DE2436985A1 - LIGHT SENSITIVE LAYER AND METHOD FOR PRODUCING A PHOTOGRAPHIC IMAGE - Google Patents

Description

Photosensitive layer and process

for making a photographic image

The invention relates to a photosensitive layer and a method for producing a positive od. negative photographic image.

The technical field of the invention belongs to the field of photosensitive compositions for the Photography or the photocopy.

Photosensitive. Compositions with silver complex compounds from thione -2-thiazoline 4 substituted in 3, with a hydrogen acid in position 3, are already known. Through these compositions, the fixation of the non-reduced silver halides is possible with the aid of a Solvent no longer required. But the traditional phases of development persist. To the A chemical agent must be added to the development of the image.

The photochromatic properties of spiropyrans and their use, especially in the field, are also known photography: closed spiropyrans are exposed to ultraviolet rays, in this way the corresponding colored photomerocyanine is obtained. However, the image obtained in this way only exists temporarily, as it is gradually destroyed by the visible radiation, with simultaneous regeneration of the spiropyran of closed form. The difficulties arise in the fixation of the photomerocyanine, so that this Types of application are not easily exploitable.

The subject of the invention is the production of a 'light-sensitive Layer in which the photochromic properties of the spiropyrans are used and thereby strengthened be that one of the two forms of spiropyran as

E09807 / 107A

Allows another reaction to act as a catalyst.

This is achieved by a layer made up of the subsequent ones Components is composed:

- at least one heterocyclic photochromatic spiropyran that is selectively transformed under the action of a certain radiation, according to the following reaction:

where the radicals R «, R ₃₁ , R ^, R ^ i , R3 and X are defined as follows:

Ro: η methyl-, η phenylthio-, -phenyl, -chloro, -bromo, methoxy-, hydroxy-, naphthyl-, chloro-4 phenyl, bromo-4 phenyl, hydroxy-4 phenyl, methoxy-4 phenyl -,

Ro ₁ : methyl, isopropyl, η hexyl, benzyl, phenylethyl,

R ₆ : nitro,

R> ,: hydrogen, oxygen, phenylthio,

R ₈ : methoxy, oxygen,

X: thio- seleno- imido- oxo-, aza-, dialkylcarbo-

- at least one thioether from orthosubstituted nitrogen heterocycle with the following formula:

INSPECTED

509807/1074

in which the radicals X and R ₁ are defined as follows :

Λ ^ H ₂

X = -N - R ₂ , - 0 -, -S-, -Se-, -R ₂ -, ^ C ^c , -R ₁ , -R ₂ and R ₂ , from the group of the alkyl and

Acylalkyl radicals;

the open form of said spiropyrane acts as a catalyst for the conversion of said thioether into thione according to the following reaction:

so that the latent image obtained by exposing said spiropyrane is enhanced; *

- at least one reagent for developing said enhanced latent image.

In this way, the amount of photons required for the formation of the latent image was reduced.

Furthermore - nachdeii ^; the; Decoloration and fixation occurs "in situ" - eliminating the development and fixation phases which usually require the use of additional chemical agents that react with the constituents of the sensitive layer.

B 0 9 8 0 7/1 0 7 4 originally inspected

The latent image was also developed to a visible and permanent one by acting on the thiones obtained in the process Image.

Said developing reagent is a component either from the group of fatty acid metal salts, which can be reduced by the thiones, or from the group of zinc, cobalt and nickel halides or from the zinc and cobalt thiocyanates, which are included in this second Case form a complex compound of the formula ML ₂ with the thione L mentioned.

Said layer preferably contains a metal oxide from the group of titanium and zinc oxides, the semiconductor properties have and see in the visible area be endowed and sensitized.

The mentioned layer can instead of the mentioned metal oxides a component from the group of cobalt, copper or. Contain nickel salts, which has the purpose of entering into a complex compound with the said catalyst in order to this. to fix.

If the said layer is in addition to its three main components contains a semiconductor metal oxide, said spiropyran and said thioether are in the adsorbed state on the surface of the particles of said semiconductor metal oxide.

