DE1931482A1 - Photosensitive masses and foils - Google Patents

Description

1931493

PATENT LAWYERS DIPL.-ING. H. LEINWEBER dipping. H. ZIMMERMANN

POS- 18338 \ β MUBcheii2.Reseiilair _f 2.Au (g.

Ti addr. utnpct Munich T.!. ton (081I) MItU

■. ■ - ".. · ■ on June 20, 1969 '.

Unier Z.ldien Lw / XIIl / C

MTSUSHITA ELECTRIC INDtJSlTiIAL CO., LTD., Osaka / Japan Photosensitive masses and foils ■

The invention relates to masses produced by active rays, such as infrared rays, visible rays, ultraviolet rays, Electron rays, X-ray rays, ^ - rays "etc. are excited can- (these masses are hereinafter referred to as photosensitive Hate). The invention also relates to photosensitive films / which are produced by applying these photosensitive films Mass produced on paper or plastic films.

There are already many photosensitive materials in shape of silver halide emulsions or containing no silver halide Masses known for direct printing. Currently, however, the application of photosensitive materials containing silver halide uneconomical due to the widespread rise in the price of silver, so that "the development of no silver halide contained- /" the photosensitive masses, especially photosensitive organic compounds is being promoted rapidly. For this reason photographic recording materials penetrate from organic

■ '■ "■ ■ ■" ■■ - ■■ -. - 2 -

1931492

-'2 - ■■;.:. , ■■ '■■. . ν. .. ■ - _■■:; ·

nis provide connections more and more. There are therefore / - known ■ already different, containing no silver salt photosensitive material is available. In general, photographic recording materials are judged in terms of (1) resolving power, (2) maximum density, (3) fogging, (4) gradient, (5) color, (6) ease of handling, (including sensitivity), and (7) costs. However, the ideal case of an organic photosensitive material in which all of the above properties are satisfied cannot yet be achieved in practice. For this reason, photosensitive materials have been developed which have some of the properties mentioned above.

In the development of the inventive photosensitive Mass was placed on a lower scale-iarbildung and -: Maintenance-free laid. ".. '.

The known photosensitive compositions using of organic compounds are made by taking Photo-r Activating agents which, through the action of light, free radicals able to form, with color formers mixed, which at, one j the effects of free radicals are subject to visible color changes. In some cases these are photosensitive masses additionally mixed with sensitizers, binders, stabilizers and fixing agents. . :

In the following the above mentioned components are briefly

explains:> I

I first Photosensitive Photoaktivierungsmittelj \

Compounds are used as photoactivating agents det, v / which form free radicals under the influence of light capital. These connections must have a large amount of free ',

000823/1610 ■ - -3 -

• ■ - - '3 -

Free radicals can form. Organohalides are best. These connections will be explained in detail later.

• 2nd color former:

Effective compounds that are colorless or white or before the reaction can be used as color formers are only weakly colored, but by reaction with by photodissociation free radicals formed result in color formers; Furthermore, compounds are suitable that have their own color, but are discolored or discolored by free radicals. Photosensitive compositions, which were produced using the first-mentioned color modifying agents, are original ' Initially colorless and develop under the action of active Radiate a color; these crowds are for the so-called Negative Posi systems used; on the other hand, the under Light-sensitive produced using the last-mentioned color-forming agents Masses used for Posi-Posi systems.

Examples of those used in the first-mentioned masses Color formers are:

(1) amine compounds:

These compounds include H-vinylamines, aryl-. amines and leuco pigments produced by reduction of figments with amino or substituted amino groups. Examples of these connections are:

H-vinyl cartasol

K-VinYlphenyl- ^ naphthylaFiin

II-vinyldiphenylamine

li-vinylindole

ii-vinyl pyrrole

N-vinylpyrrolidone · ·

009823/1619

8ADORfGiNAL

N-vinylsuecinimide, N-vinylacetanilide-. "_
I-vinyl methylacetamide
-li-Vinyilphenylaeetamid
li-vinyl diglycolimide
Diphenylamine
Dibenzylamiri '.

Triphenylamine

Η, Ν-diethylaniline -. . =.-.-. ■. "" - - ^r

p-jp'-Kethylenbis-lijI-dimethylanilim. ".. - ■" -

ρ, ρ'-Benzylidene-bis-N, N-aimethylaniline

p, p ¹ ^ "- Hethylidene-tris-lJjN-dimethylaniline. .- r

Mixture -. ■ - ■ '■. ": .." .- ■■ _.

from '.aniline, p-toluidine and o-toluidine;

Leuco crystal violet. .--

Leuco opal blue.

Leucorosaniline. . ; ^: ·

Leuco-p-rosaniline ■■ · ■ ■ -:

p, p ¹ , p "- ^r Priiiiethylleueoopalbiau

ρ, ρ ¹ , ρ '' - trichloro leucoopal blue

Ρ, ρ'-bis-tetramethyldiaminodiphenylmethane 3, (S-bis-Iiiinethylamino ~ 9-p-dimethylaiiiinophenylxanthen 3,6-bis-diethylamino-9-p-dimethylaiiiinophenylxänthen 3,6-bis-Diäthylaiiiino-9-p-diäthyiaininophenylxanthen 3, - 6-bis-dimethylamino-9-p-diethylaitiinophenylthioxanthene 3,6-bis-dimethylaiiiinoselenoxanthene

3, ö-bis-dimethylamino ^ -cyanoselenoxanthene. V

(2) Quaternary salts and N-oxides of nitrogenous heterogeneous

roP-yclic connections :. ' ■ '·

8AO GRSOiNAl.

■. ■ - 5 - ■ ■ ■ ■ ".

• Examples of these compounds are quaternary salts, for example: ■ ^;

2-methylbenzothiazoleflethyl iodide '

• 2-methylbenzothiazole ethyl iodide. - ■ "

\ 2-Ithylbenzothiazplffiethylbromid
Quinaldimethyliodid and: 2, .5-I ^ imethylbenzo. thiazoline thyl p-toluenesulfonate

as well as if oxides, e.g.

