DE1572087A1 - Thermographically usable imaging material - Google Patents

Description

kSO- \

Konishiroku Photo Industry Co., Ltd., Tokyo (Japan)

"Thermographically usable image Brnaterlal"

The present invention relates to a themography useful Material that provides an image is a carrier and a photographic silver layer that creates an image, drawn thereon, the layer or its photographically adjacent layer being incorporated therein finely divided sulfur contains »Dae goal of the preceding Invention iet ee, a new and useful material to create that after the formation of a photographic image on it as a mother sheet for a thermographleehee process Can be used to make a large number of copies to received

To make reproductions of originals such as handwritten documents BAD ORIGINAL 009814/1616

To keep ments, prints and the like, various processes have been developed in a conventional manner, of which the thermographic process found by the applicant using supercooling phenomena (Japan Printer, Volume 47, No. 4, page 12 ( 1964)) A new process with many peculiarities The present invention intends to make these processes more advantageous by providing a new and useful imaging material. Since the above-mentioned supercooling process is of the thermographic type, it usually has the defect to give no clear reproductions lower parts IR absorbing Nature "In contrast, that imaging material of the present invention provides an image by using a silver photography process and hence there may be a clear copy regardless of the Färb" dEB used original create _f said copy ale Mother arch for a thermographis In addition, the supercooling process can only be used for copying, while the use of the material according to the invention enables enlarged or reduced reproductions to be obtained by using a photographic process. Furthermore, when using the material according to the invention, any original can easily be reproduced that is completely opaque and so thick,

0098U / 1616

OBiGlHAt

groco oiler is difficult that it is for an ordinary copier-'.-— ochjne is not acceptable

According to the present invention, a thermographic useful imaging material created from a Support and a photographic silver layer providing an image soaked on it, this layer or its photographically adjacent layer being finely distributed Incorporated sulfur contains «according to one embodiment of the present invention can fine sulfur particles in the part: the image-providing photographic silver layer of the imaging material is present. Another embodiment According to the present invention, they can be present in a protective layer, such as a coating on the photographic silver layer providing an image with or without an intermediate layer. It should be made clear that the term "photographieoh adjoining layer "means a layer that * u the one Ab ~ ' image-providing photographic silver layer is adjacent, regardless of whether there is an intermediate layer. The aforesaid imaging silver layer is typically a photosensitive photographic object Silver halide emulsion layer or a silver diffusion transfer pick-up layer The above adjoining

0098U / 1616
BATH ORIGINAL

The photographic layer is a protective layer which is well known in photography

The invention is explained in detail below. As already indicated, the material according to the invention contains a a layer providing a silver image and optionally a photographically adjacent layer, one of these layers containing finely divided sulfur incorporated therein, the Sulfur is one of the heat-sensitive substances that can be used in the supercooling process. Ale heat-sensitive substances There are many substances in the overcooling process outside of sulfur known. In the present invention in which the silver photography method is used, those substances which act on the light-sensitive emulsion substances or the diffusion transfer B image recording substances adversely affect »Furthermore, in the present invention, in which photographic treatments such as developing and fixing are necessary, as are water-soluble heat-sensitive materials unusable as they flow out during the treatment steps. For example, benistriazole is a water sensitive Substance and is frequently used in the supercooling process. However, this substance causes marked desensitization in the light-sensitive photographic emulsions and is therefore not relevant to the present invention

0098U / 1616

8AD ORIGINAL

suitable »p-Toluenesulfonamide is so highly soluble in water that that eo during the photographic treatments as well Layer flows out and is therefore heat-sensitive Substance useless in the present invention »In contrast to this, sulfur flows, which is completely insoluble in water is during use in the present invention the treatment steps fail and neither does it cause obfuscation or desensitization of the photographically sensitive emulsions. It is therefore complete suitable as a heat-sensitive component of the invention Illustrative material »Also has sulfur in it many advantages that it is excellent in transferability, remains long in the overcooled state, which is possible makes it possible to obtain a stable, dust-retaining latent image, and can be incorporated into the layer in a coarse amount, thereby making a large number of reproductions can be obtained from a single mother arch. The fact j that sulfur is commercially available and its cheaper Price are further advantages. From the prior art, the presence of sulfur in a photographic Emulsion as a cause of serious photographic problems Properties have been considered “If you pull them into consideration, the present invention is based on the preamble