The invention also relates to the method for producing a photosensitive layer with a semiconductor metal oxide, wherein said spiropyran and said thioether are mixed in a solvent, then this solution will be particles of the said

509807/1074

Metal oxide is added, the whole thing is stirred vigorously for at least 10 minutes in order to adsorb effect, then a binder is added which contains said developing reagent in solution, and at least Stirred for 10 minutes; only a thin layer is applied to a solid support and the said Solvent is evaporated.

In order to get a photographic image with the aid of the photosensitive layer according to the invention, said layer is exposed either to ultraviolet radiation if said layer initially contains a spiropyran of closed form, or to visible radiation if said layer initially contains a spiropyran of contains open form; this creates a latent image through the selective transformation of the from. the irradiation 'detected points. .

The said layer is then heated at a temperature of 100 140 ° C. in order to enable the said latent image to be intensified by the catalytic conversion of the said intensifying reagent into a thione and then the formation of the visible image through a reaction between the said thione and the metal salts mentioned. '".-".

The result of the invention is a new product consisting of a photosensitive layer which enables the production of a positive or negative photographic image.

The main advantage is the achievement of a quantum power that is well above the usual power. at

509807 / TÖ74

243698b

This invention requires fewer photons than the conventional methods, since to catalyze the Conversion reaction of thioether to thione only requires a small amount of spiropyrans.

This chain reaction has other advantages: its speed can be controlled by temperature.

The temperature required to carry out the reaction is' perfectly above the ambient temperature, whereby the preservation of a light-sensitive layer containing the spiropyran of the open form is easily possible, Since this has no effect on the conversion of the thioether if the layer mentioned is not heated sufficiently will.

Once the thione is recovered, there are several reagents for latent image development that go into making it enable a visible and permanent image.

Another great advantage is that development and fixation takes place with the reagents that be inserted into the photosensitive layer from the beginning and that is controlled by the temperature given is.

This layer also has a high sensitivity and Resolution. ,

Further advantages consist in the possibility of using two different processes for the production of photographic images Pictures.

The first for direct images, either negative from a negative, or positive from a positive, is done in the way,

609807/1074

that a layer containing spiropyran in open form, exposed to visible radiation.

The second for the inverted image, either negative from a positive, or positive from a negative, takes place in the Way that a photosensitive "layer, which contains spiropyran in closed form, is exposed to ultraviolet radiation is exposed.

A final advantage of the invention is the possibility the development of images in the form of complex compounds the thiones that are either in the ultraviolet range or absorb in the visible range.

Further features and advantages of the invention will become more readily understood with reference to the accompanying drawings, in which. the figures show the following:

Fig. 1 is the schematic representation of the process for Making a positive image from a negative by inversion. ;

Fig..2 is the schematic representation of the procedure for the direct creation of a negative image from a Negative.

Fig. 3 is the schematic representation of the process for the direct creation of a positive image of the object itself.

These three figures illustrate in schematic form the production of a light-sensitive layer, " standing from two different, adjoining and superimposed layers. It will be special, however

509 807/107

it should be noted that the invention is not limited to this embodiment and the photosensitive Layer can very well consist of just one layer that contains all of the components.

The term "photosensitive layer" embraces any means which follows in one or more layers Components contains:

- at least one heterocyclic spiropyran, which according to the radiation to which it is exposed, in "open" or "closed" form exists. These two forms are schematic in the reversible reaction below shown:

.Vrti * .2.-;. .

This spiropyran is preferably made from the benzothiazoline, benzoseleniazoline, benzoxazoline, benzoimidazoline, benzoindoline spiropyran selected that can be replaced by the radicals summarized in the following table:

(See the next page!)

