediately.
Example 2 Baso paper or the diazotype process of 80 g/m was providcd on cither side wi~h a sealing laycr having a dry weigllt of approxima~cly 2 g * Trade Mark _9_ 1066107.
per square metre, using a liquid of the following composition:
ml of a 50 per cent aqueous dispersion of a copolymer of 60% by weight of styrene witll 40% by weight of butadiene ml of water.
One side of the support was then coated with a light-sensitive layer having a dry weight of 5 g per square metre, using the sensitizing liquid described in Example 1, with the proviso that it now contained 7.5 ml of n-propanol. The diazotype material obtained was exposed imagewise and developed in the way described in Example 1.
The development of the material proceeded quickly. The copy showed no curl, it immediately felt dry to the touch, and yielded a strong, black image on a clear background.
Example 3 Base paper for the diazotype process of 65 g/m2 was provided on either side with a sealing layer having a dry weight of approximately 7 g per square metre, using a liquid of the following composition:
60 ml of a 50 per cent aqueous dispersion of polyvinyl acetate 40 ml of water.
One side of the support was coated with a light-sensitive layer having a dry weight of approximately 4 g per square metre, by means of a liquid containing:
3.2 g of 4-N-methyl-N-cyclohexylamino-3-methoxy-2-N-methyl-N-ethoxycarbonylamino benzene diazonium-chlorozincate 0.6 g of citric acid 3 g of polyvinyl alcGhol having a degree of hydrolysis of approximately 77% (Gohsenol KH 17*of Nippon Gohsei, Osaka, Japan) g of rich starch ml of n-propaJIol water up to 100 ml.
The diazotype material was exposed imagewise and dcvelopcd in thc way described in Examp]e 1. A strong, non-curling copy i~nediately feeling * Trade Mark L
1~66i~7 dry, and showing a black image on a white background was obtained.
Example 4 Base paper for the diazotype process of 65 g/m was provided on one side with a sealing layer having a dry weight of 5 g per square metre, using a liquid of the following composition:
ml of a 50 per cent aqueous dispersion of a copolymer of 70%
by weight of styrene and 30% by weight of butadiene 8 g of amorphous silica with a primary particle size of 30 nanometres ml of water.
The reverse side of the paper was then provided with a sealing layer having a dry weight of 4 g per square metre, using a 35 per cent aqueous dispersion of polyvinyl acetate. The front side of the paper was then coated with a light-sensitive layer having a dry weight of 7 g per square metre, using a liquid containing:
1.8 g of 4-N-benzoylamino-2-N-methyl-N-ethoxycarbonylamino-5-methoxy-benzene diazonium-chlorozincate 0.4 g of citric acid 2 g of high-molecular polyvinyl alochol with a degree of hydrolysis of approximately 98%
g of wheat starch 0.5 g of saponine water up to 100 ml.
The diazotype material was then exposed imagewise and developed in the way described in Example 1.
A strong copy with a brown image on a white background was obtained.
The development of the material proceeded quickly. The copy did not curl and it immediately felt dry.
Example 5 Natural transparent paper of 75 g/m2 was provided on either side with a sealing layer having a dry weight of approximately 2.5 g per square metre, using a liquid of the following composition:
i107 ml of a 50 per ce'nt aqueous dispersion of a coyol~mer of 60%
by weight of styrene with 40% by weig}-t of butadiene ml of ethanol.
One side of the paper thus coated was then providcd with a light-sensitive layer having a dry weight of approximately 5 g pcr square metre, by means of a liquid containing:
2.7 g of 4-N-benzoylamino-2-N-methyl-N-ethoxycarbonylamino-5-methoxy-benzene diazoniumhydrogensulphate 3 g of high-molecular polyvinyl alcohol with a degree of hydrolysis over 98% (Gohsenol N~126) g of rich starch 0.5 g of saponine.
The diazotype material was exposed under a line original until the diazonium compound underneath the white areas of the original had just been bleached out and, subsequently, developed in the l~ay described in Example l.
The development of the material proceeded quickly. The copy did not curl and it immediately felt dry. It showed a strong brown image on a clear background, and could be used as an intermediate original for further copying on diazotype paper.
Example 6 ~l.'hite base paper of 65 g1m2 was provided on one side with a sealing layer having a dry weight of approximately 6 g per square metre~ using liquid of the following composition:
40 ml of a 50 per cent aqueous dispersion of a copolymer of 60%
by weight of styrene with ~0% by weight of butadiene 5 g of clay 60 ml of water.
The reverse side of the paper was then provided with a sealing layer having a dry weight of 3 g per square metre, using an aqueous polyvinyl chlor-ide dispersion (Lutofan 300 D*of B.A.S.F., Ludwigs1lafen/Rhci1l, Gcrmany).