4-methylquinoline-I-oxide, 2,2 ¹ -dipyridine-N-oxide disulfide, and ghinoline-II-oxide.- - ''

The above color modifiers are used in Negative Posi systems applied. '.

The following modifiers are used in Posi-Posi systems used: ' . . -

(3) dyes made from diphenyl methane, triphenylmetban, thiazine, Oxazine, Zanthene, Anthraquinone, Iminonaphthoquinone and Azomethine:

Examples of these dyes are: ^ ..

Auramine (CI. 41000)

Victoria blue (CI. 44045) - ·

Brilliant Milling Green B (C.I. 42565) Benzoyl methylene blue

p-anisoylmethylene blue.

leues methylene blue (CI 51195)
Nile Blue A (CI. 51180)
■ Bhodamin B: '(CI. 45170), ■: ■

Sudan Black G (CI. 61525) ■. '.-. ■;

Celliton Blue (CI. 64500)
^ p-Diethylamoniphenyliminonaphthaquinone
2-Carbostearyiamino-4-p-dihydroxyethylaminophenyliminonaphthoquinone

Cyano-p-diethylaminophenyliminoacetanilide j

1-ß-naphthyl-3-methyl ■ -4-ρ-diethylaminophen ■ ylimino-.5- j pyrazolone "/,

3. sensitizers _·:;

The sensitivity, especially to visible ones _; Rays, of photosensitive materials for direct; pressure can be further increased by adding suitable sensitizers. These sensitizers i are divided into zv / ei groups, namely spectral sensitivities; sizing agents, by which the sensitivity of photosensitive materials as a result of a broadening of the.
Wavelength zone for sensitivity to visible
Increased radiation, and chemical sensitizers, _through: that the sensitivity of photosensitive materials! increased regardless of the sensitive wavelength zone _; vdrd. '.- ,. ■ "■.."'""".'"'"■".

Suitable spectral sensitizers are Gyaninfarbstoffe, merocyanine dyes, acridine dyes, and styryl ι: dyes _f. Examples for this are:

Acridine orange

Bengal pink

Methylene blue ^J.

Pinacyanol

.; - - ... ; . ■ ■■■ .. ■■ "■.. ^V ■; ■■. - 7 -

_—- 0 ^ 9823/1 §IS. ---———_ — _--

: ■■ -.- ■ - 7 - ■

1- (3-Ethyl-2-3H-benzothiazoliden) -4-butylidene di'beiizotliiazolmetlian

. 5-2- (3-iithylbenzoxalideTi) -äthyliden-2-phenyliniid-5-phenyl ' 4-ketotetrahydrothiazole. '-.

i ^ -DiethylthioM -'- carboxyaninjodid- '

1.3 ^l ~ Bimethyloxa-2'-carbocyanine-p-toluenesulfonate 5-1-Methyl-2 (1H) -quinoliden-2-butylidene-3-ethyl-2-thio-2,4-oxazolidenedione.

5-lütroacenaphthen, 1,2-3enzoanthraquinone are also suitable and N-phenylacrydone.

Aldehydes are also used as chemical sensitizers very effective. Examples for this are:

Benzaldehyde

Dirnethylarainobenzaldehyde

Salicylaldehyde

Anisaldehyde

Phenylacetaldehyde

Benzaldeli3 ^r sulfonic acid.

By suitable use of the above-mentioned anti-sibilants can increase the sensitivity of light-sensitive materials by 2 to 15 times.

Light-sensitive masses are made by using isan the above-mentioned photo-activating agents, color formers and sensitizing agents together with binding agents: film-forming plastics in a suitable solvent dissolves. So the novelty of a photosensitive mass depends on the content of individual compounds.

0O3823 / 161S

BAOÖRiQINAL

(J

According to the invention, new color formers are used, -which! photosensitive compositions with great sensitivity, essential; less fogging and at the same time easier handling; availability arise.

In the ₌ attached drawing are the characteristics for
3.3-bis-p-Diraethylaminophenylphthalid, which
is substituted in the 6-position by LTIp, NOp and LUCH ^ p groups; the characteristic curve for light-sensitive diazo paper is also shown.

The invention relates to photosensitive compositions that
by mixing photoactivation mortars - which free
Radicals form when exposed to active rays, and color balaners, which visible color changes through reaction with
the free radicals; form, were produced; the '"special" lead of these cash registers consists in the fact that one as a color artist; various lactone, lactam or sulphon color bases are used, which contain LactGnringeV in the molecule and the following ^
noc ;. correspond to the general formulas to be displayed. |

The invention creates light-sensitive materials that have little fogging and an excellent gradient! have and are easy to handle. _: ■ "'- ,; ■:

. The known photosensitive compositions, the leuco-; Containing dyes have the disadvantage that due to ^; low kengen, during the storage of free radicals formed a fogging occurs. To this haze too. " ^:
Avoid adding stabilizers such as urea, thiourea or weakly basic compounds

0098 2 3/1615

BATH ORIGINAL

Masses comparable to light-sensitive diazo papers Giving eyelid sensitivity was an additional one too Stabilization by the above-mentioned sensitizers required.

Photosensitive compositions, which according to the invention are colorless; Contain lactone, lactam and sultone basic ingredients for Nega-Posi-Systems v / ends. These dyes correspond the following general formulas:. :

(1) Compounds of the "general formula

in w'elcher IL, Ep "■ ^{un% (^} - ^ -α may be identical or different and each is hydrogen, alkyl," aralkyl "or aryl, P represents hydrogen, halogen, alkoxy, nitro, amino, monoalkylamino , Dialkylamino, aryl or a substituted aryl group; and χ denotes a number from 0 to 4, so that Px denotes that 0 to 4 identical or different substituents P can be introduced into the corresponding aromatic ring. ...