5Q9807 / 1074

ORIGINAL INSPECTED

"Λ"

CR '''■. ■ - 'NO ₀ ''/■''' · '"' / '. Ν'. '·,' OCH ^ ;.". Radical isopropyl. ^; '. >>.'7>.'^ *. 0

· ■ ■ • -NO «^ ; ''"'.'-'.'Λ' OCH ₀ * ¹ .-. 'Üadical

h ■■ · "■■ · ^; '■! ' -., - ■■ '■ · ■.'. ·· .''- '. ·' ■■. ν ···; · '·; ■ - - ■ Γ. * · Ν phenylethyl 7l · \ * Vpv; V * f '- *

phinyl "Λ · ■ - chloro-4 phßnyl ■ 'Lromo- ^ phenyl' "

liyilro> -. yH -phenyl, ^ φ ^ ν. ^

CH-, ■ '· ■

509807 / 107A

ORIGINAL INSPECTED

- at least one thioether from a nitrogen heterocycle following formula:

with "« leu? - X is a radical from the group of the following radicals;

^ ET - E ₂ , -0 -, - S-, -Se-, -R ₂ -,

^E 2

R ^, Rp, Rp, is £ .this is a monovalent radical from the Group of the illcy "! -; Dd. Acylalkylr adikal e.

One of the following components is preferably selected, which are given as non-limiting examples

the alkyl thio-2- and acyl-methyl-thio-2-benzothiazoles and -benzoxazole,

«- Hk3LL-tJiip-2 · = and acyl-methyl-thio-2-Kalkyl-imidazole and thiazoles,

-at least one reagent for developing the image, which is a metal salt from one of the following two groups:

a) the fatty acid metal salts reducible by the thiones, which are good cation vectors because they are known to become liquid when heated.

These salts are preferably:

the behenates, resinates, naphthenates, bonzoates and stearates dee silver, cadmium, copper, cobalt, tin, magnesium, manganese, nickel, lead and zinc.

509807/1074 _ n -

ORIGINAL IMSPEOTSD

2A36985

b) the zinc, cobalt and nickel halides and the zinc and cobalt thiocyanates. ·

These three components of the photosensitive Layer another component can be added, which enables the fixation of the spiropyran of the "open form", about its destruction when the said layer is heated that is necessary to enhance and develop the image. This optional component is either a semiconductor metal oxide or a metal salt.

Among the metal salts may be mentioned as non-limiting examples ·: the cobalt, copper and nickel salts, which form a complex compound with the open form of the spiropyran, these components are used for doping the metal oxides.

Of the metal oxides having semiconductor properties, is preferred uses an oxide belonging to the group formed from titanium and zinc oxides. These oxides become properly endowed and sensitized in the visible area. Experience has shown that with excellent results in copper-doped titanium oxide and with in nickel or nickel-cerium doped zinc oxide can be achieved.

These two oxides are doped as follows stated:

The oxide particles are left in an oily copper sulphate solution (or in a 0.78% nickel chloride solution) for about 10 minutes. pearl under movement. The oxide particles are then filtered and dried. Then they become one Heat treatment subjected to the titanium oxide in a

509807/107 4

One hour of heating at 100 ° C consists of one Four hours of heating at 420 ° C follows, and with zinc oxide This treatment consists of heating at 100 ° C for one hour, followed by heating at 50 ° C for five hours follows.

This doping process makes the semiconductor sensitive to visible light and no longer to ultraviolet light. Thus, the semiconductor can contribute to the photons absorb visible light, which changes its electronic structure and changes the open form of the spiropyrane can fix.

This metal oxide must also be adsorbent. This adsorption takes place in a liquid medium: the different components of the photosensitive layer are dissolved in an ordinary solvent, which is then evaporated. This adsorption by the semiconductor gives the photosensitive layer great sensitivity and high resolution.

The various ingredients listed above can be combined in a single layer, which form the photosensitive layer. The method for making such a layer is as follows Example illustrates:

100 mg of spiropyran are dissolved in 100 ecm of solvent (2/3 toluene, 1/3 ethanol). 55 g of titanium oxide are added. Mix for about 10 minutes while stirring vigorously. Then 500 mg of thioether are added. Homogenize and then add 20 g of the resin in solution (which is the binder in which a fatty acid metal salt, reducible by the thiones, is in the form of small 2 - 5 μ large particles). This is followed by mixing for about 10 minutes.

