DE1797198B2 - IMAGE RECEIVING MATERIAL AND PHOTOGRAPHICAL RECORDING MATERIAL FOR THE DYE DIFFUSION TRANSFER PROCESS - Google Patents

Description

The invention also relates to a photographic material for which is already known

Recording material for dye diffusion - black and white photography with the help of other

Transfer process, consisting of several, ionic, water-soluble, optical brighteners

vis-à-vis different areas of the spectrum sen- of the type of diaminostilbene optically brighten and

sensitized light-sensitive silver halide to fix the brightener so firmly that bleeding of the

sion layers with adjacently arranged dye brighteners during the development process

developer, which is changed with a breakable, an aqueous one. The fixation of the brighteners takes place

container 65 containing alkaline developer nutty with the aid of cationic polymeric compounds,

and forms a unit with an image receiving part. which form addition compounds with the brighteners.

It is known e.g. B. from the USA. Patents According to the USA. Patent, brighteners and 983 606. 3 146 102 and 3 161 506, the British polymer of a layer of photographic recording

3 4

Drawing material are incorporated, or an optical brightener are, for example, those as brighteners

photographic material with a common known triazine-stilbene, coumarins, antracenes,

Terphenyls, tetraphenylbutadienes and quinoxalines,

bathes, with a bond of the optical brightener to Ak optical brighteners suitable triazine stilbenes

the polymer is made in the patent specification is also a 5 are, for example, from the USA. patents

Image receiving material for the Sflbersalzdiffusions- 2933 390, 2171427, 2 473 475, 2 595 030 and

procedure described. In this image receiving 2 660 578 and British patents 595065,

material are optical brightener and polymer in a 623 849, 624051, 624 052, 678 291, 681642 and

Interlayer between substrate and image 705 406 known

receiving layer arranged ip

The object of the invention is to provide an image receiving examples of such brighteners are:

material and a recording material for the coloring 4,4'-bis [4- (3'-sulfoanilino) -6-amino-s-triazine-

stoffdÄusioi ^ transfer ^ procedure to be specified in the case of 2-ylarmno] -stilbene-2,2'-disulfonic acid and their use of color images of better clarity

Brightness and purer shades as well as pleasing 15 4,4'-bis [4,6-di (# - hydroxyäthylarnino) -s-triazine-

white finders. 2-ylamino3-stben-2,2'-disulfonic acid.

The invention relates to an image-receiving material for the Farbstoffdiffusionsübertragungsver- Optical brighteners suitable Cumarinverbindunfahren consisting ^smc from § * ^s for example, the British patent from the

2o script 786 234 known 3-phenyl-7-ureidocoumarins.

a) a support.

b) a layer applied thereon from one of the following examples:

polymers containing acidic groups. _XT , _r , _{w ,,, 1V} . ,, _ ,,, "

c) a spacer layer for controlling the dif- ^ - [S - ^ - methylphenyl-cumannyl-7-urine off; rate of fusion, containing polymers with _a _ N-propyl-NM3-phenyl-cumannyl-i7)] - urea; hydrophobic and hydrophilic groups, and * ⁵ N-3-sulfoethyl-Ni-3-phenylcumannyl- (7) -ur-

d) an image receiving agent containing a mordant

layer, j-jj _e K _onzen concentration ^of optical brightener in a

which is characterized in that in ikr polymeric image receiving material or image receiving part of a Acid layer b) or in the spacer layer c) a recording material according to the invention can do a lot optical brightener is included. to be different. Appropriately contains an image

The invention also relates to a photo-receiving material or image-receiving part in at least a graphic recording material for the dye - one of the specified layers about 0.027 to about diffusion transfer process, consisting of more than 1.076, preferably about 0.108 to about 0.538 mg, against different areas of the spectrum 35 optical brighteners per dm ^{2 of support} surface. Higher irums-sensitized, light-sensitive silver halide concentrations of optical brightener generally have no advantages in nide emulsion layers with adjacent layers.