009814/1818

BATH ORIGINAL

tells of the state of leehnik unexpected and surprising,

Each of the usual known lichterapfindliohen photograph - surfaces silver halide can be used to Hero of a division of an image supplied photographic silver layer in the present invention successfully used v / ground "Furthermore, all emulsions in the present invention uses v / ground" receiving the to HerBtellung a an illustration Layer can be used in the silver diffusion transfer process, these emulsions being hereinafter referred to as "image-receiving emulsions" or Herechel effect can be used. Emulsions which can be treated quickly for the stabilization process or heat-developable emulsions are also useful Chen emulsions can be treated before use by parbo-sensitization, noble metal sensitization or reductive sensitization or by adding additives such as stabilizers, hardnesses and development control agents. The image-receiving emulsion of the silver diffusion transfer process

009814/1616

BATH ORIGINAL

which is suitable for the purposes of the present invention, etellt a dispersion of a colloidal noble metal or Metal sulphides as bacteria that precipitate the picture in one layer forming binders as protective colloids.

The application of the material of the present invention will now be explained below with reference to the case of using a photosensitive direct positive photographic emulsion. First, the material according to the invention becomes the original bearing an image in the. The desired magnification is irradiated and then photographic treatments are subjected to development and fixing according to known processes, a mirror-image silver image being produced on the material according to the invention. All of the "material", which is now usable as a mother sheet, is put on a paper as a recording sheet and the unit which results in calibration is subjected to infrared radiation, whereby the sulfur of the image part is transferred to the paper as a result of the action of heat on the infrared-absorbing silver part of the image which results in a latent sulfur image on the paper in an overcooled state. Ale third is developed which achieved on paper latent image, however, on such a fine coloring powder is scattered, usually as ee in electro-photographic processes used

0098U / 1616
BAD RIGSN ^AL

is (hereinafter referred to as toner) * The developed image can be fixed by using a solvent vapor _p whereby a copy is obtained which bears a correct copy of the original. The infrared irradiation and image transfer can be repeated up to a maximum of about 200 times, whereby a large number of reproductions can be obtained from a single master sheet.

In the present invention, the conventionally known silver halide photography method is used for the formation of images, and therefore it is possible to obtain fabrics having any desired sensitivity within a very wide range according to the desired objects. Can / Y eiterhin the use of many known methods such as Parbaenaibilisierung, the direct conversion and the like. Abbildungestoffe duroh be obtained useful for various purposes Bind. Since the image formed by the application of the present material is composed of infrared absorbing probes and thermally conductive silver metal parts , the warnings of the image parts can also be transferred well to the heat-sensitive sulfur particles, with reproductions showing clear images being highly effective Application of thermography can be obtained.

0098 U / 1616

BAD OBiGiNAU

572Ü87

The he co-division deo invention-based illustration in terlain can be done as follows:

Sulfur is conveniently encapsulated as DisperaLon fiber particles, the dispersion then being mixed with a light-sensitive photographic emulsion or the like. Daa means that the sulfur is added to a solution which has been prepared by first forming a solution of a high molecular weight hydrophilic diapersion medium and then adding a suitable surface active agent and the resulting mixture becomes a DiB persio ' is machine, such as a ball mill, exposed to form a dispersion of finely divided sulfur having a particle size below 50 µ, preferably below W µ au. Any high molecular weight dispersion medium is generally preferred, gelatin. In addition, gum arabic, polyvinyl alcohol, carboxymethylsellulose and sodium alginate can also be used. It is important that the sulfur does not contain any impurities which impair the photographic properties and the sulfur can be in any form of crystalline sulfur or sublimed sulfur as long as it is pure