; The front sidc of the paper was then coated Wit}l a light-sensitive layer having a dry weight of 4 g per square metre, by means of a ]iquid con-* Trade Mark ~066107 taining:
2 g of 4-morpholino-2,5-dibutoxy-benzene diazoniumhydrogcn-sulpllate 2 g of polyvinyl alcohol with a dcgree of hydrolysis of 98%
~Elvanol 72-60)*
g of corn starch ml of n-propanol.
The diazotype material thus obtained was exposed imagewise under a line original and then developed in the way described in Example 1, using now a developer of the composition:
10.8 g of phloroglucinol 13 g of resorcinol g of thiourea g of sorbitol 100 g of potassium tetraborate (5 aq.) 3 g of isopropylnaphthalene sulphonic acid 1,000 ml of water.
The copy showed a strong image on a clear background. It did not curl and felt dry to the touch almost immediately.
Example 7 Base paper for the diazotype process of 90 g/m2 was provided with a sealing layer having a dry weight of approximately 5 g per square metre, by means of a liquid containing:
40 ml of an aqueous 50 per cent dispersion of a copolymer of 65% by weight of styrene with 35% by weight of butadiene 12 g of silica with a particle size under 10 micrometres 60 ml of water.
The reverse side of the paper was then provided with a sealing layer having a dry weight of 3.5 g per square metre, by means of a liquid contain-ing:
ml of ~n aqueous 50 per ccnt dispersion of a copolymcr of 65% by weight of styrenc with 35% by weight of butadiene * Trade Mark : J -13-~066~07 7 g of rich starch ml of water.
The front side o the paper was thcn coated with a light-scnsitive layer having a dry weight of approximately 3.5 g per square metre, by means of a liquid containing:
1 g of 4-N-ethyl-N-(2'-hydroxyethyl)amino-benzene diazonium-chlorozincate 3 g of tartaric acid 1 g of 2,3-dihydroxynaphthalene-6-sulphonic acid (sodium salt) 2 g of high-molecular polyvinyl alcohol with a degree of hydroly-sis over 98% (Gohsenol NH26 20 g of rice starch 7 ml of n-propanol water up to 100 ml.
~ The sheet of the diazotype material thus obtained was exposed under a line original and then developed by spreading over the light-sensitive layer of the paper approximately 3 ml per square metre of developing liquid having the following composition: -48 ml of triethanolamine 43.5 ml of diethyleneglycol monomethylether 8.5 ml of oleic acid.
The copy obtained showed a blue image on a clear background.
Trade Mark .' h-~
The diazotype material was exposed imagewise and dcvelopcd in thc way described in Examp]e 1. A strong, non-curling copy i~nediately feeling * Trade Mark L
1~66i~7 dry, and showing a black image on a white background was obtained.
Example 4 Base paper for the diazotype process of 65 g/m was provided on one side with a sealing layer having a dry weight of 5 g per square metre, using a liquid of the following composition:
ml of a 50 per cent aqueous dispersion of a copolymer of 70%
by weight of styrene and 30% by weight of butadiene 8 g of amorphous silica with a primary particle size of 30 nanometres ml of water.
The reverse side of the paper was then provided with a sealing layer having a dry weight of 4 g per square metre, using a 35 per cent aqueous dispersion of polyvinyl acetate. The front side of the paper was then coated with a light-sensitive layer having a dry weight of 7 g per square metre, using a liquid containing:
1.8 g of 4-N-benzoylamino-2-N-methyl-N-ethoxycarbonylamino-5-methoxy-benzene diazonium-chlorozincate 0.4 g of citric acid 2 g of high-molecular polyvinyl alochol with a degree of hydrolysis of approximately 98%
g of wheat starch 0.5 g of saponine water up to 100 ml.
The diazotype material was then exposed imagewise and developed in the way described in Example 1.
A strong copy with a brown image on a white background was obtained.
The development of the material proceeded quickly. The copy did not curl and it immediately felt dry.
Example 5 Natural transparent paper of 75 g/m2 was provided on either side with a sealing layer having a dry weight of approximately 2.5 g per square metre, using a liquid of the following composition:
i107 ml of a 50 per ce'nt aqueous dispersion of a coyol~mer of 60%
by weight of styrene with 40% by weig}-t of butadiene ml of ethanol.
One side of the paper thus coated was then providcd with a light-sensitive layer having a dry weight of approximately 5 g pcr square metre, by means of a liquid containing:
2.7 g of 4-N-benzoylamino-2-N-methyl-N-ethoxycarbonylamino-5-methoxy-benzene diazoniumhydrogensulphate 3 g of high-molecular polyvinyl alcohol with a degree of hydrolysis over 98% (Gohsenol N~126) g of rich starch 0.5 g of saponine.