Dye developers which can be used with a frangible, The image receiving material according to the invention

contain an aqueous alkaline developer liquid - one of the commonly known photographic ones have the container as well as with an image receiving part a 40 layer support, e.g. B. a layer support Forms unit, which is characterized in that the paper, coated with polyethylene, one Recording material as the image receiving part is an image-transparent film or a white pigmented one contains receiving material of the specified characteristics. Cellulose ester layer carrier, for example made of Cellu-Durch the invention is achieved that in the context of loseacetat. Optionally, the support can be more customary Dye diffusion transfer process 45 additionally contain an optical brightener. Color images can be obtained whose clarity, the layer b) contains in a conventionally known manner

Color saturation and brightening are significantly better, non-diffusible polymers with acidic groups that than they can be achieved with known image receiving materials with alkaline compounds or polymeric bases are rich. The edges are also the ones that can react with the image. The layer can also contain compound receiving materials 50 genes prepared according to the invention contain which have substituents leading to Color images are no longer suitable as previously gray-white to yellow - binding of basic reactants, spotty, but pleasing white. Layer b) preferably contains water-soluble,

If the optical brighteners are in or above the carboxyl-containing polymers, their Na image-receiving layer housed, then trium and / or potassium salts are water-soluble. In the Due to the fluorescent properties of the top layer, however, it can also contain polymers, lighter images with reduced color saturation and which initially contain acid anhydride residues that are pure Preserved shades of color. End of the development process into free carboxyl residues The familiar "optical brighteners" have been passed over. As a polymer, the layer can thus be colorless or practically colorless organic, for example cellulose or polyvinyl derivatives, or else to understand bonds that contain that from sunlight or 60 acids of other polymeric compounds, UV light derived from fluorescent light. Examples of these are: dibasic half-esters of cellubates and the absorbed energy in the form of non-seeing derivatives with free carboxyl radicals, e.g. B. Cellubarem Emit blue or blue-green light. The Loose Acetate Hydrogen Phthalate, Cellulose Acetate Hydrogen Bonds thus contain in contrast to colored glutarate, cellulose acetate hydrogen succinate, ethyl cellulose, which contain colored chromophoric groups, 65 loose hydrogen succinate, ethyl cellulose acetate hydrogen fluorescent chromophoric groups. succinate, ethyl cellulose acetate hydrogen phthalate; ether-For the production of the image receiving material and the and ester derivatives of cellulose, which are combined with sulfoanhydric recording material according to the invention suitable, for. B. o-sulfobenzoic anhydride or poly

5 ^f 6

styrenesulfonic acid are modified, carboxymethyl- Preferably, the optical brightener is then used

cellulose, polyvinyl hydrogen phthalate, polyvinyl acetate in the form of a latex dispersion, & h. of a mixture

hydrogen phthalate, polyacrylic acid; acetals from poly- des brighteners with latex particles, too.

vinyl alcohol or carboxy or sulfo-substituted. In this procedure, the water-insoluble

Aldehydes, e.g. B. o-, m- or p-Benzaldehydsulfon- 5 brighteners preferably together with a vinyl

acid or carboxylic acid, partial esters of ethylene maleic resin, e.g. B. a poly (alkyl acrylate), poly (alkyl

acid anhydride mixed polymers or partial esters of methacryiai), poly-vinyl acetal) or an alkyl

Methylvinyläthermaleinsäureanhydridaipolymeri- acrylate-alkyl methacrylate copolymer, in one

sateo. water-immiscible solvents, such as

The function of layer b) is to dissolve the ent- io, for example, ethyl acetate or chloroform,

to finish winding and to stabilize the finished image, whereupon the resulting solution in an aqueous solution

Ren by using the alkaline solution to be a hydrophilic, film-forming binder, such as

treatment of the photosensitive photographic for example gelatin, or an ethyl acrylate

Material from which the dyes are emulsified depending on the acrylic acid copolymer. On that

diffuse from exposure and development, 15 the resulting emulsion is allowed to settle and

was used, reacts and its pH value is determined by evaporation of the solvent and the water

low dried The dried material is then

The between layer b) and the Büdempfangs- ßend by soaking in water under mechanical

layer arranged spacer layer c) has processed the stirring into a coating compound. the

If there were, the diffusion speed of the individual coating compound obtained may ultimately depend on

Components of the alkaline developer solution in the desire for addition of the polymeric acid (in the case of

Control layer b). The spacer layer ensures that an acid layer is to be produced), one

ensures that both the material suitable for complete development for an intermediate layer, such as

of the exposed photographic recording material, for example polyvinyl alcohol (in the event that a

rials as well as those for transferring the dyes from the intermediate layer) or as

the photosensitive recording material to which such are applied.

