DE2329141A1 - LIGHT HOUSE PROTECTION LAYER FOR PHOTOGRAPHICAL MATERIALS - Google Patents

Description

AGFA-GEVAERTAG

PATENT DEPARTMENT LEVERKUSEN f "ß, JtIH!

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Antihalation layer for photographic materials Addition to patent application P 19 25 55 9.2

The present invention relates to silicon halide film photographic materials with an antihalation layer on the back of the film base, the antihalation layer contains a water-insoluble alkali-soluble polymeric binder.

In the main patent (P 1 925 559) are light-absorbing oxonol dyes has been described for use as filter dyes and antihalation dyes in photographic non-photosensitive colloid layers, especially in gelatin layers, and as screen dyes in photographic photosensitive silver halide emulsion layers.

These dyes conform to the following general formula:

, N - C _{v y} C - N _v

O = C ^ C = L ₁ - (L ₂ = L, -) _i ~ C ^ ^ C = O

- -IHI (\ 1

Ax 0 0 ^K "

where mean:

A is a straight-chain or branched-chain alkylene radical which interrupted by one or more heteroatoms such as oxygen can be,

X is an Alkoocycarbonylrest with a maximum of 5 carbon atoms in the alkoxy group, a hydroxyl group, one in acid or A sulfo group present in salt form, a cyano group

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Halogen atom for example a chlorine atom or the group SO-R » wherein R is an alkyl radical, a substituted alkyl radical, an aryl radical or a substituted aryl radical,

R ^ hydrogen, an alkyl radical, a substituted alkyl radical, for example the radical AX or an aralkyl radical, a cycloalkyl, allyl, aryl or substituted aryl radical,

L _7. , Ig and L, each a methine radical or a substituted methine radical, for example methine substituted by alkyl, aralkyl, aryl and carboxyl,

M is a cation, for example a proton, a metal cation or an onium cation of an inorganic or organic compound, like ammonium and pyridinium, and

ρ 1,2 or 3.

It is known to use silver halide photographic film materials provided with an antihalation layer to prevent light from passing through the light-sensitive Emulsion layer (s) penetrates, is reflected by the carrier and attacks the emulsion layer (s) a second time. the Antihalation layer (the one on the back of the film base can be applied) contains dyes selected to absorb the light passing through the emulsion layer (en) penetrates.

The binders that are used on the side of the film support applied antihalation layers can be used that of those opposite the emulsion layer (s) are usually hydrophilic colloids, especially gelatin. It is however, water-insoluble, alkali-soluble, polymers are also possible To use binders so that the layers in an alkaline processing bath, especially the alkaline developer solution, be completely removed. The latter binders are preferred over gelatin, for example, where the gelatin layers, which are not removed during processing, are too soft and as in microf! immaterial cause cause treatment problems, or where the adhesion of the polymer layers to the hydrophobic film carrier, e.g. a polyethylene

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ORIGINAL INSPECTED

terephthalate carrier, superior to the adhesion of gelatin layers is.

Light absorbing dyes should meet stringent requirements to be useful for photographic film material be. You should check the intrinsic sensitivity or spectral sensitivity of the photosensitive emulsions that you are using they can come into contact, not influence. they should have good absorption properties and do not give rise to fogging. They should continue in at least one of the photographic processing liquids is quickly rendered ineffective, i.e., discolored or destroyed and removed can be.

Although many dyes have been used successfully in antihalation layers that contain gelatin as a binder, most of them are unsuitable for use in antihalation layers that contain a water-insoluble, alkali-soluble, contain polymeric binder. For example, some dyes will not work in the alkaline developer solution fast enough or not completely decolorized so that the remaining dye, although even the polymeric layer in the alkaline solution is removed, the photographic material and the developer bath contaminated. Other dyes are im organic solvent insoluble, which is generally a lower alcohol, of which the water-insoluble, alkali-soluble, polymeric antihalation layer is applied, or they are incompatible with the polymeric binder, so that they precipitate or give rise to crystallization in the layer.