The diazotype material was exposed under a line original until the diazonium compound underneath the white areas of the original had just been bleached out and, subsequently, developed in the l~ay described in Example l.
The development of the material proceeded quickly. The copy did not curl and it immediately felt dry. It showed a strong brown image on a clear background, and could be used as an intermediate original for further copying on diazotype paper.
Example 6 ~l.'hite base paper of 65 g1m2 was provided on one side with a sealing layer having a dry weight of approximately 6 g per square metre~ using liquid of the following composition:
40 ml of a 50 per cent aqueous dispersion of a copolymer of 60%
by weight of styrene with ~0% by weight of butadiene 5 g of clay 60 ml of water.
The reverse side of the paper was then provided with a sealing layer having a dry weight of 3 g per square metre, using an aqueous polyvinyl chlor-ide dispersion (Lutofan 300 D*of B.A.S.F., Ludwigs1lafen/Rhci1l, Gcrmany).
; The front sidc of the paper was then coated Wit}l a light-sensitive layer having a dry weight of 4 g per square metre, by means of a ]iquid con-* Trade Mark ~066107 taining:
2 g of 4-morpholino-2,5-dibutoxy-benzene diazoniumhydrogcn-sulpllate 2 g of polyvinyl alcohol with a dcgree of hydrolysis of 98%
~Elvanol 72-60)*
g of corn starch ml of n-propanol.
The diazotype material thus obtained was exposed imagewise under a line original and then developed in the way described in Example 1, using now a developer of the composition:
10.8 g of phloroglucinol 13 g of resorcinol g of thiourea g of sorbitol 100 g of potassium tetraborate (5 aq.) 3 g of isopropylnaphthalene sulphonic acid 1,000 ml of water.
The copy showed a strong image on a clear background. It did not curl and felt dry to the touch almost immediately.
Example 7 Base paper for the diazotype process of 90 g/m2 was provided with a sealing layer having a dry weight of approximately 5 g per square metre, by means of a liquid containing:
40 ml of an aqueous 50 per cent dispersion of a copolymer of 65% by weight of styrene with 35% by weight of butadiene 12 g of silica with a particle size under 10 micrometres 60 ml of water.
The reverse side of the paper was then provided with a sealing layer having a dry weight of 3.5 g per square metre, by means of a liquid contain-ing:
ml of ~n aqueous 50 per ccnt dispersion of a copolymcr of 65% by weight of styrenc with 35% by weight of butadiene * Trade Mark : J -13-~066~07 7 g of rich starch ml of water.
The front side o the paper was thcn coated with a light-scnsitive layer having a dry weight of approximately 3.5 g per square metre, by means of a liquid containing:
1 g of 4-N-ethyl-N-(2'-hydroxyethyl)amino-benzene diazonium-chlorozincate 3 g of tartaric acid 1 g of 2,3-dihydroxynaphthalene-6-sulphonic acid (sodium salt) 2 g of high-molecular polyvinyl alcohol with a degree of hydroly-sis over 98% (Gohsenol NH26 20 g of rice starch 7 ml of n-propanol water up to 100 ml.
~ The sheet of the diazotype material thus obtained was exposed under a line original and then developed by spreading over the light-sensitive layer of the paper approximately 3 ml per square metre of developing liquid having the following composition: -48 ml of triethanolamine 43.5 ml of diethyleneglycol monomethylether 8.5 ml of oleic acid.
The copy obtained showed a blue image on a clear background.
Trade Mark .' h-~
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Diazotype material consisting of a paper support, the same side of which is coated successively with a sealing layer containing a polymeric, film-forming binder and a light-sensitive layer, characterized in that the film-forming binder in the sealing layer is polyvinyl acetate or a co-polymer of styrene with butadiene, and that the light-sensitive layer has a dry weight of at most 8 g per square metre and comprises a diazonium com-pound, polyvinyl alcohol with a degree of hydrolysis over 75% and starch particles, whereby the weight ratio polyvinyl alcohol to starch particles is 1 : 5 to 20.
2. Diazotype material according to claim 1, characterized in that the sealing layer is formed by means of a dispersion of the binder.
3. Diazotype material according to claim 1, characterized in that the sealing layer contains at most 1 part by weight of filler per part by weight of film-forming binder.
4. Diazotype material according to claim 3, characterized in that the filler is silica with a particle size under 10 micrometres.
5. Diazotype material according to claim 2, characterized in that the sealing layer is formed from an aqueous polyvinyl acetate dispersion containing a cross-linking agent.