Image receiving material required time observed The following examples are intended to illustrate the invention. The spacer layer expediently has one to illustrate it.
Thickness from 3 to 25, preferably from 8 to 15 microns. . .
The spacer layer can e.g. B. from polyvinyl acetate, 30 13 e 1 s ρ 1 e 1 1
Polyvinyl alcohol and gelatin are made up. It can 1. First, a photographic recording remote, such as. B. from the Belgian patent nungsmaterial produced in that it is known to one with 699 757, contain a white pigment. Cellulose acetal film provided with an adhesive layer. If necessary, the following layers can also be applied:
Additives, such as coating aids, 35
Hardeners and the like. A. a cyan dye developer layer

The one containing a pickling agent for receiving the

The dye image-specific image-receiving layer is in an aqueous gelatin solution with the blue-green

Usually permeaber for alkali. You can use the developer S.S-Dihydroxy-M-bis-K / J-hydroquinonyl-

customary known mordant for 1 dyes contained 40 «-methyl) äthylamino] -anthraquinone was in one

th. For example polymeric vinyl methyl ketoamino mixture of N-n-batylacetanilide, 4-methyl-cyclo-

giianidine derivatives of the US patent specification hcxanon and a common dispersant (alkali

2,882,156 of the type described, poly (2-vinylpyridynol B) dispersed. The obtained mixture became

metho-p-toluenesulfonate) and corresponding compounds passed several times through a colloid mill to the

fertilizing the from US Pat. No. 2,484,430 45 adhesive layer of the cellulose acetate film backing applied

known type as well as cetyltrimethylammonium and dried to the 4-methylcyclohexanone

bromide. Particularly advantageous pickling agents are used in volatilizing,
Belgian patent 634 515.

Suitable cationic or basic, organic, ß. a red sensitive emulsion layer

Dye-staining compounds are, for example, 50

quaternary ammonium and phosphonium and on top of the cyan dye developer layer A.

ternary sulfonium compounds, in which one opposite the red area of the spec-

Nitrogen, phosphorus or sulfuronium atom in the center sensitized gelatine silver bromoiodide module

at least one hydrophobic ballast group, such as applied for example,

a long-chain alkyl group or a substi- 55

tuated alkyl group, is connected. C. an intermediate layer

The optical brightener can be used in layers b)

and c) incorporated by known methods. On the red-sensitive emulsion layer B was

If the brightener is water-soluble, it can be applied to one of the intermediate layers of gelatin,

between the support and the image receiving 60

layer located in the form of an aqueous D. a magenta dye developer layer
Solution to be incorporated. However, the image receiving materials according to the invention preferably contain an aqueous gelatin solution with the magenta water-insoluble optical brighteners. A water-based dye developer 2- [p- (2 ', 5'-dihydroxyphenethyl) -insoluble or at most slightly soluble on-phenylazo] -4-n-propoxy-1-naphthol was in a lighter layer in the form of a solution in a mixture of cyclohexanone, Nn-butylacetanilide and an organic solvent, such as, for example, a customary dispersant (alkanol B), disper-methanol, ethanol or pyridine. greed. The resulting mixture was repeated several times

. ι

passed a colloid mill, on the intermediate layer C c) an image receiving layer

applied and dried to the cyclohexanone

to evaporate. 12.5 g of a 10% polyvinyl alcohol solution, 0.5 ml

Acetic acid, 0.1 ml isooctylphenylpolyethoxyethanol

E. a green-sensitive emulsion layer ^s and 0.05 g of l-phenyl-5-mercaptotetrazole were added to

a solution of 1.25 g of poly-4-vinylpyridine in 25 ml

Distilled water was added to the magenta dye developer layer D. The received Miwurde a green-sensitive silver bromoiodide mixture was made up with distilled water to a total of sion applied. 50 g topped up and placed on the spacer layer in one

ίο Thickness, measured when wet, of 0.1524 mm F. applied an intermediate layer.