It has now been found that the light-absorbing dyes that described in the main patent for use in antihalation layers which contain a hydrophilic colloid, in particular gelatin, as a binder, work very well suitable for use in antihalation layers which are used as Binders contain a water-insoluble alkali-soluble polymer, provided that they are in their molecular structure

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contain no sulfo group or carboxyl group in acid or salt form. You are alkali-soluble with the water-insoluble polymeric binders are well tolerated and do not give rise to crystallization, they can easily be dissolved in organic solvents, 2.B. in a lower alcohol like Ethanol used to dissolve and apply the polymeric material. They are in alkaline developer solutions discolored without leaving any unwanted residual color.

The present invention therefore relates to a photographic silver halide material, as a support and a or more radiation-insensitive silver halide emulsion layers, as well as on the ßeite of the support, which the The opposite side of the radiation-sensitive silver halide emulsion layer (s) is an antihalation layer which has a contains water-insoluble alkali-soluble polymer as a binder and a dye which is the general given above Formula corresponds, with the difference that its Moärill free is of sulfo or carboxyl groups in acid or salt form.

Representative examples of light absorbing dyes corresponding to the above general formula are shown in listed in the following table:

Tabel

fearti- AX ^R 1 ^ I »L ₂ , Lx P. M. btoif CH ₂ COOC ₂ H ₅ C ₂ H ₅ CH 2 H 1 CH ₂ COOC ₂ H ₅ HC ₄ H ₉ CH 2 H 2 CH ₂ COOC ₂ H ₅ HC (CH,) j CH 2 H 3 CI C ₂ H ₅ ] CH 2 H 4th I ₂ CH ₂ OH

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5 CHgCHgOH ° 6 ^H 5 nC ₄ H ₉ CH 2 H 6th CHgCHgOH nC ₄ H ₉ CH 2 H 7th CHgCOOCgH ₅ CgH ₅ CH 3 H 8th CHgCOOCgH ₅ HC (CH ₃ ) g CH 3 H 9 CHgCOOCgH ₅ 11-C ₄ H ₉ CH 3 H 10 CHgCOOOgH ₅ H CH 3 H 11 CHgCHgOH C ₂ H ₅ CH 3 H 12th CHgCHgOH ° 6 ^H 5 CH 3 H 13th CHgCHgOH BC ₄ H ₉ CH 3 H 14th CHgCHgOCHgCHgOH C ₂ H ₅ CH 2 H 15th H ₃ CCH (OH) CH ₂ C ₂ H ₅ CH 2 H 16 CHgCHgCHgOH CgH ₅ CH 2 H 17th CHgCHgCl 11-C ₄ H ₉ CH 2 H 18th CHgCHgCN 11-C ₄ H ₉ CH 2 H 19th CHgCH ₂ BOgCH ₃ ^C 6 ^H 5 CH 2 H 20th CHgCHgOCHgCHgOH ⁰ A CH 3 H 21 CH ₂ CH (OH) CH ₃ CgH ₅ CH 3 H 22nd CHgCHgCHgOH CgH ₅ CH 3 H 23 CHgCHgCN 11-C ₄ H ₉ CH 3 H 24 CH ₂ COOCgH ₅ rt \ tf ^ XJ f ^ XJ ^ * ^ * · ' 5 CH
J 2 H 25th CHgCOOC ₂ H ₅ J CH
5 3 H 26th CHgCHgCOOC ₂ H ₅ rf CH 2 H 27 CH ₂ CHgCOOCgH ₅ CH 3 H

These dyes can be prepared as described in the main patent.

The polymeric binders for the Idchthofschuteechichten der present invention are water-insoluble! should however

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be alkali-soluble, so that they dissolve quickly in alkaline photographic developer tape. These polymers can belong to different classes of polymers.