BAD ORIGINAL 00981 A / 1616

- ίο -

made with a light-sensitive photograph emulbion or ilerglo, and the mixture is applied to a suitable support and then dried to obtain the imaging material of the invention. When the amount of sulfur incorporated is excessively large, the sensitivity of the photosensitive emulsion ion is deteriorated due to the diffusion of light, while no effect is obtained when the amount is excessively small. In general, sulfuric acid is preferably used in an amount which is essentially the weight of the silver halide in the light-sensitive emulsion:] However, the amount may suitably be in the range of 0.05-5 parts per part of silver. halide varies, EULn commercially available photographlocheo paper contains 2 - 3 g of silver per ar and sulfur can therefore be used in an amount in the range 0.1 - 15 β ₃ Paper is generally used as a carrier, the imaging material according to the invention will be used later be subjected to a thermographic process and therefore the use of a thin paper is preferred because it is favorable in terms of infrared density. There are, however, some cases where a thin paper is used as a recording sheet in the theraographic process raw photograph! «·

0098U / 1616

3AD

aclien paper alu carrier can be used, Auaaer paper can a film base such as cellulose acetate or polyethylene terephthalate can also be used as a carrier »

The typical applications of the imaging materials according to the invention are explained below. Let the imaging material be irradiated using the conventionally known photographic technique in the form of the image. In this case, the irradiation is desirably effected by the use of an optical system, since it is the most common thermosetting method to make a mirror image on the imaging material. However, is a thin paper used as the recording sheet, and the copy can be viewed from d # r Rückeei te, is such irradiation to give a riclitigee image _f dch "copying, anfcehabar. The irradiated imaging material is then developed and fixed to give a silver image. In this case, the material can then be subjected to a rapid treatment using a stabilization process, heat development or tanning development, after which the unirradiated parts are washed off with hot water. The tanning development is particularly advantageous because the subsequent thermographic process can be carried out easily, since sulfur is not used as a heat-sensitive material in any other

0 0 9 8- U / 1 6 1 8 ^{ßAD 0RIQi} NAL

Tel1 is present except for the image part. All of the ancestors mentioned above and work aachritto are known photography things Methods, further explanations in this direction are therefore not necessary

Dao material on which - "as described above - a silver image is produced is then ale mother bow for daa thermographic ancestors used" a large number of reproductions to ¹ get thermograph Dae aohe process is carried out by the mother bow! An ordinary paper is placed as a recording sheet and this unit is subjected to IR radiation, as a result of which the sulfur in the image part is transferred to the recording sheet with the formation of tineo usable latent ilildee in an over cool state, then the latent image becomes a bit developed toner and anschliesBend the image is fixed, whereby a copy is obtained, the IR irradiation of the unit dee Muttorbogens and dso übortrngungspaplere iJam under Anwenfleag

an etarkon infrared fire tube are durohgefUlirt «whereby the silver image part is on the lighter IH-permeable The Daa above can be applied a commercially available themtographic machine with a transparent quartz infrared ray lamp with a power of 30-100 W / cm are carried out typically for this

0098U / 1616

BAD ORlGSNAi-

like thermographic machine is the copier machine Thermofax Secretary type (trademark, manufactured by Minnesota Mining & Manufacturing Co., USA) "The tanned mother sheet does not contain sulfur in other parts than the image part, and therefore a networked unit thereof can be attached to the receiving sheet. Whole rollers can be punched with a surface temperature of about 150 ⁰ O, whereby a dust-containing latent image can be formed in simple catfish on the recording sheet. Due to the deaf-containing »tlhsrkUhlto latent image; which is formed in the above orphan on the receiving furniture is then developed by dusting with a toner. The toner is produced by incorporating a coloring substance into a thermo-meltable or chemical-containing vapor-high resin and the mixture is finely serialized. Any dopant as such which is currently commonly used in electro-photographic processes can be used. Development can be carried out using any method used in the electro-photographic process, such as the Magnot brush method, cascade method, or smoke chamber method. A dye is used in the toner; The Belbst stable int and the resulting copy is therefore extremely stable and does not have the disadvantage