509807/1074 -

The viscous composition obtained is then applied in the form of a thin film to a solid base, for example on paper, plastic or metal (these examples are not to be understood as limiting). Afterward the solvent is evaporated.

If you want to produce a light-sensitive layer consisting of two superimposed layers:

- of which the first covers the backing and the thioether and contains the metal salt;

- and the second covers the first layer and is intended to be the first to receive the light radiation; these Layer contains the spiropyran and the semiconductor metal oxide or the metal salt. ■■ \

so one only has to separate the components of each layer Mix and apply the layers one after the other, waiting until the first layer is dry.

Referring now to Fig. 1, 2 and 3 referred to are intended to illustrate the, process of forming a photographic image.

Fig. 1 shows a light-sensitive layer which contains the following components: "-" - ..

- in (2) a spiropyran of closed shape;

- in (3) an amplifying reagent and a reagent for developing the image.

In Figures 2 and 3, the components of the ¹ light-sensitive layer differ from the previous one in that the spiropyran in (2) is of open form.

-.14 509807/1074

In the case shown in Fig. 1, the light-sensitive © Layer through the negative (1) irradiated with a wavelength \, which corresponds to the range of ultraviolet rays is equivalent to. The required exposure time is a few seconds to a few minutes, depending on the nature of the components. The radiation penetrates only the transparent zones of the said negative and reaches the corresponding ones Zones of (2) in order to convert the spiropyran of the closed form into photomerocyanin according to the following reaction:

The photomerocyanin in the open form is then used as a catalyst for the conversion of thioether from ortho-substituted nitrogen heterocycle used according to the following reaction:

This conversion is preferably carried out at a selected between 100 ^ö C and 140 ° C temperature ^ it is carried out a chain reaction, the catalyst is regenerated and the speed depends on the temperature: attempts were made with temperatures below 100 ° .C, the reaction was then much too slow.

If, on the other hand, one works at 120 ° C, the conversion of 50 % of the amplifying reagent is achieved in a few minutes.

509807/1074

OHiQlMAL IiMSFEGTED

The metal salt present in (3) now goes with the above Thion initiates a reaction, which ultimately causes it to emerge of a visible and permanent image.

There are two different ways of obtaining a visible image Responses planned:

a) - the first consists of a reduction of one or more Metal salts from fatty acids, such as:

the behenates, resinates, naphthenates, benzoates and stearates of the Silver, cadmium, calcium, copper, cobalt, tin, magnesium, manganese, nickel, lead and zinc.

The aforementioned metal salts are in the form very fine particles of the size of a few microns, e.g. 2-5 microns, are used and the said particles are used dispersed in a suitable binder.

The following products may be mentioned as binders, the Means listed as an example are not to be understood as limiting are:

Polyvinyl alcohol, methyl ^ cellulose, hydroxymethyl cellulose, Polyvinylpyrrolidone, the "Pliolit" styrene-butadiene copolymers.

This reduction process is facilitated by heating the sensitive layer, which makes the fatty acid metal salt liquid and thus enables the ion mobility that is required for a reduction with the thione }

b) - the second reaction, which leads to the development of a permanent image, is based on the complex formation of the thiones.

- 16 50 9 8 07/1 07 4 ^: ■ "- ■ -

One now uses salts such as:

Chloride, bromine salt and zinc iodide, cobalt and nickel and the Zinc and cobalt thiocyanates; these examples are not to be understood as limiting.

Salts of this kind form a complex compound together with thione of type 1/2, with one metal salt molecule on two coordination molecules.