6. Diazotype material according to claim 5, characterized in that the cross-linking agent is hexamethoxymethylmelamine.
7. Diazotype material according to claim 3, characterized in that the sealing layer is formed from a dispersion comprising a copolymer of 50 - 75% by weight of styrene with 80 - 95% by weight of butadiene and a filler, the weight ratio of said copolymer to filler being 1:0.25 to 0.75.
8. Diazotype material according to claim 1, characterized in that the polyvinyl alcohol in the light-sensitive layer possesses a degree of hydroly-sis over 98%.
9. Diazotype material according to claim 8, characterized in that a polyvinyl alcohol is present, of which a 4 per cent aqueous solution of 20°C
has a viscosity of at least 25 centipoises.
has a viscosity of at least 25 centipoises.
10. Diazotype material according to claim 1, characterized in that the light-sensitive layer has a dry weight between 3 and 6 g per square metre.
11. Diazotype material according to claim 1, characterized in that the light-sensitive layer also contains an azo-coupling component.
12. Process for the manufacture of copies, in which a diazotype material is imagewise exposed and then developed by spreading 1.5 to 4.5 cm3 per square metre of developing liquid over the light-sensitive side of the diazotype material, characterized in that the diazotype material comprises a paper support, the same side of which is coated successively with a sealing layer containing as a film-forming binder polyvinyl acetate, or a copolymer of styrene with butadiene, and a light-sensitive layer having a dry weight of at most 8 g per square metre and comprising a diazonium compound, polyvinyl alcohol with a degree of hydrolysis of at least 75% and starch particles, whereby the weight ratio polyvinyl alcohol to starch particles is from 1 : 5 to 20.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NLAANVRAGE7407161,A NL178452C (en) | 1974-05-29 | 1974-05-29 | DIAZOTYPE MATERIAL THAT CAN BE DEVELOPED BY APPLICATION OF A LOW AMOUNT OF DEVELOPMENT FLUID. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1066107A true CA1066107A (en) | 1979-11-13 |
Family
ID=19821446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA227,895A Expired CA1066107A (en) | 1974-05-29 | 1975-05-28 | Paper support with sealing layer and layer containing diazonium compound, polyvinyl alcohol and starch particles |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5820419B2 (en) |
| BR (1) | BR7503390A (en) |
| CA (1) | CA1066107A (en) |
| CH (1) | CH599567A5 (en) |
| DE (1) | DE2522173C2 (en) |
| FR (1) | FR2275799A1 (en) |
| GB (1) | GB1464514A (en) |
| IT (1) | IT1033000B (en) |
| NL (1) | NL178452C (en) |
| SE (1) | SE403406B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61146809U (en) * | 1985-03-04 | 1986-09-10 | ||
| DE4429741C1 (en) * | 1994-08-22 | 1996-06-05 | Renker Gmbh & Co Kg | 1-component diazo blueprint material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE632667A (en) * | 1962-05-25 | |||
| NL172373C (en) * | 1972-05-26 | 1983-08-16 | Oce Van Der Grinten Nv | METHOD FOR MAKING DIAZOTYP COPIES |
-
1974
- 1974-05-29 NL NLAANVRAGE7407161,A patent/NL178452C/en not_active IP Right Cessation
-
1975
- 1975-05-17 DE DE2522173A patent/DE2522173C2/en not_active Expired
- 1975-05-21 SE SE7505810A patent/SE403406B/en not_active IP Right Cessation
- 1975-05-23 GB GB2284575A patent/GB1464514A/en not_active Expired
- 1975-05-24 JP JP50062422A patent/JPS5820419B2/en not_active Expired
- 1975-05-27 CH CH674375A patent/CH599567A5/xx not_active IP Right Cessation
- 1975-05-28 IT IT68380/75A patent/IT1033000B/en active
- 1975-05-28 CA CA227,895A patent/CA1066107A/en not_active Expired
- 1975-05-28 BR BR4335/75D patent/BR7503390A/en unknown
- 1975-05-29 FR FR7516772A patent/FR2275799A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| SE403406B (en) | 1978-08-14 |
| NL178452C (en) | 1986-03-17 |
| BR7503390A (en) | 1976-04-27 |
| IT1033000B (en) | 1979-06-20 |
| DE2522173C2 (en) | 1985-01-10 |
| GB1464514A (en) | 1977-02-16 |
| SE7505810L (en) | 1975-12-01 |
| JPS5820419B2 (en) | 1983-04-22 |
| FR2275799A1 (en) | 1976-01-16 |
| FR2275799B1 (en) | 1981-09-25 |
| NL178452B (en) | 1985-10-16 |
| DE2522173A1 (en) | 1975-12-18 |
| NL7407161A (en) | 1975-12-02 |
| JPS513221A (en) | 1976-01-12 |
| CH599567A5 (en) | 1978-05-31 |
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