Suitable alkali-soluble polymers are, for example - (8tyrene / haloic acid) -hiechpolymerieat

- partially or completely nitrated (ßyrene / maleic acid) copolymer

- (vinyl acetate / maleic acid) copolymer (50:50 mol- *)

* (Styrene / acrylic acid) -machpolymeri8at (70:30 weight per liter)

- (styrene / methacrylic acid) copolymer (30:70% by weight)

- (n-Buty 1 acry 1 at / Methacrylelture) copolymer (70:30% by weight)

- (methyl acrylate / acrylic acid) - olfactory polymer (60:20 wt .- #)

- (asstTol / mono-i8obutylaaleate / maleic acid) copolymer (41: 57i2 wt .- *) ·

- (vinyl acetate / crotonic acid) odor polymer (9 ^: 6% by weight) and other copolymers of vinyl acetate and crotonic acid which contain 5 to 20% by weight of crotonic acid, as in French patent 2,078,629 was described,

- copolymers of 20 to 50 wt -.% Of acrylic acid or methacrylic acid, 15-79 parts by weight of a C ^ Jtf -CG-alkyl acrylate and 1 to 50 parts by weight X of a Cj-C ^ -Alky methacrylate, as described in French Patent! 2,078,630, optionally together with polymethylene hydroxybenzoic acid which, as described in • the patent mentioned that promotes the adhesion of the antihalation layer to the film carrier, so that no special subetrated layer is necessary.

These copolymers include, for example:

- (Methacrylic acid / n-butyl acrylate / methyl methacrylate) -michpolymerisat (30: 67: 3 wt .- ^)

- '(Methacrylic acid / n-BUyl acrylate / methyl methacrylate) mixed polymer ■ erisate (35:35:30 wt.

- (Acrylic acid / n-butyl acrylate / methyl methacrylate) mixed polymer (20: 79: 1 wt .- #)

- Hethacryleiure ^ ethylhexyl acrylate / methyl methacrylate) copolymer (40:30:30 wt .- #)

- (methacrylic acid / ethyl acrylate / n-butylaethacrylate) mixed polymer ■ erieate (20: 78: 2 wt.

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- (MethacrylBSure / Ethylacrylat / Itethylinethacrylat) -lüechpoly-

merisat (26:37:37 wt. -Jl)

- (Methacrylsfiure / Xthylacrylftt / Methylbethacrylat) -copolymerisat (35:15:50 Gew.-Jjf)

- (Methacrylic acid / n-butyl acrylate / methyl methacrylate) copolymer (30: 68: 2 % by weight).

Normally the above-mentioned polymers are insoluble in their acidic form in water, but dissolve in an alkaline, photographic developers quickly, eo that the halo composition is removed from the photographic film base and a clear photographic film remains.

The thickness of the halo chute layer is not critical, though generally thicknesses of 0.5 to 3 µm can be used. the The thickness of the layer and the amount of dye are preferably so dimensioned so that the layer obtained has an optical density of about 0.5 to 3.

The casting composition for the antihalation layer can furthermore contain one or more surface-active agents as casting additives and matting agents, e.g. finely divided Silica, finely dispersed folymethyl methacrylate particles and finely dispersed particles of the reaction product (according to British Patent 961 198) of starch with urea and Formaldehyde.

The antihalation layer can be applied to the film carrier by spraying, Brush, roller, Bakel, air brush or paint brush techniques are applied. Examples of film carriers are films made from Cellulose triacetate, polyalkylene terephthalate or polycarbonates.

In certain cases, particularly when using polyalkylene terephthalate films such as a film of polyethylene terephthalate as the film base can be used to which the antihalation layer composition of the present invention is to be applied prefer to remove the carrier before attaching the antihalation

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to provide layer with a known adhesive layer or to pretreat the carrier surface according to known techniques. The polyester film carrier can be provided, for example, with an adhesive layer which is a copolymer of at least one of the chlorine-containing monomers vinylidene chloride and vinyl chloride contains.

This adhesive layer is described in British Patent 1,234,755 been. Good results are also obtained when the surface of the adhesive layer is subjected to a high-voltage electrical corona discharge as in British Patent 1,286,457 Occasionally, treatment of the polyester film support with the corona discharge alone are sufficient.

The surface of the polyester film carrier can also be treated with a solution of a swelling agent for the polyester, as described e.g. in Belgian patent 754 145.