^BA 0 0 9 8 U / 1 6 1 8

eng VerUliiCiseiiB au Γ> Y / it is also possible to use the toner approx HiLb can be incorporated into an i'arbstjff of each shade can, not only preserve Iopia, the black colored show pictures, but also pictures in the desired Colors, flat of the completion of toner development, that will Ingestion sheet by the application of heat or Lö'uungamltteidaiuof treated, obtaining a copy with dom-fixed image. In the case of the inventive material "can “Ine a / iHehnliiih a large amount of sulfur ale heat nipples ütoff η the layer can be worked on and therefore can bLo to about 200 clear copies of a single mother sheet be obtained

The materials shown in the illustration use light-sensitive materials photographic silver compounds for hero division the image and therefore aind of sensitivity Can be varied in a wide range. The present materials kcnneii can be processed according to many known methods, for example through direct unikehr, tanning development and the like » The present material can therefore not only be used for reproduction of handwritten documents and printouts but be used in a variety of areas for copying and printing. For example, letters are right on top the material by using a photographic typesetting

00 98 U / 161 6

ORIGINAL BATHROOM

machine printed and the material is used as 8 mother sheets, to get a gromui number of copies, odor a meter of oil ogincheo radar image is photographed directly and a multitude of copies is made immediately by the photographic made, no then the copies to the appropriate departments can be divided into two parts The toner is used to whitewash and therefore is It is possible to obtain a copy in natural colors by removing three /. parent arches of three Parbauoas from the halftone negative produced, the pictures on the mother Hogon Transfer an image flower and the images through the application by cyan, yellow and kagenta toners.

The following games are intended to advance the present invention vernnochaulionen, without oils but cu limit as within Numerous modifications are possible within the scope of the present invention. In the examples are all T "il"? voluntary

Example 1

150 g of sublimated sulfur powder are added to a solution of 5 g of saponin in 11 1- ^ iger aqueous gelatin, The oioh

0 0 9 B 1 / ♦ / 1 6 1 6
BATH ORIGINAL

The resulting meowing is in a porcelain ball mill for 20 hours treated to obtain a homogeneous sulfur dispersion that is then used to produce both samples A and B *

A: 0.8 parts of the sulfur dispersion are mixed with 1 part of a
gelatinous silver chloride emulsion (gelatin concentration 3 i>) mixed. The resulting mixture is called
Coating applied to a thick tracing paper to a dry thickness of 5 _P 5 p- and then dried *

B: To 1 part of a gelatinous silver chloroboramide emulsion (Ge-Xatine concentration 3 ^a / °) there are O _n B parts of 1% gelatine
The mixture is given as a coating on a thick
Tracing paper applied to a drying gap of 5-5 p- and then dried on the dried paper
the SchwefeldisperBic-n prepared above is applied as a separate layer as a coating to a dry thickness of 2 _£ 5 / i _;

G: To 1 part of a: * S gelatinous ί LBER ^ hJ.orbromidemuLaion (Gelatinekonzenüration 3 ^ο / °) are _0: ü parts ¹ -% gelatin
The misunderstanding is given as a coating on thick tracing paper to a dry thickness. 5 _r 5 u applied and dried

0098U / 1616

BATH ORIGINAL

The whether: gene samples A and B are erfindungagemäese Abbildungsmateriilien, the sample G is a comparative sample "These samples grazing in the form of the image is irradiated and then developed at 20 ⁰ C Mi.nute photographiechen The properties of these samples immediately after their preparation and after their two-day incubation at 55 ⁰ C measured. The results are given below:

Specific speed

Maximum density obfuscation

sample Immediately after
the her
position 2 days _rt
at 55 ⁰ C
incubated Immediately
after d.
Ήθγ-
Division 2 day·
at 55 ⁰ C
inku
beer Immediately
after d _e
Her
stel
lung 2 days
at
55 ⁵ C
inku
beer A. 93 90 1.9 1.8 0.01 0.01 B. 94 94 1.6 1.6 0.01 0.01 C.
(Ver
same) 100 99 2.1 2.1 0.01 0.01

The above results show that the deposition amaterioli · » are stable during their storage under rather severe conditions and that their photographic properties are essentially free from the adverse influence of sulfur.