-. 10 009823/1619

8AD OR5GINAL

- ίο -

Examples of such connections are:

3,3-bis- (p-dimethylaminophenyl) -phthalide 3 _v 3-bis- (pI) imethylaminophenyl) -6-dimethylaminophthalide -3,3-bis- (p-diethylaminophenyl) -6-nitro]: ithalide 3.3 -bis- (p-dimethylaminophenyl) -6-monomethylaKiinoplitlia-. -lid

3,3-bi's- (p-Whore thylaminophenyl) -6-chlorophthalide 3,3-bis (p-diethylaminophenyl) -6-ethoxyphthalide 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide

These connections are made according to the following Processes described in the literature produced:

1. B.K. Green: U.S. Patent 2,548,328

2. Moriga and Yoshida: J. Chem. Soc. Japan (Ind..Ed. ■), 64, 7, pages 1226 to 1230 (1961).

(2) Compounds of the general formula

= O

00982 3 / T619

-11 -

in which Z the meaning of oxygen, sulfur, or selenium a similar one required to form a heterocyclic king Atoms owns; it .., lip, ii, and IL same or different can be and in each case chemical, alkyl, "aralkyl or aryl; P the meaning of hydrogen, 'halogen, Alkoxy, Kitro, Amino, Monoalkylanino, Dialkylanino, Aryl or has substituted aryl; and χ denotes a number from 0 to 4, so that Px has 0 to 4 identical or different substituents -P means which is introduced into the corresponding aromatic catch could be.

..Examples of these connections are:

3, b-bis-diethylamino- ^ hydroxy-'r-xanthencylbenzoic acid lactone

3,6-bis-Dinetii3 ^r Lan! Ino-9-i-5-hydroxy-9-xanthenoyl-6-dimethylaninobenzoic acid lacticn

3,6-bis-Dine thylaniino-S'-hydroxy-9-thioxanthenoyl-c-di-diethylaminobenzoic acid lacticn

3, c-bis-dinethyla: p.inc-Q-hydrcxY-3-thioxanthenoyl-6-chlorobenzoic acid lactone

(3) Compounds of the general formula

^Αι 1

009823/1619

SAO

1931487

. - ■ .. ■■■■ ■ - - ■ .. "- ■ - 12-- - ■ ^-;, - .. · ■■■:

in which E- ,, "Ep, E? and E * be the same or different can and in each case ". denote hydrogen, ■ alkyl, aralkyl or aryl; P is hydrogen, halogen or alkoxy, nitro, amino, monoalkylamino, dialkylamino, aryl or substituted aryl; and χ is a number between 0 and 4, so that Px Ö to 4 identical or different substituents P denotes which can be introduced into the corresponding aromatic egg. :. V

Examples of such connections are: -'.-. * '

^, S-bis-p-Dimethylaminophenyl-ö-diraethylaminosulfon-

phthalophenon ;; .- .... "■:.

3,3-bis-p-diethylaminophenyl-6-monomethylaminosulfonphthalophenone

3,3-bi sp-Dimethylaminophenyl-6-ethoxysulfonphthalophenOn 3j 3-bis-p-Dimethylaminophenyl-5 -chlorosulfonphthalophenon

Sulfone _: ■; Λ

(4) Compounds of the general formula

in which Z the meaning of oxygen, sulfur. Selenium barren - '''- A] Om. -ir,, -: .- ■ -

has a similar one to form a heterocyclic ring V; ' ^: ß |, B ^, E, and ^ can be the same or different

009823/161 9

can and each have the meaning of hydrogen, alkyl, aralkyL or aryl; P is hydrogen, halogen, alkoxy, nitro, amino, monoalkylamino, dialkylamino, aryl or substituted aryl has; and χ a number between 0 unc. 4 '. - means., So that Px means 0 to 4 identical or different subscripts P which can be introduced into the corresponding aromatic i fiing. "..".-; _ ·

Examples of such compounds are: j

3,6-bis-dimethylamino-9-hydroxy-9-xanthenoylbenzenesulfone acid sulton "

3,6-bis-dimethylamino-9-hydroxy-9-thioxanthenoylben-bolsulfonic acid sultone . . ■

(5) Compounds of the general formula

in which Z denotes oxygen, sulfur, selenium or a similar atom required for the formation of a heterocyclic xiings; iL, Iu-, K ^ and Ii, can be the same or different and · each denotes hydrogen, alkyl, aralkyl or aryl; and Px means that. 0 to 4 groups in the form of hydrogen

_ 14 _ 0098 23/1 619

8ADORtGJNAL

Halogeη, alkoxy, nitro, amino, monoalkylanino, dialkylamino, aryl or substituted aryl can be introduced into the corresponding aromatic "i Hing ^.;

Examples of such compounds are: "; 3,6-bis-dimethylamino-9-xanthenyl-o-benzoic acid lactam ' 3, '6-bis-diethylamine O-9-xanthenyl-TO-benzoic acid lactam

Color formers which contain the above-mentioned colorless color bases develop excellent colors when in contact with free radicals formed by the action of light ^: come kalen. For example, 3,3-bis-p-dimethylamino-j. phenyl-6-dimethylaminophthalide a brilliant deep blue color. ; and 9-p-nitroanilino-5,6-bis-diethylamino-S-xarithenyl-o-benzoe-; • Acid lactani a brilliant red color when you look at one; equimolar solution of these compounds with iodoform to one | applying photographic baryta paper, and the resulting light-sensitive paper ί exposed and then fixed at 15O ⁰ C. ^:

,. Iodoform and similar compounds which can be used according to the invention and which, under the influence of light, free lia.dical. to form the following are: ' _, _ -

(1) Compounds of the general formula '■

/ R- CXv

in which H the meaning of hydrogen, halogen, -alkyl or ^/ r; And X represents a halogen atom.

Examples of such connections are ^:!

Carbon tetrachloride ^:

Carbon tetrabromide ■:

Tetraiodocarbon ₀ . _{Λ Λ} '

. SAt) ORfGWAL

- 15 00982 3/1613

p-nitrobenzene tribromide

Ilexabr oma than '.

Iodoform

1,1,1-Tribrorn-2-Möt! Iyl-2-prop8nol 1,1,2,2-tetrabromoethane.

(2) compounds, the general j'orniel

in which Ιΐ one, heterocyclic est; X, Y and Z are each hydrogen or halogen, but all of them at the same time; mean hydrogen.