The following phenomena were found:

The complex compounds of the formula: Zn Cl ₉ L ₀ , Zn Br_ L ₀ Zn I ₀ L ₀ , Zn (NCS ) ₀ L ₀ absorb in the ultraviolet range;

- The complex compounds of the formula: Co Cl ₂ L ₂ , Co Br ₂ L ₂ Co I ₂ L ₂ , Co (NCS) ₂ L ₂ , Ni Cl ₂ L ₂ , Ni Br ₂ L ₂ , Ni I ₂ L ₂ absorb im visible area.

In the cases shown in Figures 2 and 3 the spiropyran in (2) is of "open form".

The layer is irradiated with a wavelength \ _{2 of} the visible range.

In Fig. 2 a negative is assumed. The rays penetrate the said negative only in the places which allow the passage, and reach the spiropyran (2) in the corresponding zones, which is according to the following Converts reaction to spiropyran of "closed form":

60980 7/1074 ORIGINAL IiMSFEGTED -

The zones not reached by the rays always contain the spiropyran of the -open "form." "The latter is thus called Act as a catalyst to initiate the amplification reaction, which leads to the formation of thipines, which in turn is a React with the metal salts to eventually form a to give a negative image.

In the case of Fig. 3, the object to be reproduced is assumed. The mentioned object is irradiated in the visible range, the X ^ rays come from the reflection from the bright areas of the mentioned object and hit the corresponding lines of the light-sensitive layer, whereby they transform the "spiropyran of the" open form "into the ^ closed form "effect. The zones not reached by the above-mentioned strands are retained by the spiropyrans in the open form ^; The conversion of the intensifying reagent into the thione part, called the thione, then undergoes a reaction with the reagent for the development of the image, in order to create a visible and permanent image that reproduces the opposite in the positive.

Without going beyond the scope of the invention; can he Expert, of course, makes various changes Means and procedures are only limited as necessary Examples blscnriebin wiärdelii ..

Claims (1)