To facilitate the removal of the antihalation layer in the developer bath, between the hydrophobic film support and the antihalation layer is provided with an intermediate layer consisting of a mixture of 1 to 3 parts by weight of a cellulose ester, e.g., cellulose diacetate, and 3 to 1 part by weight of at least one alkali-soluble polymer, followed by was referred to above. Further details on such intermediate layers can be found in Belgian patent 773 being found.

The following examples illustrate the present invention.

example 1

A cellulose triacetate film of 140 µm thick at 15% by weight Triphenyl phosphate is used in a ratio of 1 liter per

2
45 m coated with the following casting composition:

Cellulose diacetate (56 wt% acetic acid) 2.5 g

Acetone 850 ml

Methanol 75 ml

Butanol 75 _m i

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H-i>: h after drying, this intermediate layer becomes in a ratio

of 1 liter per 45 m with the following atrium protective layer

tongue coated:
Dye 3 10 g

2 ^> tfcw .-%, ethanolic solution of

(otyrol / aerylic acid) copolymer! sat

C70: .- 50 wt .- #) '120 ml

Methanol. ? 8o ml

tert-butanol 100 ml

35% strength by weight aqueous solution of hydrochloric acid. 1 ml

The yellow antihalation layer discolors and dissolves in a ordinary alkaline developer solution completely without leaving any residual staining.

Example 2

A biaxially oriented polyethylene terephthalate film of 100 µm Starch is coated with an adhesive layer of a copolymer of vinylidene chloride, vinyl chloride, η-butyl acrylate and itaconic acid as in Example 3 of British Patent 1,234 is described.

The adhesive layer is covered with the following antihalation composition in a ratio of 1 liter per 50 m:

Dye (9) 10 g

(Styrene / acrylic acid) copolymer

(70:30 wt%) 30 g

Ethanol 450 ml

n-butanol 50 ml

Acetone 500 ml

The dye on the antihalation layer discolors and dissolves completely in an ordinary photographic developing solution.

Example 3

The surface of a biaxially oriented polyethylene terephthalate

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films becomes a high-tension, electrical corona discharge exposed, whereupon the film in a ratio of 1 liter per

55 m coated with the following antihalation layer composition becomes ι

(Styrene / maleic acid) copolymer

(50:50 MoX%) 30 g

Dye 16. 10 g

Methanol 900 ml

tert-butanol 100 ml

The side that is the side with the antihalation layer is provided with a silver halide emulsion layer.

Post-exposure development in an ordinary alkaline silver halide developer becomes the antihalation layer completely decolorized and dissolved without leaving any residual color.

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Claims (2)

Claims Photographic light-sensitive material comprising at least a silver halide emulsion layer and an antihalation layer according to the main patent (P 1 925 559), characterized in that it acts as a binding agent for the antihalation layer contains a water-insoluble alkali-soluble polymer and an antihalation dye that does not contain any suIfo- or contains carboxyl group in acid or salt form in its molecular structure, the dye of the following Formula corresponds to: B ₁ O OR. I'M HI , J - C _n - .CN O = CC »I.- (L ₀ = L _x )" - (J ' ^ N - C ^{x Ί 2 5} P- ¹ * C - N ' · - IJ «0 I AX O O ^ AX in which: A is a straight or branched chain alkylene group through one or more heteroatoms can be interrupted, X is an alkoxycarbonyl group which contains at most 5 carbon atoms in the alkoxy group, a hydroxyl or cyano group, a halogen atom or a SOpR group where R is alkyl substituted alkyl, aryl or substituted aryl, R- hydrogen, an alkyl, substituted alkyl, cycloalkyl, Allyl, aryl or substituted aryl group, M a cation, L ^, Lp and L, any methine or substituted methine and ρ 1, 2 or 3 2. Photosensitive photographic material according to claim 1, characterized in that the antihalation layer is applied to that side of the carrier which is opposite the side which is the light-sensitive silver halide emulsion layer (en) carries. 3 · Photographic light-sensitive material according to each of preceding claims, characterized in that a GV.624 309883/1 273 - AZ - 2329U1 Adhesive layer between the support and the antihalation layer is appropriate. GV, 624 309883/1273