Examples of such Verbinduu _t e :. are:

U, U, U-Tribrc: .. clii: aldi :; W, U-pDibromc-hinaldii.

tJ _f (J-Dibromniethylc'.iir-olii...

1 _f -! 'Ethyl-2-chloromethylbeuzinida2ol 2, i3-Di * -tribrOimaethyl-3,4-dibrcc.thiop: ie; ..

(3) compounds of all ^ e ^ eir.ei, Fornel. "

00 9823/1619

8A0

..- ■ ■■■■. · ■■; .- .- ;. 16 -. " ^: ..." ■■■■ - ■. '-... "■ ■■;' ■■

in which Px is hydrogen or 1 to 5 substituents on the benzene ring in the form of halogen, «nitro, alkyl, haloalkyl, acetyl, Has haloacetyl or alkoxy and nidi all substituents P must have the same meaning * ■■ -. ■■ .-

Examples of such compounds are: ^v

o-Iitro- ^ LjdL ^ C-tribromaeetophenen
ot. ^ j ^ -tribromoacetophenone

^, ^, ^ - m-Tetrabromacetophenone '...-> -

^ , jL, j _> -tribromo-3,4-dichloroacetophenone j ^, ^, ^ - tribromo-2,5 ~ dichloroacetophenone JL, ^, ^ - tribromo-2,5-dimethylacetophenone ^, ^, j ^ -p- Tetrabromoacetophenone 'JL / JLjJL »Jl ¹ ti! , dL ^! -Hexabromo-p-diacetylbenzene ',

(4) Compounds of the general formula

in which E is the meaning of optionally substituted Alkyl or aryl; and X has the meaning · of halogen.

Examples of such connections are:

2,4-dinitrobenzene olsulfenyl chloride
o-nitrobenzenesulfenyl chloride

(5). Compounds of the general formula

'. ■ L-SO ₂ - X '. '

in which. E is the meaning of alkyl, aryl, or substituted Aryl; and X is halogen. . '■

-M- 009823/1619 \ "'~

BAOORiGSNAL

Examples of such connections are:

1,3-benzene disulfonyl chloride

2,4-dinitrobenzenesulfonyl chloride

o-nitrobenzenesulfonyl chloride

m-Hydrobenzenesulfonyl chloride

3,3-diphenylsulfone disulfonyl chloride Ethanesulfonyl chloride

p-bromobenzenesulfonyl chloride

p-nitrobenzenesulfonyl chloride

p-iodobenzenesulfonyl chloride

p-chlorobenzenesulfonyl chloride

p-toluenesulfonyl chloride

Benzenesulfonyl bromide

(6) Compounds of the general formula

.X ₁ ο χ.

ES- C: Xn or ESC X ₂

X ₃ 0

in which E is substituted or unsubstituted aryl or a heterocyclic ester; and X ₁ ,

Xp and Xv are each hydrogen or halogen, but not all;

at the same time hydrogen. j

-. ■■■ V- - S

Examples of such connections are: - ■ -. i

Hexabromodimethyl sulfoxide> |

Hexabromodimethyl sulfone - - j

• Trichloromethylphenylsulfon · ',

Tribromomethylphenyl sulfone. - - 18 - |

009823/1619 ~ "

Tribromomethyl p-nitrophenyl sulfone

4,6-dimethylpyrimidyl-2-tribromomethyl sulfone

2,4-Bichlorophenyltrichloromiethylsulfone °

2,5-dimethyl-4-chlorophenyltrichloromethylsulfOn

2-methyl-4-chlorophenyltrichloromiethyl sulfone

2,4-dichlorophenyl tribromomethyl sulfone

Bromomethyldibromomethylsulfone ■

(7) Photosensitive diazonium salts:

These salts are detailed by Kosar in "Light-Sensitive-Systems", John Vley & Sons Inc., New York (1965), pp
to 214 described. All of these salts are in accordance with the invention
useful.

Examples of such salts are:

p-ethoxybenzoldiazanium chloride
p-Dimethylaminobenzene diazonium chloride -.
1-Diazo-4-ne.thylbenzylamino-2,5-diethoxybenzene
1-diazo-2,5-diethoxybenzoylaminobenzene
1-Diazo-4-tolylmercapto-2,5-diethoxybenzene

The binders used according to the invention consist of j

out-connections,: which have a firm adherence of the above-mentioned j

th components, namely the color bases and photoactivation l

medium, able to effect on the surface of paper or film-like _'} \ substances and are not easy to
Discolor warmth. ■

Examples of such binders are polyvinyl chloride, polyvinylidene chloride, polystyrene, ethylene-ethyl acrylate

Copolymers, s'tyrol ^ butadiene copolymers, acrylonitrile- j - -:. . ■ "■ - 19 - j

Vinyl chloride copolymers, epoxy resins, cellulose derivatives, e.g. ethyl cellulose, ethyl cellulose, nitrocellulose and acetyl cellulose, and synthetic rubbers such as acrylic rubber,
Butadiene mixtures, etc.

The photosensitive materials according to the invention mainly consist of the above-mentioned three components. However, their sensitivity can be increased further, ie they ^! can be further sensitized if one kengen appropriately
admits other compounds which are able to form free radicals under the action of active rays or in heat; furthermore, visual sensitizers for spectral or
chemical sensitization or compounds with electron withdrawing groups in the molecule. As compounds which produce free radicals under the action of active rays or heat capable of forming, organic peroxides or azobisiso- ^[ butyrnitrile are suitable. Examples of useful organic peroxides are J benzoyl peroxide, lauryl peroxide, dicumyl peroxide, Methyläthylketon- ι peroxide and tert-butyl peroxide. Spectral and \ chemical sensitizers have already been described and therefore need here \ no further discussion. Preferred compounds j. with electron-attracting groups are tetraeyanoquinodimethane, Γ tetraxyanoethylene, bromanil, chloranil, etc.