BATH

0098 U / 1616

The samples Λ and B v / are used in the following Wels3 » to get copies:

A milk film negative bearing an original picture _? is transferred to the sample of an imaging material with the desired magnification, and a mother sheet with a mirror-image silver image is obtained. Ordinary paper is placed on the sensitive side of this mother sheet as a recording sheet and the unit is exposed to infrared radiation from the back of the mother sheet using a thermographic copier. The recording sheet is removed from the mother sheet (md manufactured trademark sale of the Xonishiroku Photo Industry Co ₀₎ according to the cascade method using Konifax toner "PP entwik Celtic u: _f .eichen id Thermis-jh fixed (by applying the Konifax-Fixiermisehine goods manufactured and?. sold by the Konlshiroku Photo Industry Go. _f Ltd. _{o) 9} with a "clear · ?. Copy received wircL .Burfih ¥ / iederholung dec above thermal transfer .. Staubent'vioklung and fixing succession to 200 sheets of clear copies from a MuiV.vbogea he "hold - / ground>

0098U / 1616

Example 2

50 mg of colloidal silver sulfide are in 1 1 of a 3 ~% strength aqueous gelatin solution suspended. To the suspension are added 30 mg of phenyl mercaptotetrazole as a color modifier to form a solution for a diffusion transfer image receiving layer to give »The solution is mixed with 0.3 1 of the sulfur dispersion used in Example 1 and the Mixture is used as a coating on a thin photographic Paper applied to a dry thickness of 2 ^ u and then dried, an inventive imaging material This material is used in the following ways: to get copies:

A negative material for diffusion transfer is brought into contact with an original to be reproduced according to the usual method and the unit is irradiated by reflex irradiation. The irradiated negate / uateria ?. is applied to the above-mentioned image material and the resulting unit is _{treated according to a diffusionBübert2 * aguB t} ^r : smethodG _s around a silver image on the. To show signs of decay, that the courage is ready for dispatch. Dan Silberbilc on the mother's sheet: - .st a correct picture, therefore a thin IR-permeable transperenteal rapier is used for the thera * iclien transmission of it the

BAD GRiGiNAt 009814/1616

Infrared radiation is applied to the side of the permeable paper after which it creates the same dust and thermal Fixing carried out as in Example 1 “around 100 sheets Receive copies

BATH

0098U / 1616

Claims (1)

Patent claims: Thermograph! Usable imaging material, thereby characterized in that it contains a support and an imaging silver photographic layer as a coating thereon, either this layer or its photographically adjacent layer containing finely divided sulfur incorporated therein. 2ο Thermographically usable imaging material Claim 1, characterized in that the delivering an image photographic silver layer a photosensitive layer a silver halide photographic emulsion containing finely divided sulfur incorporated therein. 3 · Educational material suitable for thermographic purposes Claim 2, characterized in that the emulsion layer is a direct-positive photographic silver halide emulsion layer. 4. Thermographically usable imaging material naoh Claim 2, characterized in that the Eottlsionaaohioht further contains a developing agent. BAD ORJGINAL 0098U / 1616 5o thermographically usable imaging device / serial. Claim 1 t characterized in that the photographic silver layer providing an image is a silver diffusion overlayed *. ^ Gungs-AifnabmeaoMcht » 6 ο Thermographically brewable imaging material according to claim 19 daduroii characterized _f that the photographically adjoining layer is a Schu'Sizschioht _{ . the remotely divided sulfur incorporated enfchälfco 7 ₃ thermographically usable imaging material according to claim 6 “characterized; there is an intermediate layer; is provided between the image-providing photographic silver layer and its photographiech angrenjsendea layer. BAD ORiGiNAL 0098U / 1 616