PATENT CLAIMS 2 * 36985 IJ A new product consisting of a light-sensitive Layer through which a positive or negative photographic image can be produced, characterized in that this layer is composed of the following components: - At least one heterocyclic photochromatic spiropyran that under the action of a certain radiation Reaction is converted: where the radicals R ₃ , R ₃₁ , Rg, R5 ■, Rq and X are defined as follows: Ro: η methyl-, η phenylthio-, -phenyl, -chloro, -bromo, methoxy-, hydroxy- ,, naphthyl-, chloip- ^ · phenyl-, bromo-4-phenyl-, hydroxy - ** - phenyl-, methoxy- ^ phenyl-, Ro,: methyl, isopropyl, η hexyl, benzyl, phenylethyl, Rg: nitro, R _Al : hydrogen, oxygen, phenylthio, Rq: methoxy, oxygen, X: thiOr, seleno- imido-, oxo-, aza-, -dialkylcarbo- at least one ortho-substituted nitrogen thioether heterocycle of the following formula: iB'Öi98Ö7 / 10-74 in which the radicals X and R ₁ are defined as follows : \ Vx-R ₂ X = ^ N - R ₂ , - 0 -, -S-, -Se- ', -R ₂ - / - ⁰ N ₁ R ₁ ^; " ^ß l ' . -R ₂ and R ₂ , from the group of the alkyl and acylalkyl radicals ; the open form of said spiropyran, which acts as a catalyst for the conversion of said thioether into thione, according to the following reaction: ^: mmMmm! k so that the latent image obtained by exposing said spiropyran is enhanced; .-..- .. · ■ - at least one reagent for developing said latent and enhanced image. . 2) layer according to claim 1, characterized in that said spiropyran is the benzothiazoline spiropyfan . 3) layer according to any of claims 1 od. 2, characterized in that said thioether is an alkylthio-2-benzothiazole. 4) layer according to any one of claims 1 bd * 2, characterized in that said thioether is an alkylthio-2- benzoxazole. 50 9 80 7/1 07 A IfSJSPECTED 5) layer according to any one of claims 1 or 2, characterized in that that said thioether is an acylmethylthio-2-benzothiazole is. 6) layer according to any one of claims 1 or 2, characterized in that that said thioether is an acylmethylthio-2-benzoxazole is. 7) layer according to any one of claims 1 or 2, characterized in that that said thioether is an alkylthio-2-N-alkylimidazole. 8) layer according to any one of claims 1 or 2, characterized in, that said thioether is an alkylthio-2-Nalkylthiazole is. 9) layer according to any one of claims 1 or 2, characterized in, that said thioether is an acyl methylthio-2-Nalkylimidazole is. 10) layer according to any one of claims 1 or 2, characterized in that that said thioether is an acyl methylthio-2-Nalkylthiazole is. . 11) layer according to any one of claims 1 - 1o, characterized in, that said developing reagent is an ingredient is from the group of fatty acid metal salts, which can be reduced by the following theons: Behenates, eesinates, naphthenates, benzoates and stearates of silver, Cadmium, calcium, copper, cobalt, tin, magnesium, manganese, nickel, lead and zinc. 12) layer according to any one of claims 1 - 1o, characterized in that that said developing reagent from the group of zinc, cobalt and nickel halides and zinc and cobalt thiocyanate derived from said thione 509807/1074 " ²¹ " a complex compound of the formula: form, in which M said halide or thiocyanate and L represents the said thione, 13) layer according to any one of claims 1 -12, characterized in that aie also a metal oxide from the group the titanium and zinc oxides »de-oil the semi-finished properties to have, , . . . 14) layer according to; Claim 13, wherein said semiconductor Titanium oxide is ,, dad; urcjh gejiej ^ visible Area with 15) Layer according to Ansp ^ u ^ n t% Ipei the diaF semiconductor is zinc oxide, that d ^ ch gefcennzeiehn ^
d © tier _: t ^: 16) layer femäß A ^ spni <ih) Ϊ ^ _Λ b ^ id ^ r de ^ Iialbl ^ iiter zinc oxide i »t, dadTareh feke ^ mae ^ fcohne ^ ti ^ daj; e ^ lyiQ:% ici ^ febaren: Bire ^ Qh with. and ^; ' If) S © hicht geipä; ß | rg ^ a ^ $ nem: der / Jtoö ^ üche % - t2v characterized by ^ d ^ ß ß && except ^ d ^ m exclude Beatandtflfiiit; the group of cobalt, - "copper * ^ * / Wi & fe ^ & $ xp> enifehäl% _r iier.dazu determined is ι for fixing the mentioned itatalysators a complex compound with the same 18} layer according to any; the. Claims 1 * 12 and any of the claims ^ e i.% -.16 “dadureh; It is recognized that the named spiropyran and the named thioether are adsorbed on the surface of the particles of the “named semi-conductor metal oxide”, i ' 19) A method for producing a photosensitive layer according to claim 18, characterized in that said Spiropyran and said thioether are mixed in a solvent; this solution becomes particles of semiconductor metal oxide added; to effect the adsorption is stirred for at least 10 minutes, then adding a binder containing said developing reagent in solution and agitating it for at least 10 minutes; only a thin layer is applied to a solid base and then the said solvent is applied evaporates. 20) Method of processing an inverted photographic An image using a photosensitive layer according to claim 18, wherein said spiropyran {2) is closed Form is characterized in that said layer is exposed to ultraviolet radiation in order to adhere to the called radiation affected places the selective conversion in spiropyran of open form to cause the aforesaid latent image emerges. 2t) Method of making a direct photographic Image with the aid of a light-sensitive layer according to An ~ Proverb 18, in which the said spiropyran (2) from open Shape, characterized in that said layer, exposed to visible radiation in order to affect the called radiation affected places the selective conversion in spiropyran of closed form, whereby the called latent image is created. 22) Method according to any of claims 20 and 21, characterized characterized in that said layer is at a temperature »Between 100 and 140 ° C is heated to strengthen the $ a- $ 8 0 7/107 4 called latent image by the catalytic conversion of said amplifying reagent in thione and then the development of the visible image through which Reaction between said thione and said metal salts. ·. :. ■ ; f 07 4 Blank page J. <