The photosensitive compositions according to the invention are produced by dissolving the irerschMenen constituents in a binder solution in the dark. Photosensitive papers,
Films, sheets and plates are made in a manner known per se
produced by applying the photosensitive hats to the appropriate support and then drying. In,
In this case, for example, the components of the light ';

- 20 - -

0098 23/1619

sensitive masses in the following weight ratio. amienden .: ■ · ".'--.". ■ - .. ■. . "'-.

. Color formers
^: Photoactivating agent Film-forming binder Sensitizing agent

(including spectral
or chemical sensitizers, free radicals \ - - forming compounds-and
Compounds with an electron-'".-.-.-." Electron-attracting group)

Stabilizing _{agent ·:} 1 - 5 solvents ~ 500 - 1500;

Ο 150 Parts by weight Ι - 750 ' Il 5 _ 100 Il 1 - 10 il

Any paper, a plastic film base layer, a glass plate or a sheet of glass can be used as a carrier Use metal foil ~. When applying a surface-coated Paper or photographic paper. a clear image with a high resolution is obtained and great density. When using a plastic film green layer you get a clear, see-through image.

The length of the light to be applied to the carrier

sensitive Hasse is preferably 5 to 15 g / m.

The photosensitive paper thus obtained becomes ■ through, an original image exposed through, where ■ Immediately get a clear picture .-- If "you get the picture like this leaves. As it is, it occurs during storage S clil an incident. Because of this, the picture gets on -. . . "''" -. '. ■' - 21 "■■ 009823/1619

BATH ORIGINAL

a · to 15O ⁰ C, heated to 120 Walze'oder in a drier of 120 to 13O ⁰ C dried. After the thermal
Fixing you get a clear picture, which can be stored for a long time
is. An effective fixing method for removing photoactivating agents or color formers without the application of heat
consists in extraction with a solvent. The kind
the solvent to be used here depends on the type of

Components of the photosensitive mass from. Become general ^;

• * ^fc alcohol

but ethyl acetate, cyclohexane, cyclohexanone, acetone / etc .. ■ alone ¹

i or used in a mixture. ';

Hachdein the photo-activating agent or the .color former ";" from the photosensitive layer with the application of heat
or a solvent has been removed, the result is a stable image that can be stored for a long time, even if it is kept in a bright place. . ;

The invention will now be illustrated by the following examples. : further explained.

3eispJ.el_J ■ ■

A photographic paper "which by application;

2
of 1.5 g / m of polyvinyl alcohol with a degree of polymerisation ι of 700 was surface-treated under a safety lamp with a light-sensitive material of the following composition, the weight of the coating ί after drying 7.5 g / m fraud. ;.

3,3-bis-p-dimethylaminophenyl-6- j

dimethylaminophthalide 25 parts by weight. I.

Iodoform 25 "

Polyvinyl chloride 10. = "" "

Tetrahydrofuran x 1000 "

-22- ^; Op 9,8-2 3/16 19

SAD

The light-sensitive paper thus obtained was added 4 seconds with a 500 watt Xenon lamp at a distance of 7 cm "exposed ,, wherein sofcnt a deep blue positive with a pale yellow background was obtained by a photographic negative. This image was 1 Kinute in an oven at 125 ⁰ C fixed, whereby a stable image was obtained. If a positive is used instead of the photograph! See negative, a negative is obtained.:

The photosensitive paper film used in this example had five times the sensitivity of the trade usual diazo paper as well as a very clear and excellent: image quality on. ■ ■ .'j

An art paper treated on one side with the tone "was" ': under a_safety lamp with a light-sensitive mass!

covered by the following composition, v / whether ei is the weight of the

Coating after drying 12 g / n was: - ·

. 3,3-bis-p-dimethylaminophenyl-6-diniethyl- - ^:

aminophthalide. 5 G parts by weight

Carbon tetrabromide 5 ".

Polyvinylidene chloride -... ^ Z "

Tetrahydrofuran. ■ 200 .. "L

. ■■■ "■■ ι

The photosensitive paper thus obtained was exposed to light under the same conditions as in Example 1 to give a blue image with a white background. This image was " ^{fixed in a 130 0} O oven for 1 minute," giving a stable image. _

- .23 -

00 9823/16 19

: - ■■■■; "'-' ■■ - ■" 1931482
- 23 -
The photosensitive paper according to this example had
practically the same sensitivity as a commercially available light
sensitive positive-diazo paper-on.
Example 3
Example 1 was repeated, except that the in Table I
listed photoactivating agents for the production of the various
which photosensitive papers were used. The ones with these
Photosensitive papers developed colors and their relative
Sensitivity, related to the sensitivity of a trade
usual photosensitive positive slide opapiefs, are in table;
I listed.
Table_I_ '":
Comparison of sensitivity between light;
using delicate papers
various photoactivating agents:. Photoactivating agents colour Relative sensitive-:
ability, related to han
the usual diazoposi-
tive paper - Hexabromoethane clau 1.5 times ■■ ■ .'I 1 1,1,2,2-T-etrabr oma than blue 1.0 times. ■. j 2
3 U /, UiUz-Tribromquinaldin blue i
2.5 times. . ■. ^? 4th «C, eC» <- Tribrcniacetopl: enon blue. 4.5 times r— 1,5-Ber ^r j? Lsulf orn ^r lc :: iorid clau T, 5-fold .: exsbrcr.? i: rcthylsulfon 5.0 times ^ -Li :: 'ethyli- \ ii: topr; ^ l- -
"^ - · · - - * -n
ulc! ^ ii ->., -.> .- i.,: _u clau C, b-fac: i ".

0 0 9 8 2 3/1619

BAD GRK5SNAL

1 9314B2

At Soiel 4 ^; . "" ..... '- .-; "■ - ■ -----

■ .... - Example 1 was repeated, but ΐ / above the. Color base was replaced by typical color bases according to the invention. The obtained Ijditempfindlichen compositions were respectively applied to the .Oberfläche a Prägers, - which consisted of a semi-synthetic paper of 80 g / m ^t ", taking the photosensitive \, papers 1 -6 were obtained with the in the following Table II listed properties. The photosensitive papers 1-4 were exposed with-different exposure times using a -500 Viatt xenon lanipe with a luminous flux of 2000 lux The curves are shown in the attached drawing, in comparison to the curve of a commercially available licnteupfindlieη diazo-positive paper -;! ^ leichei-den Densitoneters IiLK-VI, manufactured by the company - ■ "I";.3γ.Γ; 1. Shokai, gemes sen; the gradient of this was measured using a step number with 22nd steps, which was also produced by the company mentioned. The gradient was. / i.ie rc ei by the Är.zar.l levels, indicated, which v / aren with the unarmed, outside recognizable. The results are in the.