3. Another image receiving material B was used

On the green-sensitive emulsion layer E was prepared that in the layer from the acidic groups an intermediate layer of gelatin is applied. containing polymers an optical brightener

15 contained. A yellow dye wrapper layer of waterproof paper was applied to a substrate made of G.

An aqueous gelatin solution containing the yellow color _{a) e} i _ne layer of acidic groups

Substance developer 1 - phenyl - 3 - N - η - hexylcarboxamido containing polymers
4- [p- (2 ', 5'-dihydroxyphenethyl) phenylazo] -5-pyrazo-20

lon was in a mixture of Ditetrahydro- A solution of 3 g resorcinol biglycidyl ether in furfuryl adipate, ethylene glycol monobenzyl ether and 20 ml of ethanol became a solution of 50 g of one a customary dispersant (alkanol B) dispersed from 60% butyl acrylate and 40% acrylic acid greed. The mixture obtained was added several times as a copolymer in 20 ml of ethanol. the a colloid mill out, whereupon the resulting mixture was mixed with ethanol to total Spersion cooled to settle and made up to 250 g to remove. Thereupon the received Bedes Ethylene glycol monobenzyl ether was washed. Layering solution, each per 25 g of coating-final The dispersion was based on the second solution, 4.4 mg of that in Example 3 of the British Patent Interlayer F applied and dried. 786 234 described optical brightener

30 N - (ß - dimethylaminoethyl) - N '- [3 - phenyl - cumari-

H. a blue-sensitive emulsion layer nyl- (7)] - incorporated urea. Eventually the

obtained coating composition on the paper backing in

On the yellow - dye developer layer G such a way was applied that, per dm ^{2 of} support surface about

a blue-sensitive silver bromoiodide emulsion - 0.22 mg optical brighteners were omitted,
wear. 35

I. a top layer b) a spacer layer

On the blue-sensitive emulsion layer H, 8 g of a 55% polyvinyl acetate latex and 0.05 g

finally one of the colorless auxiliary dye developer l-phenyl-5-mercaptotetrazole with 12.5 g of a

4'-methylphenylhydroquinone containing gelatin 40 10% polyvinyl alcohol solution mixed. Which he-

layer applied. Holding mixture was made up with distilled water

2. Furthermore, an image receiving material A was filled up to a total of 25 g and the resulting coating

prepared as follows (comparative material): sealing compound on the first applied layer in

On a substrate made of waterproof paper with a thickness, measured when wet, of

were applied: 45 0.1016 mm applied.

a) a layer of an acidic group _x . ". ,,.

containing polymers ^c > ^eme image receiving layer

25 g of a 60% butyl acrylate and 40% acrylic 6.25 g of a 10 ⁰ / o polyvinyl alcohol solution and

Acid-formed copolymer were dissolved in 50 ml of 50 0.05 ml of isooctylphenylpolyethoxyethanol to give denatured ethanol. 1 g of resorcinol biglycidylic acid was added to the resulting mixed solution of 6.25 g of poly-4-vinylpyridine in acetic polymer solution. The mixture obtained was added with ether in 5 ml of ethanol, whereupon the mixture of distilled water was made up to a total of 25 g and made up to a total of 100 g with ethanol. The resulting coating mass was then applied to the spacer The resulting mixture was then applied to layer b) in a thickness, measured in the moist area, of 0.1524 mm per dm * of carrier,
area about 2.7 ml of coating material, corresponding to 4. Another image receiving material c),

about 269 mg of acidic resin, accounted for. as described under 3., but with the

The exception is that the polymer which has _{a spacer layer ^ the} ^^ group _{] used} to produce the layer from b)

8 g of a 55% strength polyvinyl acetate latex dispersion and 8.8 mg of the optical load were incorporated into 12.5 g of a 10% strength polyvinyl alcohol brightener, so that solution was added to the acid layer. The mixture obtained was made ^{up to a total of 25 g with a total of 0.43 mg of the AufWasser per dm 2} of support surface, whereupon the brighteners were accounted for.