^^ T ^ CiT-l'-O C * τ Γ * I "Γ

- 25 -

009 823 / 1619-

BATH

"" Λ - 25 - ■■ "" ■. "
Table II ■
•
Color properties of photosensitive papers
due to the Αηγ / esheit of color formers colour ran .exion density Effective
density * Color formers blue (jrund-
layer
-H
veil Maximum
density 0.32 1 3,3-to-p-Di-
- methylaminophe-
nylphthalide blue 0.03 0.35 0.15 gradient 2 3,3-blS-P-Di-
methylamino
phenyl-6-amino-
ghthaiid " Red 0.12 0.27 0.13 10 3 3,3-to-p-Di-
rnethylaraino- *
phenyl-6-ni-
trophthalid deep
blue 0.08 0.21 0.62 "-j
( 4 3,3-to-p-
Dimethylamine
nophenyl-6-
dimethylani-
nophthalide blue
Red 0.05 . 0.67 0.66 6: 5 9-p-bitroani
lino-3,6-to-
diethylamino
9-xanthenyl-
o-benzoic acid
lactam purple
blue 0.04 0.70- 0.72 15th 6 3,6-bis-diethyl
amino-9-hydroxy
9-xanthenoyl-o-
- benaolsulfonic acid
resuiton 00982 0.04 0.76. 14th 3/1619 " 15th - 26 -

To investigate the influence of binders photosensitive hats with different binders each applied to the surface of a semi-synthetic paper of 80 g / m, so that the weight of the mass applied as a coating

.9

after drying was 10 g / m 2. The photosensitive mass was made according to the following recipe: '. ■

^, J-bis-p-dimethylaminophenyl-ö- 5 parts by weight dimethylaminophtlialid - "-. '

Iodoform 5 "

Triphenyl phosphate 1 "

Binder .2 "

Solvents'. ~, 200 "

lla.ch dem. Drying was the photosensitive paper each time. two holes with a 100 watt ultra-high pressure mercury lamp at a distance, exposed 5 cm and then thermally fixed. Thereafter, the back reflection density and the gradient of the light-sensitive paper exposed in each case are measured, the results given in Table III below = j being obtained: - · . -. .. ^:

0 0 9 8 2 3/1 6 W 7

\ ^{■■■■:} DPSS

193H82

-'27 -. -
- Table III
Influence of the binder on the photosensitive Solution
middle . . iieilexionsdiciite. - density effective
density Dimensions: ' T Tetrahy
drofuran Reason-
layer
veil 0.84 - 0/82 Gradieii-t Binder j Il 0.93. 17th 1 none Il :, 04 - 1.35 1.23 - 20th 2 polyvinyl
chloride se methyl
ethyl
ketone 100
Toluene DO 0.96 0.90 .20 ' 3 acrylonitrile
Vinyl chloride
Ki schpolyme-
res toluene ), - C6 υ, approx 3.57 - -19 4 ethoxy cellulo toluene 0.05 3.53 15th; 5 polyvinyl
butyral - :, C4 13th ο styrene-Bu-
tadien-
L'ischpc-
lyr.eres ...

0 0 9 8 2 3/1619

BAD OfliGlNAL

iiätill

00 9 8 23716TF '^ ""

BATH

For this example it was investigated whether one was light-sensitive Cash registers with the dye bases according to the invention by known ones -Sensitizers can sensitize. The borrowed ind-i Each cash register was made according to the following recipe

3 i ^ -bis-p-Dimethyläminophehyl-ö-

diaminophthalide, 5 parts by weight

Tribromomethylphenyl sulfone 5 "

Polyvinyl chloride .... · ■ -, 2 .. ". '..'.

Aeeton-tetrahydrofuran (iOÖ: - iÖO) 100 · '

Sensitizers 0> 1 "-. '.

The light-sensitive masses are in each case on the

Surface of a half-art paper of ¹ SO ^ gZm applied, see above

■■? ■■■■ - '' -

that the weight of the coating 7j5 g / m was / The photosensitive paper obtained in this ■ manner, each exposed JO seconds with a 100 watt ultra-high pressure mercury lamp at a distance of 5 cm and then to fixing by a H'eiSwalse of 15O ⁰ C passed through. The results are summarized in the following table IY:

• -.29 - _
i
-
- • "PieTIexIönsHi cnTe" maximum Effective Example 7 , 4 5in electrical level 5 parts by weight 5 " -30- reason density density Pie la ti ve sensation . ■ j . Table IV : Influence of the sensitizer ¥ a \ 1 1 none - layer likelihood, bezogeri A photosensitive composition was prepared according to the following - 0.01-1.0 " ; _. 2 4-p-diamino +. on commercial _; Eezept made: "- Sensitive styrylchino veil before see light sensation 3,3-bls-p-DimethylamiTioph.enyl.-6 ^ 2 " ization lin liches diazoposi- * dimethylaminophthalide 100 " middle 3 thiosalicylic
aldehyde 1.23 1.15 tive paper Tribromomethylphenyl sulfone 0.08 . 5 times · Sensitizers 1.73 1.63 (organic peroxide or 0.10 ^v 11-fold '.' ■ - Acceptor) 1.45. 1.37 Polyvinylidene chloride "■ _ - 0.08 8.5 times Acetone tetrahydrofuran (100: 100) In this example the influence of the addition of a organic peroxide and a compound with < attractive group "investigated. ■

0Ö9823 / T6Tr

BATH ORIGINAL

- ': -' ■■. - 3o - - ",. Ι
-ν- ' ^V --- / ■' - ■ '■ ^; ■■ - ■ "■ / -:""^ -V ---,: - -ί
The photosensitive mass' was applied to the surface
2 '
a semi-synthetic paper of 80 g / m applied so that the
■ 2 -
The dry weight of the coating was 7.5 g / m 2. That on this one
The way obtained photosensitive paper was 10 seconds
with a 100 watt ultra high pressure mercury larape at a distance
exposed from 5 'cm and then for fixing by a hot roller'_;
of 15O ⁰ C passed through. The results are in the following
Table V listed: = ".-"""!
r
Table V
Influence of Sensitizer No. 2 1 none Reflection density maximum
density Effective
density Kelative sensation
opportunity, related
on trade standard
ch'es photosensitive-
liches diazoposi-j
tivpapier .- ■ _. j Sensitive
ization
middle 2 Laurylper-
oxide
0.6 weight
share Reason-
layer
veil 1.23 1.16 · 5-fsch ■. · ^; 3, Tetracyano
ethylene
0.6 weight
share 0.08 1.73 1.62 7-fold 0.11 1.95. 1.72 9-fold ■■; ■■; ; _Ί \ 0.23 I 3/16 T9 ~ -
- 31 - \ ϊ
". ■■■" ■ - 00 9 8;

BATH ORIGINAL

Various color bases, which colors are able to develop with the action of free radicals, were introduced into the photosensitive mass according to the invention to color the cash register after exposure and other examples; It is wise to produce a photosensitive composition of the following composition without influencing the sensitivity, whereby a photosensitive paper is obtained, in which there are no stains in the background:

3,3-bis-p-Dimethyläminophenyl-G ^ dimethylaminophthalid - *

3,3-bis-p-dimethylamino-D-nitrophthalide 'Bensoylleucomeiiylen blue

Ge ¹ Wi e'hts' parts ir . " ϊί ti 2.0 ti 12.0 ti 2.5 150.0

-.
Polyvinylidene chloride

Tetrahydrofuran j

This lichtöffipfiridlichen masses was applied as a coating the surface of a photograph! see paper applied, v / el-; whether it had previously been surface treated with ethyl cellulose. The dry weight of the mass that was brewed as fat;

2 * -. "" - ■■ ■ '■ ■ i

8.0 g / m The photosensitive paper thus obtained was 5 l Seconds with a 50,000 lux xenon tape through a hegative

film "lent through and sum fixing by an ice roller-e ^? '

from 15O ⁰ C. A rotliehschwarzes- .: ι

a clear picture with a white background; Lent paper showed ötwa the five-fold light sensitivity compared to a commercial liclitempiihdiielKn Diazopösitiv-!

on. . ■ ■ .- "■■■. P ⁵ P ^{ier /}

. ■■■■■ - 52 -, d ö % 8 217Ί 6 ti

SAO

193T4B2

As can be seen from the above examples, the photosensitive compositions of the invention from Phptoak- ■ activating agents, color formers and binders and contain in particular color bases that are stable in storage and are clear Dye images result when you come into contact with them Brings light formed free radicals. The color development philosophy the color bases due to the action of free radicals has not yet been clarified. However, it is to be assumed that the free radicals attack the color bases and the Rj.ng of the Lactons, Lactams or Sultons open so that on in this way triphenylmethane dye molecules with a quinoid structure form. The color bases according to the invention can, however, be chewed are referred to as leuco bases of triphenymethine dyes. As can be seen from the previous preparation examples, they are made from completely different raw materials and cannot be simply reduced by tri

- ■ - ■ "■ - ■ - '-.- ι

win phenylr.etfian dyes. In addition, the colorless]

- ■ ι

Laotian., Lactan: - and Suiton Farocases compared to the Leuc bases the Triplienylmethanfsrustcffe ·· (the so-called H-, OE- and Cll type) have the property that they are more stable and a. show less fogging during storage and those from the 4 sen color base; developed. Colors have a stronger opacity and are more dry Density sufv; iron.

Trcts of these useful properties are exhibited by the light-sensitive properties of the invention Masses im. the following;

Your effect suf:

; ■■ '■■■. (D

the substituents in the 6-position of.

- \ 33

SAO

As can be seen from the accompanying drawing, the characteristics of the 'photosensitive papers according to the invention, which contain these phthalides substituted in the 6-position,' are practically the same as or slightly higher than the characteristic for a commercially available photosensitive disazo-positive paper. With regard to the gradients, ie the value denoted by o in Pfctochemistry, the properties of the photosensitive papers according to the invention depend essentially on the substituents in the 6-position. The degree of dependence lies in the order of N (CIu) ₂ >H> M ₂ ^ NO ₂ , This is related to the electron affinity of the substituents introduced in the 6-position: and it can be assumed that a ring opening of the lacto .nrings. and at the same time more easily enters the formation DER resonance structure and a \ larger color density, the greater the amount \ of the introduced electron donor is. It is therefore to- _; . take that "3,3-bis-p-dimethylaminophenyl-6-dimethylaminophtha- j

lid- among the above-mentioned phthalide compounds of herrqrra-;

/.,.endste color former is, j

ι (2) Influence of photo-activating agents:

The photoactivating agents are very influential; on the light-sensitive. To increase the sensitivity of the In order to achieve this, it is preferable to use photolysable ". - I Plrtoaktivieriingsraittel on. Are best suited for this purpose organic halides. The C - I bonds of organic -halo-; ^ onids can be more easily sorted into the order F <T Cl * ^ Br ^ J. | classify; for this reason organic bromides J, and iodides are used. Furthermore, from the table I cited results with regard to steric factors and

- 34 0 0 9 8 2 3/1619 8AD

λ · - -; ■ ν V - 34 - - -; '- ■■■. ■ ο _: ' ■

electrical stability of the molecules that 'form compounds; the

Formula ^: v - * ' ₇ . .. ". ■.".