The recording material was divided into three parts of acidic group-containing polymers in a thickness that measured red and green under a step wedge in the moist state, exposed from 0.1016 mm up and blue filter and then in contact with was carried. the individual image receiving materials listed under

2, 3 and 4 were described, with an aqueous activator of the composition:

High viscosity hydroxyethyl cellulose .. 3.5%

Sodium hydroxide 4.5%

Benzotriazole 2.0%

l-phenethyl-2-picoliDium bromide 2.0%

have been moistened. In any case, a transfer of the blue-green, purple-red and yellow

10

Dye developer images from the undeveloped areas were observed on the image receiving material

will. In each case, a transfer time of 1 minute and a roller opening of 0.4304 mm, selected according to the thickness of the activator layer.

The obtained color copies were checked for their density,

investigated their reflectivity and their relative brightness. The ones obtained during the investigations Results are given in Table I below:

Table I.

Image reception
material

Dmax

(Neutral scale)
Red I green I blue

(Neutral scale) Red I Green Blue Percentage
Reflectivity at

400πιμ J 4Ο5πιμ | 410ηιμ

Relative brightness *) at
410ιτιμ Ι 420πιμ 430ηιμ

1.47
1.61
1.53

1.83
1.88
1.85

1.82
1.93
1.92

0.18 0.20 0.19

0.21 0.22 0.23

0.23 0.25 0.25

76.5 82.5 85.5

78.0
80.5
81.5

79
87
87

80
90
94

82.0 90.5 94.5

*) The values were determined from the image receiving materials which did not contain any transferred image dyes.

Example 2

An image receiving material with a layer of an acidic polymer was obtained and an image receiving layer corresponding to the image receiving material 2 of Example 1, however, with the exception that the spacer layer is a optical brightener was incorporated:

8 g of a 55% polyvinyl acetate latex and 2.25 g of a poly (alkyl acrylate) latex containing 9.2% solids, in which 2.6% of the optical brightener is N - (β - dimethylaminoethyl) - N '- 3 - phenylcoumarinyl - (7) urea were added to 12.5 g of a 10% polyvinyl alcohol solution. The mixture obtained was made up to a total of 31 g with distilled water and applied to the layer of a polymer containing acidic groups in a thickness, measured in the moist state, of 0.1016 mm, with about 0.16 mg of the optical ^{per dm 2 of support surface} No brighteners were used.

The image receiving material prepared in the manner described was, as described in Example 1, for transferring a dye image from the recording material described in Example 1 For comparison purposes, the relative brightness of the image receiving material with the brightness was used of the image receiving material A of Example 1 was compared. The results are in the table below compiled:

Tables

Example!

Relative brightness at 410ΐημ 1 420πιμ Ι 430πιμ

79
86

80.0 89.5

82.0 89.5

Example 3

A. The recording material and the image receiving material of Example 1 were as in Example 1 treated, but with the exception that the negative material before treatment completely exposed and then the transfer to determine the influence of the treatment conditions on the image receiving material in the absence of a color transfer image.

B. For comparison purposes, an image receiving material with a layer of an acidic group was used containing polymers and an image-receiving layer such as the image-receiving material A of Example 1 manufactured in the manner described below:

b) spacer layer

The spacer layer corresponded to the spacer layer of the image-receiving material of Example 2, except that the coating composition used to manufacture the spacer layer g 4.5 of poly (alkyl acrylate) -latexdispersion contained so as mg per dm ^{2 of} support surface about 0.34 of optical brighteners were omitted.

The obtained image receiving material was prepared in the manner described using the recording material of Example 1 treated and tested, but with the exception that the recording material fully exposed before treatment.