H- C - Χ,

excellent as a photo-activating agent. , ". _: _-

The influence of sensitizers on the photosensitive compositions according to the invention is shown in Table IV. The cash registers according to the invention can be effectively sensitized both chemically and by dye; the increase in sensitivity is about 1.5 to 2.5 times that of the same mass without a serisibilizer. ^:

(3) Influence of the binder: *, '

■ Binders are not always required, can ■ j. but-. Use effectively to bond the basic materials or activators, ... medium firmly to the surface of plastic lines and thereby increase the density. .As can be seen from the results. according to Table III results, cause-high molecular weight compounds ' lit ■■ 'halogen atoms in the molecule or large dielectric constant'; a sensitization in color development; on the other hand are not * -, polar high molecular compounds; ineffective. ^v

(4) Introduction of the color base mixture:

Introducing a mixture of the color former is a very difficult problem-■ If the individual color bases, including; j .- the influence of free Badikalen the same Ue ak ti ons ge schw domestic;.:. Speed, ie the same Farbentwicklungsgeschv / indigkeit on iron, ₍ is-this is no problem:. '"Most of the time, however, these substances have different

■■ .-: -. . ^: - ■ .. "■; - 35

00 9 8 2 37 1 619

BAOORfGlWAL

■ - 35—
the reaction speed. Dabar is first received

i 8Γ0 "~

Image of the color former with greater / Aitwicklungsgeschwindig-; and then the color gradually occurs through the color former with the lower color development speed, accordingly the equilibrium reaction and at the same time the hue also changes. Preferably, rr.an brings a mixture of colorless color bases made of lactone, lactam or SuItOh- j Compounds that differ only in terms of the substituents- ·> differentiate into the mix. In. Future should, however, be light sensitive wet enough for direct printing examines v / earth to obtain images of desired color and so to further develop the hates according to the invention ..

It can be assumed that when producing a color image by exposing one or more colorless color bases ^! on lactam, lactone or Sultonbasis one or several ^triphenyl: nylmethanfar * bstoffe arise with quinoid due iiingöffnung, which then form the final color image.

Kit according to the invention light sensitive. Cash registers can be, egalgülii,;, from the Kecuanisr.us at the Color developing from the colorless basic color substances on lactone, Lactam or SuIton base actually on an IiincOffr.uLg based on active rays, visible 3ilier on the. exposed Surfaces herctellei-. The erfiiiuunrs ^ o ^ äEen licl: ter. Sensitive Maεcen 'icnne ". Applied as a coating on egg-i: Triiger or in these a ^ e ^ racLt; alc Treuer für cie lichteicpfindlic ': en Masses are Fepier, Zuns'tstoffilne, Ketallfolie. or G-Iasplatter ..

009823/1619

BAO ÖFÜGINAL

Claims (2)

. - Patent claims: λ.) Light-sensitive composition, containing as an essential component a photo-activating agent, which is able to form free radicals under the influence of active rays, and a color former, which is able to form a visible image under the action of free radicals, characterized in that, .that the color former consists of one or more colorless lactone, lactam or sultone color bases of the following general formulas. ■ ■ (I) = 0 (II) > 37- ■:.; · ■■ ", 5 2 37161B - ■ 37 - 193 H82 2 Ί (IV) 009 82 37 16 1 9 ~ in which "Z- the meaning of oxygen, -sulfur, selenium or- ¹ " has a similar atom required for the formation of a heterocyclic ring; it., lip, Ii, and R, same or different. and are each hydrogen, alkyl, aralkyl or aryl: mean; P is hydrogen, halogen, alkoxy, ^ Ni tr'o, amino ", monoalkylamino, dialkylamino, aryl or substituted:. -Aryl; and X is a number from 0 to 4 _f > where: Px means that 0 to 4 identical or different substituents. P can be introduced into the corresponding aromatic ring!. · 2. ■ - .. Light-sensitive film, produced by applying! gene of the photosensitive composition according to claim 1 on a ₍ ; carrier in the form of paper, art st of film, glass plates and Met al l · - ■ foils, and subsequent drying * ^; - 3. .Light-sensitive [mass according to claim!, '. gekennzeichne ty ~ that the cash register for fixed connection to a: -;.! ■ carrier a soluble in a solvent ¹¹ in plastic, the form of polyvinyl chloride, polyvinylidene chloride, polystyrene,
. Ethylene-ethyl acrylate-Mischpolymerem, styrene-butadiene-Mischpoly- i Merem, 'acrylonitrile · - ¥ inylchlorid-MischpolvmereJn, epoxy resin, CeIIu ^ loose derivatives such as ethyl cellulose, EpoxyceHulose, ilitrocellulose and acetyl cellulose, synthetic sovrie ^{Käütschukarten:} such as acrylic rubber or butadiene mixed polymer, contains * ■■■■ ". -: ... - ■ -.";, ^: -.:■;-. ■ "'. ■■. ^: ■ - ■■ "■ ■ -. ■ -.- ■; ~ ■; ■. ■; ι 4. Photosensitive film, produced by applying] the photosensitive composition according to claim 1, on a support r the end. Paper, plastic film, glass plates or metal forums. V. "■;. ■■■: ■." ■. ^.::: -> ■: /; :: - 39-- 00 9 8 2 3Ύ T ΒΤΨ ~ ~ - -; ^ —— ■ ---------- r —--- ■■ · ■, · - -39- ■ .. j 5 »Photosensitive composition according to claims V to 3 _; characterized in that the mass of a sensitizer in the form of · used in photography spektralsensibilisie- \ ■ Governing dyes or mix before sensitizers in the form of; Contains compounds with> CO bonds in the molecule. 6. Photosensitive mass according to claims 1 to 3, - characterized in that the mass is an under action
of ultraviolet rays, electron ^{raysoC rays:} or heat-free. Radical-generating compound in the form of | ^; contains organic peroxides or azoisobutyrnitrile. 7. The photosensitive composition according to claim 1, ^{characterized:} in that the register contains a compound having a βίελ-tronenansiehenden group. 8. Photosensitive film, produced by application I gene of the photosensitive composition according to claims 5 and 6 | on a support made of paper, Kimststoffilm, glass plate or; Metal foil. : 9. Lichteiupfindlichen film according to claim 2, characterized in that; characterized in that the amount of photosensitive ] 2 "
borrowed cash from 5-15 g / m amount irr + SAD blank e e