The values of the relative brightnesses of the copies, which were obtained with the image receiving sheets are summarized in the following table ΓΠ:

Table III

attempt

Relative brightness at 410τημ 420ΐημ Ι 43Οΐημ Ι 440ΐημ 450ΐημ 460ΐημ 470τπμ 480πιμ 490 πιμ

500πιμ

600τημ

700πιμ

52

55

54.0
60.0

56.0 57.5 62.0 62.5

62.5

59.0 63.0

60.5

62.0

64.5

63.0
64.5

68.5
72.5

80.5 52.0

From the breadth of the table it can be seen that those with image receiving materials according to the invention obtained color copies have better brightness and density, as is the case with dye developer diffusion transfer systems means a significant advantage

Claims (4)

1 2 patent specification 804971 and the French patent claims: writing 1313 767, for the production of color images by the diffusion transfer process photo- 1. Image receiving material for dye-graphic recording materials with so-called diffusion transfer processes, to use consisting of 5 th dye developers. This up- \ - ei, - 1, + t ^ a drawing materials usually have several a) a contractor,. light sensitive super halide emulsion layers b) a layer of emem ^ applied thereon, each of which is sensitized to a different polymer containing acidic groups, _{region of the spectrum} . the c) A spacer layer for the control of the _{10 dye} developers are arranged adjacent to the individual diffusion speed, enitoltend poly-overhalide emulsion layers, with more hydrophobic and hydrophilic _{color of} the dye developer of the color of the superhalide emulsion layer, which is visible through group and ^ _6. d) is _{practically complementary to a source of light that} contains a pickling agent. The ^{x c} '15 development of the recording materials takes place with characterized in that in the aid of alkaline treatment solutions, when em- polymeric acid layer b) or, in the spacing effect on the exposed recording material, the layer c) contains an optical brightener. recorded latent images in the negative image 2. Image receiving material according to claim 1, developed there- fore with the help of the dye developer, characterized in that it is the optical on- 20. The latter are immobilized in the negative image brightener in a concentration of about 0.027 to areas, ie made immobile, about 1.076, preferably from about 0.108 to about. The dye developer of the unexposed areas contains ^{0.538 mg / dm 2 of substrate area.} In contrast, they diffuse to the surface in a way that is true to the image 3. Image receiving material according to claim 1, there- of the recording material and are from there characterized in that it appears as an optical image with the formation of a positive multicolored copy lighter a water-insoluble triazine-stilbene compound- an image receiving material transferred. dung, an optionally substituted coumarin It is also known, for. B. from the German or contains 3-phenyl-7-ureidocoumarin. Patent i 155 673, which after the diffusion 4. A photographic recording material for transfer processes producing color images thereby the dye diffusion transfer process, prior to destruction by ultraviolet radiation standing from several, against different protect that one the development of the exposed Areas of the spectrum sensitized light recording material in the presence of an ultra-sensitive Silver halide emulsion layers performing violet light absorbing compound, with adjacently arranged dye developers their diffusion rate in the alkaline one Learn that with a breakable, an aqueous 35 treatment solution is less than that of the alkaline color Substances generating developer water and those with the paint container as well as having an image receiving part in one of the substances on the image receiving material forms, characterized in that the separation is. The ultraviolet light absorbing Drawing material as an image receiving part an image connection can be used from the beginning in the alkali receiving material according to claim 1 contains. 40 see treatment solution to be present or also be present in an outer layer of the image receiving material from which it is made by the processing solution is released. The disadvantage of using the previously known 45 image receiving materials is that the colors of the The invention relates to an image receiving material for holding color images not always the desired clarity the dye diffusion transfer process, persistence and brightness and the edges of those obtained based on color images does not have the desired degree of whiteness cu-i, - wise. These disadvantages are also not eliminated by the a) a layer carrier,. ₅₀ known use of ultraviolet light absor- b) a layer applied thereon made of a _{polymer which contains} acidic groups during the development process and which is made of a binding compound is eliminated. Rather, by pulling up the c) a spacer layer for controlling the diffusion-absorbing _{ultraviolet light} compounds at the rate of fusion, containing polymers with _{the image-receiving layer containing the mordant-} containing hydrophobic and hydrophilic groups, and _{an impairment of the} color saturation. d) an image receiving agent containing a mordant be taken ^layer - From the USA patent specification 3,269,840 it is finally